Radiation-sensitive composition, method for manufacturing lens, display element, display device, solid-state imaging element, imaging device, and compound

Abstract

To provide a radiation-sensitive composition which has good patterning characteristics, can be melted by low-temperature heating, and can give a cured product having high reliability and a high refractive index.SOLUTION: The radiation-sensitive composition contains a component (A): a reaction product of a compound represented by formula (1) and a compound represented by formula (2), a component (B): a photopolymerization initiator, and a component (C): a compound having a polymerizable carbon-carbon unsaturated bond (excluding the component (A)). In the formula (1), Ar1 and Ar2 are aromatic ring groups; X1 and X2 are groups represented by formula (1x); and n1 and n2 are integers of 1-6. In the formula (2), R7 is an r-valent organic group; and r is an integer of 1-4.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a radiation-sensitive composition, a method for producing a lens, a display element, a display device, a solid-state imaging element, an imaging device, and a compound. [Background technology]

[0002] Various image sensors, such as CCD (Charge-Coupled Device) image sensors and CMOS (Complementary Metal-Oxide-Semiconductor) image sensors, are used as solid-state imaging elements in imaging devices such as cameras. In solid-state imaging elements, tiny condenser lenses (hereinafter also referred to as "microlenses") are regularly arranged in order to collect light on a light receiving element (photodiode) and improve the sensitivity of the sensor.

[0003] In addition, in various display elements such as organic electroluminescence (OLED) elements and liquid crystal display elements, a structure in which a microlens is provided on the light output side of each pixel is also adopted for the purpose of improving light extraction efficiency and adjusting the viewing angle. In self-luminous displays such as OLED display devices, attempts are being made to improve brightness and adjust the viewing angle by forming microlenses out of highly refractive materials.

[0004] A thermal flow method is known as one method for forming microlenses (see, for example, Patent Document 1). The thermal flow method is a method for forming a hemispherical microlens array by forming a pattern corresponding to the arrangement of microlenses on the upper part of a light receiving element or a light emitting element using a radiation-sensitive composition, and then subjecting the pattern to a heating process.

[0005] Conventionally, in a process for forming a cured film (e.g., a planarizing film) in an organic EL element or a liquid crystal display element, a method has been adopted in which a radiation-sensitive composition is applied onto a substrate to form a coating film, the coating film is exposed to light through a photomask having a predetermined opening pattern, and then the coating film is brought into contact with a developer to dissolve and remove the unexposed areas, thereby obtaining a patterned cured film (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2020-101659 A [Patent Document 2] JP 2017-107024 A Summary of the Invention [Problem to be solved by the invention]

[0007] When a patterned cured product having a high refractive index is to be obtained, the radiation-sensitive composition for obtaining the cured product is required to have a sufficiently high solubility in an alkaline solution used as a developer, while at the same time increasing the refractive index of the resulting cured product, thereby exhibiting good patterning properties.

[0008] As a method for forming a high refractive index material such as a microlens or a planarization film, a method using a high refractive index filler such as a metal oxide is known. However, the method using a metal oxide has a disadvantage that the cleaning of the manufacturing line becomes complicated in the manufacturing process of the high refractive index material, and the equipment is easily contaminated. In addition, in the case of a material containing a high refractive index filler, the pattern after exposure and development is unlikely to melt due to heat, and it is difficult to form a microlens by the thermal flow method.

[0009] A method has also been proposed in which a pattern made of a photosensitive resin layer is melted by heat treatment to form a lens shape without using a high refractive index filler such as a metal oxide. However, when forming a microlens by melting a photosensitive resin layer, a high-temperature process of 150°C or more is required, and there is a concern that it is not suitable for a process that requires low temperature. In particular, in an organic EL element, when a microlens is provided on the light output side of each pixel for the purpose of improving light extraction efficiency and adjusting the viewing angle, it is required that the microlens can be formed at a low temperature (for example, 100°C or less) in the manufacturing process of the organic EL element, considering that the organic light-emitting material is easily deteriorated by heat. In addition, in a planarization film for an organic EL element, if a pattern after exposure and development processing can be melted by heating at a low temperature, it can be said that a cured film with a high degree of planarization can be formed while protecting the organic light-emitting material from heat.

[0010] Furthermore, if the components in the cured product formed using the radiation-sensitive composition are prone to generate decomposition products, there is a concern that the decomposition products may cause a deterioration in the quality of the element (e.g., a change in transmittance). On the other hand, in order to meet the demand for further high quality in recent years, the cured product is required to have high reliability.

