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

Abstract

The invention provides a radiation-sensitive composition capable of forming a cured product having a high refractive index in a desired shape by fluidization caused by low-temperature heating, a cured product, a display device, an imaging device, and a method for producing the cured product. A radiation-sensitive composition containing component (A): a compound represented by formula (1) (wherein, not having a (meth) acryloyloxy group), component (B): a photopolymerization initiator, component (C): a polymerizable compound (wherein, component (D) is excluded), and component (D): a compound having a fluorene structure, an acidic group, and a (meth) acryloyloxy group in the molecule. (In formula (1), each symbol is as defined in the description. # imgabs0 #

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 Art

[0002] 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 elements, tiny focusing lenses (hereinafter also referred to as "microlenses") are usually regularly arranged to focus light into the light receiving element (photodiode) to improve the sensitivity of the sensor. In addition, in various display elements such as organic electroluminescent (organic EL (electroluminescence)) elements or liquid crystal display elements, display elements with a structure in which microlenses are provided on the light emitting side relative to each pixel for the purpose of improving light extraction efficiency or adjusting the viewing angle are also used. Furthermore, in self-luminous displays such as organic EL display devices, attempts are made to achieve brightness improvement or viewing angle adjustment by forming microlenses using high-refractive materials.

[0004] As one of the methods for forming microlenses, a heat flow method is known (for example, see Patent Document 1). The heat flow method is a method in which a pattern corresponding to a microlens is formed on the upper part of a light receiving element or a light emitting element by using a radiation-sensitive composition, and then the formed pattern is heated to flow the pattern, thereby forming a hemispherical microlens array.

[0005] Conventionally, in organic EL devices and liquid crystal display devices, a radiation-sensitive composition is applied on a substrate, a pattern is formed by exposure and development, and then a heat treatment is performed to form a planarized film.

[0006] [Prior art literature]

[0007] [Patent Document]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2020-101659 Summary of the invention

[0009] [Problems to be solved by the invention]

[0010] As a method for forming a microlens or a flattening film with a high refractive index, a method using a high refractive index filler such as a metal oxide is known. However, the method using a metal oxide sometimes has disadvantages such as troublesome cleaning of the manufacturing line and easy contamination of the device. In addition, in the case of a large amount of materials containing a high refractive index filler, the pattern after exposure and development is not easy to flow due to heat, and it is mostly difficult to form a microlens or a flattening film by heat treatment (heat flow).

[0011] In addition, there is also a known method of forming a microlens or a planarization film by heat treatment (heat flow) without using a high refractive index filler such as a metal oxide. In the previous methods, a high temperature process of 150°C or above is often required during the heat treatment. In the previous methods, there is a concern that they are not suitable for processes requiring low temperature processing. In particular, when a microlens is provided on the light emitting side relative to each pixel in an organic EL element for the purpose of improving light extraction efficiency or adjusting the viewing angle, or when a planarization film is provided in an organic EL element, in the manufacturing process of the organic EL element, it is sometimes required to be able to form a microlens or a planarization film at a low temperature (e.g., below 100°C) in consideration of the fact that the organic light-emitting material is easily degraded by heat.

[0012] In addition, it is known that when a microlens is formed by a heat flow method using a conventional radiation-sensitive composition, the portion of the microlens formed by the heat flow that is in contact with the substrate (adherend) (hereinafter also referred to as the "hem") wets and spreads, and the shape of the formed microlens becomes a shape that is greatly different from the desired shape. In addition, it is believed that when a planarized film is formed by a heat treatment, if the portion of the planarized film formed by the heat flow that is in contact with the substrate (adherend) (hem) wets and spreads, the formed planarized film also becomes a shape that is greatly different from the desired film shape, such as a taper angle that becomes too small or a contact hole is buried.

[0013] The present invention has been made in view of the above problems, and one object of the present invention is to provide a radiation sensitive composition that can be formed into a cured product having a high refractive index in a desired shape by fluidization caused by low-temperature heating.

[0014] [Technical means to solve the problem]

[0015] The present inventors have found that the above-mentioned problems can be solved by the following structural 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 can be provided.

[0016] The following shows a configuration example of the present disclosure.

[0017] [1] A radiation-sensitive composition comprising

[0018] (A) Component: a compound represented by the following formula (1) (which does not have a (meth)acryloyloxy group),

[0019] (B) component: photopolymerization initiator,

[0020] (C) component: a polymerizable compound (except for (D) component), and

[0021] (D) Component: A compound having a fluorene structure, an acidic group and a (meth)acryloyloxy group in the molecule.

[0022] [Chemistry 1]

[0023]

[0024] (In formula (1), Ar 1 and Ar 2 are independently aromatic ring groups;

[0025] R 1 and R 2 are independently a monovalent substituent, or represent R 1 With R 2 Bonded to each other and Ar 1 and Ar 2 The condensed ring structure formed together; the condensed ring structure has two aromatic rings connected by a single bond, -O-, -S-, -NR 5 -, carbonyl, methylene or ethylene; R 5 A hydrogen atom or an alkyl group having 1 to 3 carbon atoms;

[0026] R 3 and R 4 are each independently a monovalent substituent;

[0027] m1 and m2 are each independently an integer from 0 to 7;

[0028] k1 and k2 are each independently an integer of 0 to 4; when k1 is an integer greater than 2, a plurality of R 3 are independently monovalent substituents, or are bonded to each other and to R 3 The bonded benzene rings together form a condensed ring; when k2 is an integer greater than 2, multiple R 4 are independently monovalent substituents, or are bonded to each other and to R 4 The bonded benzene rings together form a condensed ring;

[0029] In formula (1), there are multiple R 1 ~R 4 In the case of multiple R 1 ~R 4 Same or Different)

[0030] [2] The radiation sensitive composition according to [1], wherein the component (D) is a compound represented by the following formula (2).

[0031] [Chemistry 2]

[0032]

[0033] (In formula (2), Ar 1 and Ar 2 are independently aromatic ring groups;

[0034] R 1 and R 2 are independently a monovalent substituent, or represent R 1 With R 2 Bonded to each other and Ar 1 and Ar 2 The condensed ring structure formed together; the condensed ring structure has two aromatic rings connected by a single bond, -O-, -S-, -NR 5 -, carbonyl, methylene or ethylene; R 5 A hydrogen atom or an alkyl group having 1 to 3 carbon atoms;

[0035] R 3 and R 4 are each independently a monovalent substituent;

[0036] X 1 and X 2 Each is independently a group represented by the following formula (2X);

[0037] n1 and n2 are each independently an integer of 1 to 7;

[0038] m1 and m2 are each independently an integer of 0 to 6;

[0039] k1 and k2 are each independently an integer of 0 to 4; when k1 is an integer greater than 2, a plurality of R 3 are independently monovalent substituents, or are bonded to each other and to R 3 The bonded benzene rings together form a condensed ring; when k2 is an integer greater than 2, multiple R 4 are independently monovalent substituents, or are bonded to each other and to R 4 The bonded benzene rings together form a condensed ring;

[0040] Among them, R 1 ~R 4 , X 1 and X 2At least one of them has an acidic group, and the compound represented by formula (2) has at least one acidic group;

[0041] In formula (2), there are multiple R 1 ~R 4 , X 1 and X 2 In the case of multiple R 1 ~R 4 , X 1 and X 2 Same or Different)

[0042] [Chemistry 3]

[0043]

[0044] (In formula (2X), R 8 An alkanediyl group having 2 to 4 carbon atoms;

[0045] R 6 is a hydrogen atom or a methyl group;

[0046] X is 0 or 1;

[0047] R 9 A hydrogen atom or -OY 1 ;

[0048] Y 1 is a hydrogen atom or "-C(=O)-R 7 -COOH"; R 7 A divalent organic group having 1 or more carbon atoms;

[0049] p is an integer from 0 to 4; when p is 2 or more, multiple R 8 Same or different;

[0050] "*" indicates a bond)

[0051] [3] The radiation sensitive composition according to [1] or [2], which is used for producing a microlens by a heat flow method.

[0052] [4] A cured product obtained by curing the radiation sensitive composition according to any one of [1] to [3].

[0053] [5] The cured product according to [4], wherein the refractive index of the cured product under light having a wavelength of 550 nm is 1.64 or more.

[0054] [6] The cured product according to [4] or [5], which is used for optical components.

[0055] [7] A display device comprising the cured product according to any one of [4] to [6].

[0056] [8] An imaging device comprising the cured product according to any one of [4] to [6].

[0057] [9] A method for manufacturing a hardened product, comprising:

[0058] A step of applying the radiation-sensitive composition according to any one of [1] to [3] above onto a substrate;

[0059] a step of irradiating the radiation-sensitive composition coated on the substrate with radiation;

[0060] a step of developing the radiation-sensitive composition after irradiation with radiation; and

[0061] A step of heating the radiation-sensitive composition after development.

[0062]

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

[0063]

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

[10] , wherein the microlens is formed by melting the pattern in the step of heating the developed radiation-sensitive composition.

[0064] [Effects of the Invention]

[0065] According to the radiation-sensitive composition of the present invention, a high-refractive-index cured product (e.g., microlens and planarized film), particularly a microlens, can be easily formed into a desired shape by fluidization caused by heating at a low temperature. Such a radiation-sensitive composition of the present invention is suitable for use in microlens production or planarized film formation. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 (a) Figure 1 (b) is an enlarged photograph of the microlens pattern observed from the front. Figure 1 (a) is the state before post-baking, Figure 1 (b) shows the state after post-baking. DETAILED DESCRIPTION

[0067] Hereinafter, matters related to the embodiment will be described in detail. In addition, in this specification, the numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower limit and the upper limit.

[0068] In the present specification, the "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

[0069] The term "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and / or a branched hydrocarbon group that does not include a cyclic structure in the main chain but consists only of a chain structure, and may be saturated or unsaturated.

[0070] The so-called "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only the structure of an alicyclic hydrocarbon as a ring structure and does not contain an aromatic ring structure. It is not necessary to be composed only of the structure of an alicyclic hydrocarbon, and a group having a chain structure in a part thereof is also included. In addition, the structure of the alicyclic hydrocarbon may be a single ring or a condensed ring.

[0071] The so-called "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. It is not necessary to be composed of only an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may be contained in part thereof. In addition, the aromatic ring structure may be a monocyclic ring or a condensed ring. In addition, the ring structure possessed by the alicyclic hydrocarbon group and the aromatic hydrocarbon group may also have a hydrocarbon group as a substituent.

[0072] In addition, in this specification, "(meth)acrylic acid" includes "acrylic acid" and "methacrylic acid". "(Meth)acryloyl" includes "acryloyl" and "methacryloyl". The so-called "alkali soluble" means that it can be dissolved or swelled in a 2.38 mass% concentration of tetramethylammonium hydroxide aqueous solution at 25°C.

[0073] 《Radiosensitive composite material》

[0074] The radiation sensitive composition of the present disclosure (hereinafter also referred to as "the present composition") contains the following components (A), (B), (C) and (D). In addition, each component may be used alone or in combination of two or more unless otherwise specified.

[0075] (A) Component: A compound represented by the following formula (1) (but having no (meth)acryloyloxy group)

[0076] Component (B): Photopolymerization initiator

[0077] Component (C): polymerizable compound (excluding component (D))

[0078] Component (D): a compound having a fluorene structure, an acidic group and a (meth)acryloyloxy group in the molecule

[0079] [Chemistry 4]

[0080]

[0081] (In formula (1), Ar1 and Ar 2 are independently aromatic ring groups;

[0082] R 1 and R 2 are independently a monovalent substituent, or represent R 1 With R 2 Bonded to each other and Ar 1 and Ar 2 The condensed ring structure formed together; the condensed ring structure has two aromatic rings connected by a single bond, -O-, -S-, -NR 5 -, carbonyl, methylene or ethylene; R 5 A hydrogen atom or an alkyl group having 1 to 3 carbon atoms;

[0083] R 3 and R 4 are each independently a monovalent substituent;

[0084] m1 and m2 are each independently an integer from 0 to 7;

[0085] k1 and k2 are each independently an integer of 0 to 4; when k1 is an integer greater than 2, a plurality of R 3 are independently monovalent substituents, or are bonded to each other and to R 3 The bonded benzene rings together form a condensed ring; when k2 is an integer greater than 2, multiple R 4 are independently monovalent substituents, or are bonded to each other and to R 4 The bonded benzene rings together form a condensed ring;

[0086] In formula (1), there are multiple R 1 ~R 4 In the case of multiple R 1 ~R 4 Same or Different)

[0087] [Component (A): a compound represented by formula (1)]

[0088] The component (A) is a compound represented by the formula (1), and is a compound having no (meth)acryloyloxy group and having a fluorene structure.

[0089] By using such a component (A), even when fluidization is caused by heating at a low temperature, the wetting and spreading of the hem can be suppressed, and a high-refractive-index cured product can be easily formed in a desired shape.

[0090] In the formula (1), Ar 1 The aromatic ring group represented by is a group formed by removing (m1+1) hydrogen atoms from an aromatic ring. 2The aromatic ring group represented by is a group formed by removing (m2+1) hydrogen atoms from an aromatic ring. 1 and Ar 2 The aromatic ring may be a single ring or a condensed ring.

[0091] As Ar 1 and Ar 2 The aromatic ring is preferably an aromatic hydrocarbon ring, and examples thereof include a benzene ring, a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring. 1 and Ar 2 The aromatic ring is preferably a benzene ring or a naphthalene ring.

[0092] In R 1 and R 2 When Ar is a monovalent substituent, it is possible to achieve a high refractive index and improve heat resistance. 1 and Ar 2 It is preferably one having a condensed polycyclic aromatic hydrocarbon ring, and more preferably one having a naphthalene ring.

[0093] In R 1 and R 2 When each of them is independently a monovalent substituent, examples of the monovalent substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxyl group, an acidic group (carboxyl group, sulfonic acid group, phenolic hydroxyl group, thiol group, phosphoric acid group, phosphonic acid group, phosphinic acid group, 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, 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 cycloalkyloxy 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 [The R A and R B are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]), -NH-C(=O)-R [wherein R may have the same 3 , R 4 alicyclic hydrocarbon group having 5 to 20 carbon atoms or aromatic hydrocarbon group having 6 to 20 carbon atoms with the same substituent], -NH-SO 2 -R [the R mentioned above has the same meaning as R in the above -NH-C(=O)-R], -NH-C(=O)-NH-SO 2 -R [the R mentioned above has the same meaning as R in the above -NH-C(=O)-R], -OC(=O)-NH-SO2 -R [the above R has the same meaning as R in the above -NH-C(=O)-R], etc. Among these, R 1 and R 2 The monovalent substituent represented is preferably a hydroxyl group, a carboxyl 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-SO 2 -R is more preferably a hydroxyl group, a carboxyl 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-SO 2 -R.

[0094] In R 1 and R 2 Indicates mutual bonding and Ar 1 and Ar 2 In the case of a condensed ring structure formed together, the condensed ring structure has Ar 1 The aromatic ring and Ar 2 The aromatic rings in the 5 -, carbonyl, methylene or ethylene. 1 and R 2 Examples of the condensed ring structure formed by mutual bonding include a fluorene ring, an anthrone ring, a xanthene ring, a thioxanthene ring, etc. Among these, a xanthene ring is preferred.

[0095] m1 and m2 are each independently an integer of 0 to 7, and can be 1 and Ar 2 m1 and m2 are preferably selected according to the type. Preferably, either one of m1 and m2 is 1 or more, and more preferably, both are 1 or more. The upper limit of m1 and m2 is preferably 3, and more preferably 2.

[0096] When either m1 or m2 is 1 or more, it is preferred that 1 and R 2 At least one of the 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) n -H [the above R" is an alkylene group having 1 to 4 carbon atoms, and n is an integer of 1 to 10], more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms.

[0097] The OR' group can be 1 and / or Ar 2 A direct bond may be included in R in the -NH-C(=O)-R, for example.

[0098] As R 3 and R 4 The monovalent substituent represented by the present invention includes a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxyl group, an acidic group (carboxyl group, sulfonic acid group, phenolic hydroxyl group, thiol group, phosphoric acid group, phosphonic acid group, phosphinic acid group, 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, 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 cycloalkyloxy 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 [The R A and R B are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]), -NH-C(=O)-R [the R and R 1 and R 2 -NH-C(=O)-R has the same meaning as -NH-SO 2 -R[The R and R 1 and R 2 -NH-C(=O)-R has the same meaning as -NH-C(=O)-NH-SO 2 -R[The R and R 1 and R 2 R in -NH-C(=O)-R has the same meaning], -OC(=O)-NH-SO 2 -R[The R and R 1 and R 2 R in -NH-C(=O)-R has the same meaning as [R]. 3 and R 4 The monovalent substituent represented is preferably a hydroxyl group, a carboxyl 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 carboxyl group, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0099] When k1 is an integer greater than 2, a plurality of R 3 are independently monovalent substituents, or are bonded to each other and to R 3 The bonded benzene rings together form a condensed ring. When k2 is an integer greater than 2, a plurality of R 4 are independently monovalent substituents, or are bonded to each other and to R 4The bonded benzene rings together form a condensed ring. Examples of the condensed ring include a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring. Among these, a naphthalene ring is preferred.

[0100] In addition, when k1 is an integer of 2, two R 3 Bonded to each other and to R 3 When the bonded benzene rings together form a naphthalene ring and k2 is 0, the component (A) can be said to be a compound having a benzofluorene skeleton.

[0101] k1 and k2 are integers of 0 to 4, preferably 0 to 2, more preferably 0 or 1, and further preferably 0.

[0102] Preferred specific examples of the compound (A) include compounds represented by the following formula (A-1) to formula (A-12), respectively.

[0103] [Chemistry 5]

[0104]

[0105] [Chemistry 6]

[0106]

[0107] The molecular weight of the component (A) is preferably 1,000 or less, more preferably 800 or less. The lower limit is not particularly limited, but is preferably 200 or more, more preferably 350 or more.

[0108] When the molecular weight of the component (A) is within the above range, the wetting and spreading of the hem can be suppressed even when the component is fluidized by heating at a low temperature, and a cured product with a high refractive index can be easily formed in a desired shape.

[0109] The content of the component (A) in the present composition is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further 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 further preferably 30 parts by mass or less, relative to 100 parts by mass of the component (D) described later.

[0110] When the content of the component (A) is within the above range, a cured product having a high refractive index can be easily obtained, and the cured product can be fluidized at a relatively low temperature (e.g., 100° C. or less). During fluidization caused by heating at a low temperature, the wetting and expansion of the hem can be suppressed, and a cured product having a desired shape can be easily obtained.