[0011] The present invention has been made in consideration of the above problems, and an object of the present invention is to provide a radiation-sensitive composition that has good patterning properties, can be melted by heating at a low temperature, and is capable of giving a cured product that is highly reliable and has a high refractive index. [Means for solving the problem]

[0012] According to the present invention, there are provided the following radiation-sensitive composition, lens manufacturing method, display element, display device, solid-state imaging element, imaging device, and compound.

[0013] [1] A radiation-sensitive composition comprising: component (A): a reaction product of a compound represented by the following formula (1) and a compound represented by the following formula (2): component (B): a photopolymerization initiator; and component (C): a compound having a polymerizable carbon-carbon unsaturated bond (excluding the component (A)). [ka] (In formula (1), Ar 1 and Ar 2 R is each independently an aromatic ring group. 1 and R 2 are each independently a monovalent substituent, or R 1 and R 2 and are combined together to form Ar 1 and Ar 2 The fused ring structure is a fused ring structure in which two aromatic rings are bonded together with a single bond, -O-, -S-, -NR 8 -, methylene group or ethylene group. 8 R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 3 and R 4 are each independently a monovalent substituent. 1 and X 2 are each independently a group represented by the following formula (1x): m1 and m2 are each independently an integer of 0 to 6; k1 and k2 are each independently an integer of 0 to 4; n1 and n2 are each independently an integer of 1 to 6. In the formula, R 1 ~R 4 , X 1 , X 2 If there are multiple R 1 ~R 4 , X 1 , X 2 are the same or different.) [ka] (In formula (1x), R 5 R is an alkanediyl group having 2 to 4 carbon atoms. 6 is a hydrogen atom or a methyl group. p is an integer of 0 to 4. When p is 2 or more, multiple R 5 are the same or different.) [ka] (In formula (2), R 7is an organic group having a valence of r. r is an integer from 1 to 4.

[0014] [2] A method for producing a lens, comprising the steps of: applying the radiation-sensitive composition according to [1] above onto a substrate to form a coating film; irradiating a part of the coating film with radiation; developing the irradiated coating film to form a pattern on the substrate; and heating the pattern.

[0015] [3] A method for producing a lens, comprising the step of ink-jet coating the radiation-sensitive composition according to [1] above onto a substrate to form a pattern. [4] A display device comprising a lens formed using the radiation-sensitive composition according to [1] above. [5] A display device comprising one or both of the display element according to [4] above and a planarization film formed using the radiation-sensitive composition according to [1] above. [6] A solid-state imaging device comprising a lens formed using the radiation-sensitive composition according to [1] above. [7] An imaging device comprising the solid-state imaging element according to [6] above. [8] A compound which is a reaction product of a compound represented by the above formula (1) and a compound represented by the above formula (2). Effect of the Invention

[0016] According to the present invention, by preparing a radiation-sensitive composition containing the above-mentioned components (A), (B) and (C), it is possible to obtain a cured product that has good patterning properties, can be melted by heating at a low temperature (for example, 100° C. or lower), and has high reliability and a high refractive index. Such a radiation-sensitive composition of the present invention is particularly suitable for use in manufacturing lenses or forming planarizing films. [Brief description of the drawings]

[0017] [Figure 1] Enlarged views of the lens pattern, (a) shows the state before post-baking, and (b) shows the state after post-baking. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Matters related to the embodiments will be described in detail below. In this specification, a numerical range described using "~" means that the numerical range includes the numerical range before and after "~" as the lower limit and upper limit. Each component may be used alone or in combination of two or more types, unless otherwise specified.

[0019] Here, in this specification, the term "hydrocarbon group" includes chain-shaped hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain-shaped hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that do not include a cyclic structure and are composed only of a chain structure. However, they may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, it is not necessary to be composed only of an alicyclic hydrocarbon structure, and it also includes those that have a chain structure as a part of it. The term "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and it may contain a chain structure or an alicyclic hydrocarbon structure as a part of it. In addition, the aromatic ring structure of the aromatic hydrocarbon group may be a single ring or a condensed ring. The ring structures of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent composed of a hydrocarbon structure.

[0020] "(Meth)acrylic" means "acrylic" and "methacrylic". "(Meth)acryloyl group" means "acryloyl group" and "methacryloyl group". "Alkali-soluble" means that it is soluble or swellable in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C.

[0021] ≪Radiation-sensitive composition≫ The radiation-sensitive composition of the present disclosure (hereinafter also simply referred to as "the composition") contains the following components (A), (B), and (C). Component (A): A reaction product of a compound represented by the following formula (1) and a compound represented by the following formula (2) (hereinafter also referred to as "compound (A)") Component (B): Photopolymerization initiator Component (C): A compound having a polymerizable carbon-carbon unsaturated bond (excluding component (A)).