[0111] [Component (B): photopolymerization initiator]

[0112] The component (B) is not particularly limited, but is preferably a photoradical polymerization initiator that generates radicals in response to radiation and initiates polymerization. Examples of the component (B) include O-acyl oxime compounds, acetophenone compounds, biimidazole compounds, and acylphosphine oxide compounds.

[0113] Examples of the O-acyl oxime compound include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), 1-(9-ethyl-6-benzoyl-9H-carbazole-3-yl)-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, ethyl ketone, -1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyl oxime).

[0114] Examples of the acetophenone compound include α-aminoketone compounds and α-hydroxyketone compounds.

[0115] Specific examples of the α-amino ketone compound 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.

[0116] Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenylketone.

[0117] 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.

[0118] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0119] The content of the component (B) in the present composition is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and is preferably 10 parts by mass or less, more preferably 7.5 parts by mass or less, and further preferably 5 parts by mass or less, relative to 100 parts by mass of the total of the components (C) and (D) described later.

[0120] 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.

[0121] [Component (C): polymerizable compound]

[0122] The polymerizable compound as 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 copolymerize with component (D) described later, and is a compound that can generate a polymer together with component (D) when exposed to radiation. Component (C) is a compound different from component (D).

[0123] When only the following (D) component is used as a polymerizable compound, a hardened material with a high refractive index can be easily formed. On the other hand, if the pattern is to be made into a desired shape (especially a microlens shape) by heat treatment, a high temperature process of, for example, 120°C or more is mostly required. In addition, when only compound (D) is used as a polymerizable compound, a high exposure is mostly required in order to fully harden the present composition. In contrast, by using component (D) and component (C) together, and utilizing a low temperature process of, for example, 100°C or less, the pattern can be melted and fluidized, and a hardened material of a desired shape (especially a microlens shape) can be easily obtained. In addition, by using component (C), the curing speed is increased, and curing can be performed with a relatively low exposure.

[0124] The molecular weight of the component (C) is preferably 1200 or less, more preferably 800 or less, and further preferably 600 or less, from the viewpoint of being able to reduce the temperature of the heat treatment for forming a cured product of a desired shape as much as possible. In addition, from the viewpoint of being able to easily form a cured product having high refractive index, excellent solvent resistance, low volatility, and excellent reliability, the molecular weight of the component (C) is preferably 100 or more. The molecular weight of the component (C) can be measured by mass spectrometry.

[0125] Examples of the component (C) include (meth)acryloyl group-containing compounds, chain vinyl compounds, aromatic vinyl compounds, and maleimide compounds, and these compounds are preferred because of their good copolymerizability with the component (D) and relatively high plasticity.

[0126] The component (C) may be any of a monofunctional compound having one polymerizable group and a polyfunctional compound having two or more polymerizable groups. In addition, as the component (C), a monofunctional compound and a polyfunctional compound may be used in combination.

[0127] Specific examples of the monofunctional compound of component (C) include: (meth)acrylates containing a chain structure, (meth)acrylates having an alicyclic structure, (meth)acrylates having an aromatic ring structure, (meth)acrylamide compounds, chain vinyl compounds, aromatic vinyl compounds, and maleimide compounds. Among these, a compound containing a (meth)acryloyl group is preferred, and a compound containing a (meth)acryloyl group is more preferred, wherein the compound containing a (meth)acryloyl group is at least one selected from the group consisting of (meth)acrylates containing a chain structure, (meth)acrylates having an alicyclic structure, and (meth)acrylates having an aromatic ring structure.

[0128] Specific examples of the compound include (meth)acrylates having a chain structure, such as alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, and polyoxyalkylene (meth)acrylates.

[0129] Examples of the alkyl (meth)acrylate 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.

[0130] Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0131] As an alkoxyalkyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, etc. are mentioned.

[0132] Examples of the polyoxyalkylene (meth)acrylate 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.

[0133] Examples of the (meth)acrylate 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 2,6 ] decane-8-yl ester, (meth) acrylic acid tricyclo[5.2.1.0 2,5 ]Decan-8-yloxyethyl ester, isobornyl (meth)acrylate, and the like.

[0134] Examples of the (meth)acrylate having an aromatic ring structure include phenyl (meth)acrylate, benzyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate, naphthyl methyl (meth)acrylate, naphthyl ethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, m-phenoxyphenyl methyl (meth)acrylate, p-phenoxyphenyl methyl (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.

[0135] Examples of the (meth)acrylamide compound include (meth)acryloylmorpholine, N-(2-hydroxyethyl) (meth)acrylamide, N-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactam.

[0136] Examples of the chain vinyl compound include propylene, butene, pentene, and hexene.

[0137] Examples of the aromatic vinyl compound include styrene, methylstyrene, α-methylstyrene, tert-butoxystyrene, and vinylnaphthalene.

[0138] Examples of the maleimide compound include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-(p-methylphenyl)maleimide.

[0139] Specific examples of the component (C) when it is a polyfunctional compound include polyfunctional (meth)acrylates, polyfunctional aromatic vinyl compounds, and polyfunctional chain vinyl compounds.

[0140] Examples of the multifunctional (meth)acrylate include difunctional (meth)acrylates, trifunctional or higher (meth)acrylates, etc. Specific examples of these difunctional (meth)acrylates include 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.

[0141] Examples of trifunctional or higher-functional (meth)acrylates 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), tri(2-hydroxy-1-nitropropane tri(meth)acrylate, tri(2-hydroxy-1-nitropropane tri(meth)acrylate, tri(2-hydroxy-1-nitropropane tri(meth)acrylate, tri(2-hydroxy-1-nitropropane tri(meth)acrylate, tri(2-hydroxy-1-nitropropane tri(meth)acrylate, tri(2-hydroxy-1-nitropropane tri(meth)acrylate, -(meth)acryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol tri(meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate, isocyanuric acid tri(2-(meth)acryloyloxyethyl) ester, carboxyl-containing polyacid-modified (meth)acrylic oligomer, a compound having a linear alkylene and alicyclic structure and having two or more isocyanate groups, and a polyfunctional urethane acrylate compound obtained by using a compound having one or more hydroxyl groups and three, four or five (meth)acryloyloxy groups in the molecule.

[0142] Examples of the polyfunctional aromatic vinyl compound include 1,3-divinylbenzene and 1,4-divinylbenzene.

[0143] Examples of the polyfunctional chain vinyl compound include 1,5-hexadiene, 1,6-heptadiene, and 1,7-octadiene.

[0144] Preferred specific examples of the component (C) include compounds represented by the following formula (C1-1) to formula (C1-50).

[0145] [Chemistry 7]

[0146]

[0147] [Chemistry 8]

[0148]

[0149] [Chemistry 9]

[0150]

[0151] [Chemistry 10]

[0152]

[0153] [Chemistry 11]

[0154]

[0155] In formula (C1-1) to formula (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.

[0156] In addition, R in formula (C1-48) is a , R b or R c , and it means that a of the six Rs is R a , b of the six Rs are R b , c of the six Rs are R c Wherein, a+b+c=6, and a is an integer greater than or equal to 1.

[0157] In terms of being able to easily form a hardened material of a desired shape by heat treatment at a low temperature and being able to easily obtain a hardened material with high heat resistance, the content of the component (C) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more, relative to 100 parts by mass of the component (D) described later. In terms of being able to suppress the reduction in the refractive index of the hardened material obtained, the content of the component (C) is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of the component (D).

[0158] The component (C) is preferably a compound containing one or two polymerizable carbon-carbon unsaturated bonds in one molecule (hereinafter also referred to as "compound (C1)").

[0159] In terms of the ability to fluidize the pattern at low temperatures (e.g., temperatures below 100° C.) and to easily form a hardened product of a desired shape, the content of the compound (C1) is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more, relative to 100% by mass of the component (C). In terms of the ability to easily form a hardened product having excellent heat resistance or chemical resistance and high reliability, the content of the compound (C1) is preferably 50% by mass or less, more preferably 40% by mass or less, relative to 100% by mass of the component (C).

[0160] In particular, the case where the component (C) is contained in the above amount relative to 100 parts by mass of the component (D) and the compound (C1) is contained in the above amount relative to 100% by mass of the component (C) is suitable in terms of being able to easily form a cured product in a desired shape by heat treatment at a low temperature and being able to easily form a cured product with high heat resistance.

[0161] [Component (D): a compound having a fluorene structure, an acidic group and a (meth)acryloyloxy group in the molecule]

[0162] The component (D) is a compound having a fluorene structure, an acidic group, and a (meth)acryloyloxy group in the molecule, has a high refractive index, and has good alkali solubility and photopolymerizability (particularly, photoradical polymerizability).

[0163] The fluorene structure includes a fluorene structure, a benzofluorene structure, a dibenzofluorene structure, and the like.

[0164] Examples of the acidic group include a carboxyl group, a carboxyalkoxy group, a sulfonic acid group, a phenolic hydroxyl group, a thiol group, an imidazole group, a triazole group, a tetrazolyl 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.

[0165] The compound having the (meth)acryloyloxy group is not particularly limited, but is preferably a compound having a group represented by the following formula (2X).

[0166] (D) The component is preferably a compound represented by the following formula (2) (hereinafter also referred to as "compound (D1)").

[0167] [Chemistry 12]

[0168]

[0169] (In formula (2), Ar 1 and Ar 2 are independently aromatic ring groups;

[0170] R1 and R 2 are independently a monovalent substituent, or represent R 1 With R 2 Bonded to each other and Ar 1 and Ar 2 The condensed ring structure formed together; the condensed ring structure has two aromatic rings connected by a single bond, -O-, -S-, -NR 5 -, carbonyl, methylene or ethylene; R 5 A hydrogen atom or an alkyl group having 1 to 3 carbon atoms;

[0171] R 3 and R 4 are each independently a monovalent substituent;

[0172] X 1 and X 2 Each is independently a group represented by the following formula (2X);

[0173] n1 and n2 are each independently an integer of 1 to 7;

[0174] m1 and m2 are each independently an integer of 0 to 6;

[0175] k1 and k2 are each independently an integer of 0 to 4; when k1 is an integer greater than 2, a plurality of R 3 are independently monovalent substituents, or are bonded to each other and to R 3 The bonded benzene rings together form a condensed ring; when k2 is an integer greater than 2, multiple R 4 are independently monovalent substituents, or are bonded to each other and to R 4 The bonded benzene rings together form a condensed ring;

[0176] Among them, R 1 ~R 4 , X 1 and X 2 At least one of them has an acidic group, and the compound represented by formula (2) has at least one acidic group;

[0177] In formula (2), there are multiple R 1 ~R 4 , X 1 and X 2 In the case of multiple R 1 ~R 4 , X 1 and X 2 Same or Different)

[0178] [Chemistry 13]

[0179]

[0180] (In formula (2X), R 8 An alkanediyl group having 2 to 4 carbon atoms;

[0181] R 6 is a hydrogen atom or a methyl group;

[0182] X is 0 or 1;

[0183] R 9 A hydrogen atom or -OY 1 ;

[0184] Y 1 is a hydrogen atom or "-C(=O)-R 7 -COOH"; R 7 A divalent organic group having 1 or more carbon atoms;

[0185] p is an integer from 0 to 4; when p is 2 or more, multiple R 8 Same or different;

[0186] "*" indicates a bond)

[0187] In the formula (2), Ar 1 The aromatic ring group represented by is a group formed by removing (m1+n1+1) hydrogen atoms from an aromatic ring. 2 The aromatic ring group represented by is a group formed by removing (m2+n2+1) hydrogen atoms from an aromatic ring. 1 and Ar 2 The aromatic ring may be a single ring or a condensed ring.

[0188] As Ar 1 and Ar 2 The aromatic ring is preferably an aromatic hydrocarbon ring, and examples thereof include a benzene ring, a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring. 1 and Ar 2 The aromatic ring is preferably a benzene ring or a naphthalene ring.

[0189] Ar 1 and Ar 2 It is preferably one having a condensed polycyclic aromatic hydrocarbon ring, and more preferably one having a naphthalene ring.

[0190] In R 1 and R 2When each of them is independently a monovalent substituent, examples of the monovalent substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, 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 cycloalkyloxy 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 [The R A and R B are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]), -NH-C(=O)-R [wherein R may have the same 3 , R 4 The same substituent is an alicyclic hydrocarbon group having 5 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms. 1 and R 2 The monovalent substituent represented is preferably the 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 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.

[0191] In R 1 and R 2 Indicates mutual bonding and Ar 1 and Ar 2 In the case of a condensed ring structure formed together, the condensed ring structure has Ar 1 The aromatic ring and Ar 2 The aromatic rings in the 5 -, carbonyl, methylene or ethylene. 1 and R 2 Examples of the condensed ring structure formed by mutual bonding include a fluorene ring, an anthrone ring, a xanthene ring, a thioxanthene ring, etc. Among these, a xanthene ring is preferred.

[0192] m1 and m2 are each independently an integer of 0 to 6, and can be 1 and Ar 2 m1 and m2 are preferably 0 to 3, more preferably 0 or 1, and still more preferably 0.

[0193] n1 and n2 are each independently an integer of 1 to 7, preferably 1 to 4, more preferably 1 or 2, and further preferably 1.

[0194] As R 3 and R 4 The monovalent substituent represented by the present invention includes a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxyl group, the above 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 cycloalkyloxy 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 [The R A and R B are independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]), -NH-C(=O)-R [the R and R 1 and R 2 R in -NH-C(=O)-R has the same meaning as [R]. 3 and R 4 The monovalent substituent represented is preferably the 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 acidic group, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0195] When k1 is an integer greater than 2, a plurality of R 3 are independently monovalent substituents, or are bonded to each other and to R 3 The bonded benzene rings together form a condensed ring. When k2 is an integer greater than 2, a plurality of R 4 are independently monovalent substituents, or are bonded to each other and to R 4 The bonded benzene rings together form a condensed ring. Examples of the condensed ring include a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring. Among these, a naphthalene ring is preferred.

[0196] In addition, when k1 is an integer of 2, two R 3 Bonded to each other and to R 3 When the bonded benzene rings together form a naphthalene ring and k2 is 0, the compound (D1) can be said to be a compound having a benzofluorene skeleton.

[0197] k1 and k2 are integers of 0 to 4, preferably 0 to 2, more preferably 0 or 1, and further preferably 0.

[0198] X 1 and X 2 Each independently represents a group represented by the above formula (2X).

[0199] In formula (2X), R 8 The alkanediyl group having 2 to 4 carbon atoms represented by the above may be linear or branched. 8 It is preferably a linear or branched alkanediyl group having 2 or 3 carbon atoms.

[0200] p is preferably 0-2, more preferably 0 or 1.

[0201] R 6 Preferred is a hydrogen atom.

[0202] In "-C(=O)-R 7 -COOH", R 7 The divalent organic group represented by may be a chain structure or a cyclic structure, or may have a chain structure and a cyclic structure. In the case where the compound (D1) is produced by reacting a (meth)acrylic acid adduct of an epoxy group-containing compound having a fluorene skeleton with a carboxylic anhydride, R 7 This corresponds to a partial structure in which the acid anhydride group (more specifically, a group formed by dehydration condensation of two carboxyl groups in one molecule) of the carboxylic anhydride is excluded.

[0203] As R 7 Specific examples include: a divalent hydrocarbon group, a divalent group containing -O- or -S-, -NR- (R is a monovalent hydrocarbon group) between carbon-carbon bonds of the hydrocarbon group, a divalent group in which any hydrogen atom possessed by the hydrocarbon group is replaced by a monovalent heteroatom-containing group (e.g., an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group), a hydrocarbon group in which two hydrogen atoms bonded to the same carbon are replaced by "=P(R 9 ) 3 "The base represented by (three R 9 are independently a divalent group substituted with a monovalent hydrocarbon group) or a divalent group having a heterocyclic structure.

[0204] 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.

[0205] In R 7 In the case of a divalent group having a heterocyclic structure, examples of the divalent group include a group having a nitrogen-containing heterocyclic structure, a sulfur-containing heterocyclic structure, or an oxygen-containing heterocyclic structure.

[0206] 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 ring structure.

[0207] Examples of the sulfur-containing heterocyclic structure include a thiophene ring structure and a 2,3-dihydro-1,4-dithiine ring structure.

[0208] Examples of the oxygen-containing heterocyclic structure include a furan ring structure and the like.

[0209] In terms of achieving both a high refractive index of the obtained cured product and the ability to form the cured product into a desired shape by heating at a low temperature, among them, R 7 It is preferably a group having one or more hetero atoms 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.

[0210] More specifically, R 7 It is preferably a group having one or more hetero atoms 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.

[0211] In addition, R 7 A group having an aliphatic hydrocarbon ring is preferred.

[0212] As R 7 Preferred specific examples include groups represented by the following formulae (y-1) to (y-4), respectively.

[0213] [Chemistry 14]

[0214]

[0215] (In formula (y-1), Ar 3 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; R 10 is a monovalent substituent; r is an integer from 0 to 6; when r is 2 or more, multiple R 10 Same or different;

[0216] In formula (y-2), Ar 4 and Ar 5 are independently a nitrogen-containing heterocyclic group or a sulfur-containing heterocyclic group;

[0217] In formula (y-3), R 9 is a monovalent hydrocarbon group; multiple R 9 Same or different;

[0218] In formula (y-4), R 11 and R 12 are independently alkanediyl; t is an integer from 1 to 3; when t is 2 or 3, multiple R 11 Same or different;

[0219] "*" indicates a bond)

[0220] Ar 3 The monocyclic aromatic hydrocarbon ring group in 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.

[0221] Ar 3 The condensed polycyclic aromatic hydrocarbon ring group in is a group formed by removing (r+2) hydrogen atoms from a condensed polycyclic aromatic hydrocarbon ring. Examples of the condensed polycyclic aromatic hydrocarbon ring include a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring, and a naphthalene ring is preferred.

[0222] Ar 3 The nitrogen-containing heterocyclic group in is a group obtained by removing (r+2) hydrogen atoms from a nitrogen-containing heterocyclic ring. Examples of the nitrogen-containing heterocyclic ring include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, and a triazine ring.

[0223] Ar 3 The sulfur-containing heterocyclic group in is a group obtained by removing (r+2) hydrogen atoms from a sulfur-containing heterocyclic ring. Examples of the sulfur-containing heterocyclic ring include a thiophene ring and a 2,3-dihydro-1,4-dithiine ring.

[0224] Ar 3 The aliphatic hydrocarbon ring group in is a group formed by removing (r+2) hydrogen atoms from a saturated or unsaturated aliphatic hydrocarbon ring. The aliphatic hydrocarbon ring may be a monocyclic ring or a polycyclic ring such as a condensed aliphatic ring or a bridged aliphatic ring. Specific examples of aliphatic hydrocarbon rings include: saturated monocyclic aliphatic rings such as cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, unsaturated monocyclic aliphatic rings such as cyclobutene ring, cyclopentene ring, cyclohexene ring, cycloheptene ring, condensed aliphatic rings such as decahydronaphthalene ring and octahydronaphthalene ring, and bridged aliphatic rings such as bicyclo[2.2.2]oct-5-ene ring and norbornene ring (bicyclo[2.2.1]hept-5-ene ring).