[0022] [ka] (In formula (1), Ar 1 and Ar 2 R is each independently an aromatic ring group. 1 and R 2 are each independently a monovalent substituent, or R 1 and R 2 and are combined together to form Ar 1 and Ar 2 The fused ring structure is a fused ring structure in which two aromatic rings are bonded together with a single bond, -O-, -S-, -NR 8 -, methylene group or ethylene group. 8 R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 3 and R 4 are each independently a monovalent substituent. 1 and X 2 are each independently a group represented by the following formula (1x): m1 and m2 are each independently an integer of 0 to 6; k1 and k2 are each independently an integer of 0 to 4; n1 and n2 are each independently an integer of 1 to 6. In the formula, R 1 ~R 4 , X 1 , X 2 If there are multiple R 1 ~R 4 , X 1 , X 2 are the same or different.)

[0023] [ka] (In formula (1x), R 5R is an alkanediyl group having 2 to 4 carbon atoms. 6 is a hydrogen atom or a methyl group. p is an integer of 0 to 4. When p is 2 or more, multiple R 5 are the same or different.) [ka] (In formula (2), R 7 is an organic group having a valence of r. r is an integer from 1 to 4.

[0024] <(A) Component: Compound (A)> Compound (A) is a compound obtained by the reaction of a hydroxyl group of a compound represented by the above formula (1) (hereinafter also referred to as "compound (M)") with an isocyanate group of a compound represented by the above formula (2) (hereinafter also referred to as "compound (N)"). By the reaction of the hydroxyl group in the above formula (1) with the isocyanate group in the above formula (2), compound (A) has a sulfonamide structure (-S(=O)2-NH-) together with a fluorene skeleton and a (meth)acryloyl group. Compound (A) having these structures has a high refractive index, and also has good alkali solubility and photopolymerizability (particularly photoradical polymerizability). Furthermore, compound (A) has a lower molecular weight than the polymer component blended as a base resin in a radiation-sensitive composition used for forming a high refractive index material such as a microlens or a flattening film. By using such compound (A) as one 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 melted by heating at a low temperature (for example, 100°C or less). In addition, by including compound (A), a cured product with a high refractive index can be obtained. Furthermore, compound (A) is unlikely to generate decomposition products, and is therefore suitable as a material for obtaining a highly reliable cured product.

[0025] ·Compound (M) The compound (M) is, for example, a (meth)acrylic acid adduct of an epoxy group-containing compound having a fluorene skeleton. 1The aromatic ring group represented by the formula (1) is a group in which (m1+n1+1) hydrogen atoms have been removed from an aromatic ring. 2 The aromatic ring group represented by the formula (1) is a group in which (m2+n2+1) hydrogen atoms have been removed from an aromatic ring. 1 and Ar 2 The aromatic ring contained in Ar may be a single ring or a condensed ring. 1 and Ar 2 The aromatic ring contained in is preferably an aromatic hydrocarbon ring, such as a benzene ring, a naphthalene ring, an indene ring, an anthracene ring, or a phenanthrene ring. 1 and Ar 2 The aromatic ring contained in is preferably a benzene ring or a naphthalene ring.

[0026] R 1 and R 2 When R is a monovalent substituent, examples of the monovalent substituent include a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), 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 cycloalkoxy group having 3 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an aralkyloxy group having 6 to 12 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkylthio group having 3 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms, an aralkylthio group having 6 to 12 carbon atoms, a cyano group, a nitro group, and a dialkylamino group. 1 and R 2 The monovalent substituent represented by the following formula is preferably 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 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.

[0027] R 1 and R 2 But, when combined with each other, Ar 1 and Ar 2 When the fused ring structure is formed with Ar1 Aromatic rings and Ar in 2 The aromatic ring in the middle is a single bond, -O-, -S-, -NR 8 -, methylene group or ethylene group. 1 and R 2 Examples of the fused ring structure formed by combining these rings include a fluorene ring, a tetrahydroanthracene ring, a xanthene ring, a thioxanthene ring, etc. Of these, a xanthene ring is preferred.

[0028] From the viewpoint of increasing the refractive index of the cured product, the compound (M) is preferably Ar 1 and Ar 2 has a condensed polycyclic aromatic hydrocarbon ring, or R 1 and R 2 and are combined together to form Ar 1 and Ar 2 From the viewpoints of increasing the refractive index of the cured product and of easy availability of materials, the compound (M) is preferably a compound having a condensed ring structure constituted by Ar 1 and Ar 2 Compounds having a condensed polycyclic aromatic hydrocarbon ring can be particularly preferably used.