[0225] From the viewpoint of being able to easily form a cured product with a high refractive index, Ar 3 The aliphatic hydrocarbon ring group represented is preferably a group formed by removing (r+2) hydrogen atoms from an unsaturated aliphatic hydrocarbon ring, more preferably a group formed by removing (r+2) hydrogen atoms 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.

[0226] As R 10 The monovalent substituent represented by can be exemplified as R 1 and R 2 In the case of a monovalent substituent, the same groups as those exemplified as specific examples are included. 10 The monovalent substituent represented is preferably a halogen atom, a hydroxyl group, a carboxyl 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.

[0227] As Ar 4 and Ar 5 The nitrogen-containing heterocyclic group and the sulfur-containing heterocyclic group in the formula (A) include groups formed by removing one hydrogen atom from a substituted or unsubstituted nitrogen-containing heterocyclic group or a sulfur-containing heterocyclic group. Specific examples of the nitrogen-containing heterocyclic group and the sulfur-containing heterocyclic group include the following: 3 The nitrogen-containing heterocyclic ring and the sulfur-containing heterocyclic ring are the same rings as those exemplified by the specific examples. As the substituent, an alkyl group having 1 to 3 carbon atoms can be mentioned. Among these, Ar 4 and Ar 5 It is preferably a substituted or unsubstituted monovalent sulfur-containing aromatic heterocyclic group.

[0228] As R 9 The monovalent hydrocarbon group in the formula (y-3) includes 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 The three R 1 and R 2 may be the same or different from each other. In terms of the ease of forming a hardened material with a high refractive index, it is preferred that the three R 1 and R 2 are 9 At least one of the R is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably three R 9 All of them are monovalent aromatic hydrocarbon groups having 6 to 12 carbon atoms. 9 Preferred is a substituted or unsubstituted phenyl group.

[0229] R 11 and R 12 The alkanediyl group in R may be straight chain or branched. 11 and R 12 The alkanediyl group represented preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0230] In addition, it is preferred that n1 X in formula (2) 1 and n2 X 2 Y 1 One or more of the 7 -COOH" group. In terms of maintaining alkali solubility during development and excellent fluidity upon heating at low temperatures, the compound (D1) preferably has one to six "-C(=O)-R7 It is more preferable to have one or two groups represented by "-COOH".

[0231] As Y 1 "-C(=O)-R 7 Preferred specific examples of the group represented by the formula (2X) in the case of "-COOH" include groups represented by the following formulae (x1-1) to (x1-25), respectively.

[0232] [Chemistry 15]

[0233]

[0234] (In the formula, “*” represents a bond)

[0235] [Chemistry 16]

[0236]

[0237] (In the formula, “*” represents a bond)

[0238] [Chemistry 17]

[0239]

[0240] (In the formula, “*” represents a bond)

[0241] [Chemistry 18]

[0242]

[0243] (In the formula, “*” represents a bond)

[0244] In terms of the fact that a hardened material having a desired shape can be easily formed with a high refractive index by low temperature heating treatment, Y 1 "-C(=O)-R 7 -COOH" is preferably a group represented by the formula (x1-1) to (x1-3), (x1-7) to (x1-13), (x1-16), (x1-17) and (x1-22) to (x1-25), respectively.

[0245] Furthermore, as the component (D), a multimer (for example, a dimer or a trimer) of the compound represented by the above formula (2) may also be used.

[0246] Moreover, as the component (D), a compound other than the compound represented by the above formula (2) (hereinafter also referred to as "compound (D2)") may be used.

[0247] Examples of the compound (D2) include compounds described in Japanese Patent No. 6263631 and the like, compounds having a polymer structure described in Japanese Patent No. 6059754 and the like, and polymers described in Japanese Patent No. 6175259 and the like.

[0248] Preferred specific examples of the compound (D2) include compounds represented by the following formula (D-4) or formula (D-5).

[0249] [Chemistry 19]

[0250]

[0251] The component (D) preferably has a molecular weight lower than that of a polymer component formulated as a base resin in a conventional radiation sensitive composition for forming a high refractive index material, for example.

[0252] By using such 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 component (D), a hardened material with a high refractive index can be easily formed.

[0253] The weight average molecular weight (Mw) of the component (D) in terms of polystyrene obtained by gel permeation chromatography (GPC) is preferably 600 or more, more preferably 700 or more, and further preferably 800 or more. When the Mw is within the above range, an organic film having good alkali developability can be easily formed, and a cured product having excellent heat resistance or chemical resistance can be easily formed.

[0254] 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 of easily forming a cured product of a desired shape by heat treatment at a low temperature and preventing the viscosity of the present composition from becoming too high.

[0255] The content of the component (D) in the present composition is preferably 50% by mass or more, more preferably 60% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, relative to 100% by mass of the solid content of the present composition (i.e., components other than the solvent in the present composition).

[0256] When the content of the component (D) is within the above range, a cured product having a high refractive index can be easily formed, and the cured product can be fluidized at a relatively low temperature (eg, 100° C. or lower), so that the cured product can be easily formed into a desired shape.

[0257] [Other ingredients]

[0258] In addition to the above-mentioned components (A) to (D), the present composition may further contain components other than these (hereinafter also referred to as "other components") within the range that does not impair the effects of the present invention. Examples of other components include polymers, solvents, polymerization inhibitors, surfactants, antioxidants, sensitizers, softeners, plasticizers, adhesion aids, and ultraviolet absorbers.

[0259] The blending ratio of these other components can be appropriately selected according to each component within a range that does not impair the effects of the present invention.

[0260] ·polymer

[0261] The present composition may also contain a polymer (hereinafter also referred to as "polymer (E)") as an additive component. By adding the polymer (E) to the present composition, the heat resistance of the obtained cured product can be improved, and a cured product with a high refractive index and better reliability can be easily formed.

[0262] Examples of the polymer (E) include alkali-soluble polymers, fluorene skeleton-containing radiation-sensitive polymers, and carboxyl group-containing radiation-sensitive polymers.

[0263] The molecular weight of the polymer (E) is preferably 2,000 or more and 100,000 or less.

[0264] Examples of the alkali-soluble polymer include (meth)acrylic acid / methyl (meth)acrylate copolymers, (meth)acrylic acid / benzyl (meth)acrylate copolymers, (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate copolymers, (meth)acrylic acid / styrene / isoprene / tricyclodecyl (meth)acrylate / 2-mono(hexahydroxyphthalyloxy)ethyl (meth)acrylate copolymers, (meth)acrylic acid-modified (meth)acrylic acid resins, and acid anhydride-modified (meth)acrylic acid resins.

[0265] Examples of the radiation-sensitive polymer containing a fluorene skeleton include polymers described in International Publication No. 2009 / 119622.

[0266] As specific examples of the carboxyl group-containing radiation-sensitive polymer, commercially available products may be used, and examples of the commercially available products include CCR-1235, CCR-1291H, ZAR-1035, ZAR-2000, ZFR-1401H, ZFR-1491H, ZCR-1569H, and ZCR-1798H (all manufactured by Nippon Kayaku Co., Ltd.).

[0267] When a polymer (E) is added to the present composition, the amount of the polymer (E) is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of component (D). When the amount of the polymer (E) is within the above range, a cured product having excellent heat resistance can be easily formed into a desired shape by heat treatment at a low temperature.

[0268] Solvent

[0269] The present composition is preferably a liquid composition obtained by dissolving or dispersing the components (A) to (D) and other components prepared as necessary in a solvent (hereinafter also referred to as “solvent (F)”).

[0270] The solvent (F) is preferably an organic solvent that dissolves the components formulated in the present composition and does not react with the components.

[0271] 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. Among these, the solvent (F) preferably contains at least one selected from the group consisting of ethers, esters, and ketones.

[0272] Surfactants

[0273] For example, the coating properties of the present composition can be improved (wetting and spreading properties or coating unevenness can be reduced) by using a surfactant.

[0274] Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

[0275] As the fluorine-based surfactant, a commercially available product can be used, and examples of the commercially available product include: Megafac F-171, Megafac F-172, Megafac F-173, Megafac F-251, Megafac F-430, Megafac F-554, Megafac F-563 (manufactured by DIC Corporation); Fluorad FC430, Fluorad FC431, Fluorad FC432, Fluorad FC433, Fluorad FC434, Fluorad FC435, Fluorad FC436, Fluorad FC437, Fluorad FC438, Fluorad FC439, Fluorad FC440, Fluorad FC441, Fluorad FC443, Fluorad FC444, Fluorad FC445, Fluorad FC446, Fluorad FC447, Fluorad FC448, Fluorad FC449, Fluorad FC448, Fluorad FC449, Fluorad FC441, Fluorad FC443 ...2, Fluorad FC443, Fluorad FC444, Fluorad FC445, Fluorad FC446, Fluorad FC447, Fluorad FC448, Fluorad )FC431 (manufactured by Sumitomo 3M Co., Ltd.); AsahiGuard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106, Surflon S-611 (AGC Qingmei Chemical Co., Ltd. (manufactured by SEIMI Chemical); Polyflow No.75, Polyflow No.95 (manufactured by Kyoeisha Chemical); FTX-218 (manufactured by NEOS); Eftop EF301, Eftop EF303, Eftop EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), etc.

[0276] As the silicone surfactant, commercially available products can 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, PAINTAD 19, FZ-2101, FZ-77, FZ-2118, L-7001, L-7002 (Dow Toray), ray)(manufactured by Shin-Etsu Chemical Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-300, BYK-306, BYK-310, BYK-330, BYK-335, BYK-341, BYK-344, BYK-370, BYK-340, BYK-345 (manufactured by BYK-Chemie Japan)(manufactured by BYK-Chemie Japan Co., Ltd.), etc.

[0277] Examples of the nonionic surfactant 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.

[0278] When a surfactant is blended in the present composition, the amount of the surfactant blended is preferably 0.01 to 1.5 parts by mass, more preferably 0.02 to 1.2 parts by mass, and still more preferably 0.05 to 1.0 parts by mass, relative to 100 parts by mass of component (D).

[0279] Antioxidants

[0280] For example, by using an antioxidant, decomposition and degradation of polymer molecules in the present composition can be suppressed, and durability can be improved.

[0281] Examples of the antioxidant include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, and diethylenethiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0282] When an antioxidant is blended in 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 still more preferably 0.05 to 1.0 parts by mass, based on 100 parts by mass of the component (D).

[0283] ·Sealing agent

[0284] By using the present composition containing the adhesion aid, the adhesion between the formed cured product and the substrate (adherend) can be improved, and the peeling of the cured product from the substrate in the development step or the like can be suppressed.

[0285] As the adhesion aid, a functional silane coupling agent having a reactive functional group is preferred.

[0286] Examples of the reactive functional group possessed by the functional silane coupling agent include a carboxyl group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

[0287] Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0288] When the adhesion aid is mix|blended in this composition, the mixing|blending amount is preferably 0.01 mass part - 4 mass parts, and more preferably 0.1 mass part - 2 mass parts, based on 100 mass parts of (D) components.

[0289] [Method for preparing the present composition]

[0290] The present composition can be prepared by mixing the components (A) to (D) and any other components.

[0291] Alternatively, after mixing the components, the obtained mixture may be filtered using a filter having a pore size of 0.5 μm or less, as necessary.

[0292] The solid content concentration of this composition (that is, the total mass of the composition other than the solvent in this composition, the ratio shared in the total mass of this composition) can be considered that viscosity or volatility etc. are appropriately selected.The solid content concentration of this composition is preferably 1 mass %~60 mass %, more preferably 2 mass %~50 mass %, and then preferably 5 mass %~40 mass %.If solid content concentration is more than the lower limit, then when this composition is applied on substrate (adherend), the film thickness of the coating can be fully ensured, etc., preferably.In addition, if solid content concentration is below the upper limit, then the viscosity of this composition can be appropriately improved and good coating properties can be ensured, etc., preferably.

[0293] In terms of making the cured product with good sensitivity and easily forming it into a desired shape by heat treatment, the content of the polymerizable compound in the present composition (i.e., the total amount of the (C) component and the (D) component) is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more, relative to 100% by mass of the solid content contained in the present composition.

[0294] The present composition can be suitably used for optical components used in at least a part of imaging devices such as cameras, organic EL elements, or various display elements such as liquid crystal display elements. In particular, when the present composition is used to form a cured product by heat treatment, it can be suitably used as a radiation-sensitive composition for microlens production or flattening film production, especially a radiation-sensitive composition for microlens production based on a heat flow method, in terms of being able to easily form a cured product having a desired microlens shape or flattening film shape.

[0295] Hardened

[0296] 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, can be formed by irradiating the present composition with radiation.

[0297] As described above, since the present cured product is formed from the present composition, it is excellent in heat resistance and transparency and has a high refractive index.

[0298] The shape of the cured product is not particularly limited, but is preferably a microlens or a planarized film, and more preferably a microlens, from the viewpoint of further exerting the effects of the present invention.

[0299] This hardened material can be suitably used as an optical component used in at least a part of an imaging device such as a camera, an organic EL element, or various display elements such as a liquid crystal display element. That is, this hardened material can be suitably used as a material for an optical component. Specifically, it can be suitably used as an optical component such as a microlens of a solid imaging element included in an imaging device such as a camera, or an organic EL element (organic light emitting diode (OLED)) or liquid crystal display element (liquid crystal display (LCD)), μLED, etc. included in a display device. In addition, it can also be suitably used as a flattening film provided in an organic EL element or a liquid crystal display element.

[0300] The refractive index of the present cured product at a wavelength of 550 nm is preferably 1.64 or more, more preferably 1.66 or more.

[0301] 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 members.

[0302] Specifically, the refractive index can be measured by the method described in the following Examples.

[0303] [Method for producing the present hardened product]

[0304] The method for producing the present cured product includes the 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 irradiating with radiation using the mask. Furthermore, heat treatment may be performed after irradiating with radiation.

[0305] The present composition is particularly suitable as a negative pattern forming material, which is used to make the following pattern (i.e., a hardened material formed by the present composition) fluidized by heat treatment, thereby forming a desired shape (e.g., a microlens shape, a flattened film shape), that is, a pattern formed by exposing a portion of an organic film formed by the present composition and dissolving the unexposed portion of the exposed organic film in an alkaline developer.

[0306] As a preferred example of a method for producing a microlens according to an embodiment of the present cured product, the following first production method and second production method can be cited.

[0307] <First Manufacturing Method>

[0308] The first production method is a method including the following steps (I) to (IV), and may further include the following step (V).

[0309] (Step (I): coating step)

[0310] Step (I) is a step of forming a coating film (organic film) on a substrate by applying the present composition on the substrate.

[0311] Examples of the substrate include glass substrates, silicon wafers, plastic substrates, and substrates having a color resist, an overcoat layer, an antireflection film, various metal thin films, a sealing film, and the like formed on the surface thereof.

[0312] Examples of the plastic substrate include resin substrates (resin films) made of plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyether sulfone, polycarbonate, and polyimide.

[0313] Various elements (for example, a light receiving element such as a photodiode or a light emitting element such as an organic light emitting diode) may be provided in advance in the substrate.

[0314] As a coating method of the present composition, for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slot die coating method, a bar coating method, an ink jet method, etc. can be used. As a coating method, spin coating method, a bar coating method, and a slot die coating method are preferable among these.

[0315] After the composition is applied to the substrate, the composition may be preheated (prebaked) for the purpose of preventing dripping. The prebaking conditions may be appropriately set according to the type or proportion of each component used in the composition, for example, at 60°C to 130°C for 30 seconds to 10 minutes.

[0316] The film thickness of the formed coating film is preferably 0.1 μm to 20 μm, more preferably 0.2 μm to 15 μm, as the film thickness after prebaking.

[0317] (Step (II): Exposure Step)

[0318] Step (II) is a step of irradiating a portion of the coating film formed in step (I) with radiation. By the irradiation with radiation, a curing reaction proceeds in the exposed portion, and a cured product is obtained in which the exposed portion is cured.

[0319] In step (II), the radiation irradiation to the coating film is performed through a mask having a pattern (e.g., a dot pattern) for obtaining microlenses having a desired shape. The mask may also be a multi-grayscale mask such as a halftone mask or a gray tone mask.

[0320] As a radiation irradiated to a coating film, ultraviolet rays, extreme ultraviolet rays, X-rays, and charged particle beams are mentioned, for example.

[0321] Examples of ultraviolet rays include g-rays (wavelength: 436 nm), i-rays (wavelength: 365 nm), and KrF excimer laser light (wavelength: 248 nm).

[0322] Examples of X-rays include synchrotron radiation.

[0323] As a charged particle beam, an electron beam is mentioned, for example.

[0324] Among these, ultraviolet rays are preferred, and ultraviolet rays having a wavelength of 200 nm to 380 nm are more preferred.

[0325] Examples of the light source used for radiation irradiation include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and an excimer laser.

[0326] The radiation exposure dose is preferably 500 J / m 2 ~50,000J / m 2 (50mJ / cm 2 ~5,000mJ / cm 2 ).

[0327] (Step (III): Development Step)

[0328] 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). The development step can remove the coating film formed on the substrate in the unexposed portion, thereby forming a pattern (for example, a concave-convex pattern formed by a plurality of regularly arranged fine cured products) in which the cured products (fine cured products) in the exposed portion remain on the substrate.

[0329] As the developer, an aqueous solution of an alkali (alkaline compound) can be mentioned.

[0330] Examples of the base 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.

[0331] Alternatively, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous alkali solution, or a small amount of various organic solvents capable of dissolving the present composition may be added.

[0332] The concentration of the developer can be appropriately determined depending on the composition of the composition, and is usually 0.01% by mass to 10% by mass, and preferably 0.5% by mass to 5% by mass.

[0333] As the developing method, for example, an appropriate method such as a coating method, a dipping method, a shaking dipping method, a shower method, or the like can be adopted.

[0334] The development time may be appropriately adjusted according to the composition of the present composition, and is, for example, 20 seconds to 120 seconds.

[0335] After the development step, a step of washing the developed patterned substrate with pure water or the like may be performed as necessary.

[0336] In addition, a step of drying the patterned substrate after development or the cleaning may be performed. The drying conditions are not particularly limited, and for example, the same conditions as those for the pre-baking may be mentioned.

[0337] (Step (IV): Heating Step)

[0338] Step (IV) is a step of heating and melting the developed pattern to form the fine hardened material on the substrate into a lens shape by heat flow.

[0339] By the heat treatment in step (IV), the present composition can be further cured while heat-fluxing the pattern of the fine cured product.

[0340] Through step (IV), a microlens (array) in which hemispherical micro-hardened objects are (regularly) arranged on a substrate can be obtained.

[0341] The heat treatment can be performed using a heating device such as an oven or a hot plate.

[0342] The heating temperature in step (IV) can be appropriately selected according to the substrate or the present composition used, and is preferably 100° C. or less, more preferably 95° C. or less, and further preferably 85° C. or less, from the perspective of being applicable to high-refractive-index materials for organic electroluminescent elements. In addition, from the perspective of being able to easily form a microlens having a desired shape and high heat resistance and chemical resistance, the heating temperature in step (IV) is preferably 60° C. or more, more preferably 80° C. or more.

[0343] According to the present composition, a microlens of a desired shape can be formed even when heat-treated at a low temperature of 100° C. or lower. As described above, by heat-treating at a low temperature of 100° C. or lower, an organic EL element or the like requiring application of a low temperature process can be used as a substrate.

[0344] The heating time can be appropriately set according to the type of heating device, etc. For example, when a hot plate is used for heating, the heating time is, for example, 5 minutes to 60 minutes. In addition, when an oven is used for heating, the heating time is, for example, 10 minutes to 90 minutes.

[0345] In step (IV), a step baking method in which the heating treatment is performed multiple times may be used.

[0346] (Step (V): Post-exposure step)

[0347] Step (V) is a step of further irradiating the developed hardened product (micro hardened product) 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 in terms of being able to easily form a microlens of a desired shape by low-temperature heat flow.

[0348] By irradiating with radiation in the step (V) (hereinafter also referred to as “post-exposure”), heat resistance, chemical resistance, etc. can be further improved, and a highly reliable microlens can be easily formed.

[0349] Among these, the type of radiation or exposure conditions in the post-exposure may be the same as those in step (II). In addition, the wavelength or irradiation amount of the irradiation light, the light source and other conditions in the post-exposure may be the same as or different from those in step (II).

[0350] <Second manufacturing method>

[0351] The second manufacturing method includes a step of inkjet coating or nanoimprinting the composition on a substrate to form a pattern. In the second manufacturing method, a spherical lens-shaped pattern can be directly formed on the substrate by inkjet coating or nanoimprinting. Alternatively, a pattern (e.g., a dot pattern) can be formed on the substrate by inkjet coating or nanoimprinting, and then the same step (IV) as the first manufacturing method is performed to form the desired microlens shape.

[0352] In addition, the second manufacturing method may include the same step as the step (V) in the first manufacturing method.

[0353] The planarized film as one embodiment of the present cured product can be produced by the same method as the first production method except that no mask is used or a pattern other than a dot pattern is used in step (II) of the first production method.

[0354] Display Device

[0355] The display device of the present disclosure is not particularly limited as long as it includes the present cured product, and may have any conventionally known structure other than including the present cured product.

[0356] Examples of the display device include a liquid crystal display (LCD), an organic EL using an organic light emitting diode (OLED), a μLED display, an electrochromic display (ECD), an electroluminescent display (ELD), and a display using a quantum dot-organic EL (QD-OLED).

[0357] Camera Device

[0358] The imaging device of the present disclosure is not particularly limited as long as it includes the present cured product, and may have any conventionally known structure other than including the present cured product.

[0359] Examples of the imaging device include: a video camera, a digital camera, a mobile phone with a camera function, an endoscopic camera, a capsule endoscopic camera, a microscope, a medical or health care camera (for example, a camera for photographing blood vessels based on infrared light reception), a vehicle-mounted camera (for example, a camera for photographing the surroundings and interior of a vehicle, a camera for detecting the distance between vehicles), a surveillance camera, a person authentication camera, and an industrial camera.

[0360] [Example]

[0361] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

[0362] The weight average molecular weight (Mw) of the compound is a polystyrene-equivalent value measured by gel permeation chromatography (GPC) under the following conditions.

[0363] Column: Made by Tosoh Corporation, TSKgelGRCXLII

[0364] Solvent: Tetrahydrofuran

[0365] Temperature: 40℃

[0366] Pressure: 68kgf / cm 2

[0367] [Preparation of radiation-sensitive composition]

[0368] The details of the compound (A) to the compound (D) and the solvent (F) used for preparing the radiation sensitive composition in the Examples and Comparative Examples are shown below.

[0369] <Compound (A)>

[0370] A-1 to A-12: Compounds represented by the following formulas (A-1) to (A-12)

[0371] [Chemistry 20]

[0372]

[0373]

[0374] Compound (A-1): 6,6'-(9H-fluorene-9,9-diyl)bis(2-naphthol) (BNF, manufactured by Jiangsu Ever Galaxy Chemical)

[0375] Compound (A-2): 9,9'-bis(4-hydroxyphenyl)fluorene (BPFL, manufactured by JFE Chemical)

[0376] Compound (A-3): 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene (BCF, manufactured by JFE Chemical)

[0377] Compound (A-4): 2,2'-[9H-fluorene-9,9-diylbis(naphthalene-6,2-diyloxy)diethanol (BNF-EO, manufactured by Jiangsu Ever Galaxy Chemical)

[0378] Compound (A-5): 100 g (0.22 mol) of 6,6'-(9H-fluorene-9,9-diyl)bis(2-naphthol), 94.5 g (0.67 mol) of methyl iodide, 92.0 g (0.67 mol) of potassium carbonate and 1 L of dimethyl sulfoxide were placed in a 2 L three-necked flask including a thermometer and a nitrogen inlet tube, and stirred at 25 ° C for 6 hours. After the reaction was completed, the reaction solution was put into 2 L of distilled water, and the precipitated solid was filtered and washed with water. Then, the filtered and separated solid was vacuum dried to obtain 103 g of white powder of compound (A-5) represented by the formula (A-5).

[0379] Compound (A-6): 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (BAHF, manufactured by JFE Chemical)

[0380] Compound (A-7): 200 g (0.53 mol) of 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 156 g (1.05 mol) of phthalic anhydride and 2 L of N-methyl-2-pyrrolidone were placed in a 2 L three-necked flask including a thermometer and a nitrogen inlet tube, and stirred at 25 ° C for 12 hours. After the reaction, the reaction solution was put into 4 L of distilled water, and the precipitated solid was filtered and washed with water. Then, the filtered solid was vacuum dried to obtain 310 g of white powder of the compound (A-7) represented by the formula (A-7).

[0381] Compound (A-8): 100 g (0.29 mol) of 4,4'-(9H-fluorene-9,9-diyl)diphenylamine, 79.3 g (0.57 mol) of salicylic acid, 92.5 g (0.29 mol) of tetrabutylammonium bromide and 178 g (0.57 mol) of triphenyl phosphite were placed in a 2L three-necked flask including a thermometer and a nitrogen inlet tube, and stirred at 120°C for 2 hours. After the reaction was completed, 1 L of dichloromethane was added to the reaction solution cooled to room temperature, and the solution was separated and washed with a 2N aqueous hydrochloric acid solution and water. Subsequently, the organic layer was concentrated under reduced pressure, and 1 L of methanol was added to the crude product for recrystallization, thereby obtaining 160 g of a white powder of the compound (A-8) represented by the formula (A-8).

[0382] Compound (A-9): 250 g (0.72 mol) of 4,4'-(9H-fluorene-9,9-diyl)diphenylamine, 358 g (1.58 mol) of naphthalene-2-sulfonyl chloride and 1 L of pyridine were placed in a 2L three-necked flask including 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 concentration under reduced pressure, and after being acidified with 2N hydrochloric acid water, it was separated and washed with dichloromethane and water. Then, the organic layer was concentrated under reduced pressure and vacuum dried to obtain 472 g of a white powder of the compound (A-9) represented by the formula (A-9).

[0383] Compound (A-10): 480 g of a white powder of compound (A-10) represented by the formula (A-10) was obtained in the same manner as in the synthesis example of compound (A-9), except that naphthalene-2-sulfonyl chloride in the synthesis example of compound (A-9) was replaced with 358 g (1.58 mol) of naphthalene-1-sulfonyl chloride.

[0384] Compound (A-11): 100 g (0.29 mol) of 4,4'-(9H-fluorene-9,9-diyl)diphenylamine and 200 mL of tetrahydrofuran were placed in a 1L three-necked flask including a thermometer and a nitrogen inlet tube and ice-cooled. Then, 119 g (0.57 mol) of p-toluenesulfonyl isocyanate was slowly added dropwise at an internal temperature not exceeding 20°C, and stirred at 25°C for 1 hour. After the reaction was completed, the reaction solution was added to 1L of ethanol, and the precipitated solid was separated by filtration. Then, the filtered and separated solid was vacuum dried to obtain 182 g of a white powder of compound (A-11) represented by the formula (A-11).

[0385] Compound (A-12): 147 g of white powder of compound (A-12) represented by the 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)diphenylamine in the synthesis example of compound (A-11) was changed to 6,6'-(9H-fluorene-9,9-diyl)bis(2-naphthol).

[0386] <Compound (B)>

[0387] B-1: 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)] (Irgacure OXE01, manufactured by BASF)

[0388] B-2: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one (Irgacure 907, manufactured by BASF)

[0389] B-3: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[0390] B-4: 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone

[0391] B-5: TR-PBG-345 (O-acyl oxime compound, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0392] <Compound (C)>

[0393] C-1: 2-Hydroxy-3-phenoxypropyl acrylate

[0394] C-2: Polyethylene glycol diacrylate

[0395] C-3: A mixture of dipentaerythritol hexaacrylate (40% by mass) and dipentaerythritol pentaacrylate (60% by mass)

[0396] C-4: Pentaerythritol tetraacrylate

[0397] C-5: Diethylene glycol modified dipentaerythritol hexaacrylate

[0398] C-6: Trimethylolpropane polypropylene glycol triacrylate

[0399] C-7: N-(2-Hydroxyethyl)acrylamide

[0400] <Compound (D)>

[0401] D-1: norbornene dicarboxylic anhydride-modified fluorene-containing acrylate (compound represented by the following formula (D-1))

[0402] D-2: Phthalic anhydride-modified fluorene-containing acrylate (a compound represented by the following formula (D-2))

[0403] D-3: Benzofluorene-containing acrylate (a compound represented by the following formula (D-3))

[0404] 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 polymerization ratio of the copolymer is 70 / 15 / 15 (mass ratio) of the copolymer of benzofluorene-containing acrylate, acrylic acid, and 3-(acryloyloxy)-2-hydroxypropyl methacrylate.

[0405] D-5: Acid anhydride-modified fluorene-containing acrylic resin (compound represented by the following formula (D-5), Mw: 4000)

[0406] [Chemistry 21]

[0407]

[0408] <Comparative compound (d)>

[0409] 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 polymerization ratio of the copolymer is butyl acrylate, acrylic acid, and 3-(acryloyloxy)-2-hydroxypropyl methacrylate = 80 / 10 / 10 (mass ratio)

[0410] [Chemistry 22]

[0411]

[0412] <Solvent (F)>

[0413] F-1: Propylene Glycol Monomethyl Ether Acetate (PGMEA)

[0414] F-2: Cyclopentanone (CPN)

[0415] F-3: N-Methyl Pyrrolidone (NMP)

[0416] F-4: Propylene Glycol Monomethyl Ether (PEGME)

[0417] (Example 1)

[0418] 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 compound (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 ("FTX-218" manufactured by NEOS Co., Ltd.) were mixed, and then solvent (F-1) was added so that the solid content concentration became 35% by mass, and then each component was dissolved by stirring. Then, the obtained mixture was filtered with a membrane filter having a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[0419] (Example 2 to Example 35 and Comparative Example 1 to Comparative Example 3)

[0420] Except having changed the kind and the usage-amount of each component as described in Table 1, it carried out similarly to Example 1, and prepared the radiation sensitive composition.

[0421] [Evaluation of radiation sensitive composition]

[0422] 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.

[0423] <Evaluation of refractive index>

[0424] Each radiation-sensitive composition was applied onto an alkali-free glass substrate using a spinner and pre-baked on a hot plate at 100°C for 3 minutes to form a coating film with a thickness of 9.0 μm. The obtained coating film was then irradiated with a high-pressure mercury lamp (illuminance at 365 nm: about 500 mW / cm 2 ) at 300mJ / cm 2 The substrate was irradiated with radiation at an exposure amount of . Then, a 2.38 mass % tetramethylammonium hydroxide aqueous solution at 23°C was used as a developer, and the substrate was developed for 60 seconds at 25°C by a liquid coating method, followed by 60 seconds of pure water washing, and then the substrate was dried. Then, the substrate was post-baked in an oven at 85°C for 40 minutes to form a cured film. The refractive index of the obtained cured product under light of a wavelength of 550nm was measured using a rotary compensator type spectroscopic ellipsometer SE-2000 (manufactured by Semilab Semiconductor Physics Laboratory Co. Ltd.), and evaluated according to the following evaluation criteria.

[0425] Evaluation benchmark

[0426] AA: Refractive index ≥ 1.66

[0427] BB: 1.66>Refractive index ≧1.64

[0428] CC: 1.64>Refractive index

[0429] <Evaluation of pattern wetting and spreading>

[0430] Each of the prepared radiation-sensitive compositions was applied onto an alkali-free glass substrate using a spinner, and then pre-baked on a hot plate at 100° C. for 3 minutes to form a coating film having a film thickness of 9.0 μm.

[0431] The obtained coating film was then exposed to light using a projection exposure apparatus (high-pressure mercury lamp; illuminance at 365 nm: about 500 mW / cm2) via a photomask having a circular residual pattern with a diameter of 15 μm. 2 ) at 300mJ / cm 2 The radiation exposure is carried out at an exposure dose of .

[0432] Then, a 2.38 mass % tetramethylammonium hydroxide aqueous solution at 23° C. was used as a developer, and development was performed by a flooding method at 25° C. for 60 seconds, followed by 60 seconds of pure water washing, and then the substrate was dried, thereby forming a pattern including a plurality of micro-bodies formed of the radiation-sensitive composition on the substrate (an enlarged photograph of the pattern at this time is shown in FIG. 1 ). Figure 1 (a)). The diameter (width) of the portion where the obtained pattern contacts the substrate is measured using an optical microscope. The diameter (width) of the pattern measured is defined as Y μm.

[0433] Then, post-baking was performed in an oven at 85° C. for 40 minutes to form a lens pattern including a plurality of micro-bodies formed of the radiation-sensitive composition on the substrate (an enlarged photograph of the lens pattern at this time is shown in FIG. Figure 1 (b)). The diameter (width) of the portion where the obtained lens pattern contacts the substrate is measured using an optical microscope. The diameter (width) of the lens pattern measured is defined as Z μm.

[0434] The wettability and spreadability of the pattern were evaluated according to the following evaluation criteria: 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 the wettability and spreadability of the pattern were suppressed.

[0435] Evaluation benchmark

[0436] AA: (ZY) ≦ Y × 0.2

[0437] BB: Y×0.2<(ZY)≦Y×0.4

[0438] CC: (ZY)>Y×0.4

[0439] -: No pattern obtained

[0440] [Table 1]

[0441]

Claims

1. A radiation-sensitive composition comprising (A) Component: A compound represented by the following formula (1) having no (meth)acryloyloxy group, (B) component: photopolymerization initiator, (C) component: polymerizable compound, in, (D) excluding ingredients, and Component (D): a compound having a fluorene structure, an acidic group and a (meth)acryloyloxy group in the molecule; In formula (1), Ar 1 and Ar 2 are independently aromatic ring groups; R 1 and R 2 are independently a monovalent substituent, or represent R 1 With R 2 Bonded to each other and to Ar 1 and Ar 2 The condensed ring structure formed together; the condensed ring structure has two aromatic rings connected by a single bond, -O-, -S-, -NR 5 -, carbonyl, methylene or ethylene; R 5 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 are each independently an integer from 0 to 7; k1 and k2 are each independently an integer of 0 to 4; when k1 is an integer greater than 2, a plurality of R 3 are independently monovalent substituents, or are bonded to each other and to R 3 The bonded benzene rings together form a condensed ring; when k2 is an integer greater than 2, multiple R 4 are independently monovalent substituents, or are bonded to each other and to R 4 The bonded benzene rings together form a condensed ring; In formula (1), there are multiple R 1 ~R 4 In the case of multiple R 1 ~R 4 Same or different.

2. The radiation-sensitive composition according to claim 1, in, The component (D) is a compound represented by the following formula (2); In formula (2), Ar 1 and Ar 2 are independently aromatic ring groups; R 1 and R 2 are independently a monovalent substituent, or represent R 1 With R 2 Bonded to each other and to Ar 1 and Ar 2 The condensed ring structure formed together; the condensed ring structure has two aromatic rings connected by a single bond, -O-, -S-, -NR 5 -, carbonyl, methylene or ethylene; R 5 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 Each is independently a group represented by the following formula (2X); n1 and n2 are each independently an integer of 1 to 7; m1 and m2 are each independently an integer of 0 to 6; k1 and k2 are each independently an integer of 0 to 4; when k1 is an integer greater than 2, a plurality of R 3 are independently monovalent substituents, or are bonded to each other and to R 3 The bonded benzene rings together form a condensed ring; when k2 is an integer greater than 2, multiple R 4 are independently monovalent substituents, or are bonded to each other and to R 4 The bonded benzene rings together form a condensed ring; Among them, R 1 ~R 4 , X 1 and X 2 At least one of them has an acidic group, and the compound represented by formula (2) has at least one acidic group; In formula (2), there are multiple R 1 ~R 4 , X 1 and X 2 In the case of multiple R 1 ~R 4 , X 1 and X 2 Same or different; In formula (2X), R 8 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 A hydrogen atom or -OY 1 ; Y 1 is a hydrogen atom or "-C(=O)-R 7 -COOH"; R 7 A divalent organic group having 1 or more carbon atoms; p is an integer from 0 to 4; when p is 2 or more, multiple R 8 Same or different; "*" indicates a bonding bond.

3. The radiation sensitive composition according to claim 1, which is used for producing a microlens by a heat flow method. 4 . A cured product obtained by curing the radiation sensitive composition according to claim 1 . The cured product according to claim 4 , which has a refractive index of 1.64 or more at a wavelength of 550 nm. The cured product according to claim 4 , which is used for optical components.

7. A display device comprising the hardened material according to claim 4.

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

9. A method for producing a hardened product, include: A step of applying the radiation-sensitive composition according to any one of claims 1 to 3 on a substrate; a step of irradiating the radiation-sensitive composition coated on the substrate with radiation; A step of developing the radiation-sensitive composition after irradiation with radiation; and A step of heating the radiation-sensitive composition after development.

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

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

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