[0029] m1 and m2 are Ar 1 and Ar 2 m1 and m2 are preferably 0 to 3, more preferably 0 or 1, and further preferably 0.

[0030] R 3 and R 4Examples of the monovalent substituent represented by the formula (I) include a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), 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 cycloalkoxy group having 3 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an aralkyloxy group having 6 to 12 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkylthio group having 3 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms, an aralkylthio group having 6 to 12 carbon atoms, a cyano group, and an acyl group. 3 and R 4 The monovalent substituent represented by the following formula is preferably 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 an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0031] k1 and k2 are preferably 0 to 2, more preferably 0 or 1, and further preferably 0.

[0032] X 1 and X 2 is a group represented by the above formula (1x). In formula (1x), R 5 The alkanediyl group having 2 to 4 carbon atoms represented by the formula (I) may be linear or branched. 5 Of these, R is preferably a linear or branched alkanediyl group having 2 or 3 carbon atoms. p is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0. 6 is preferably a hydrogen atom.

[0033] Specific examples of the compound (M) include compounds represented by the following formulas (M-1) to (M-6). [ka] (In formulas (M-1) to (M-6), Z 1 ~Z 4 are each independently a group represented by the above formula (1x).

[0034] ·Compound (N) In the above formula (2), R 7 The r-valent organic group represented by the formula (1) may have a chain structure, a cyclic structure, or a combination of a chain structure and a cyclic structure. 7 Specific examples of the above include an r-valent hydrocarbon group; an r-valent group containing -O-, -S-, -NR- (R is a monovalent hydrocarbon group) or the like between the carbon-carbon bonds of the hydrocarbon group; an r-valent group in which any hydrogen atom in the hydrocarbon group is replaced by a monovalent heteroatom-containing group (e.g., a halo group, a cyano group, a nitro group, a carboxy group, a dialkylamino group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an alkylthioalkyl group, a cycloalkylthioalkyl group, an arylthioalkyl group, an aralkylthioalkyl group, etc.); and a group in which two hydrogen atoms bonded to the same carbon in a hydrocarbon group are removed to form "=P(R 9 A group represented by "(three R 9 are each independently a monovalent hydrocarbon group); an r-valent group having a heterocyclic structure; and the like.

[0035] R 7Examples of the hydrocarbon group constituting the above include a group obtained by removing r hydrogen atoms from an alkane having 1 to 10 carbon atoms, a group obtained by removing r hydrogen atoms from an alkene having 2 to 10 carbon atoms, an r-valent saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an r-valent aromatic hydrocarbon group having 6 to 20 carbon atoms. The alkane having 1 to 10 carbon atoms and the alkene having 2 to 10 carbon atoms may be linear or branched. Examples of the r-valent saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms include a group obtained by removing r hydrogen atoms from a saturated alicyclic hydrocarbon such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, bicyclo[2.2.2]octane, and adamantane; and an unsaturated alicyclic hydrocarbon such as cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, indane, and benzocyclohexane. Examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms and a valence of r include groups in which r hydrogen atoms have been removed from an aromatic ring such as benzene, naphthalene, anthracene, indene, and fluorene.

[0036] R 7 When is a r-valent group having a heterocyclic structure, the heterocyclic structure may be a nitrogen-containing heterocyclic structure, a sulfur-containing heterocyclic structure, or an oxygen-containing heterocyclic structure. Specific examples of these heterocyclic structures include a pyridine ring structure, a pyrimidine ring structure, a pyridazine ring structure, a pyrazine ring structure, an imidazole ring structure, a thiazole ring structure, and a 1,3,4-thiadiazole ring structure as a nitrogen-containing heterocyclic structure; a furan ring structure, a benzodioxane ring structure, and the like as an oxygen-containing heterocyclic structure; and a thiophene ring structure, a 2,3-dihydro-1-benzothiophene structure, a 2,3-dihydro-1,4-dithiin ring structure, a thiazole ring structure, and a thiadiazole ring structure as a sulfur-containing heterocyclic structure. These heterocyclic structures may have a substituent. Examples of the substituent include a monovalent hydrocarbon group, a halogen atom, a cyano group, a nitro group, a dialkylamino group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, and an aralkylthio group.

[0037] From the viewpoint of achieving a high refractive index of the cured product obtained by using the compound (A) and realizing melting at a low temperature, R 7 is preferably a group having a monocyclic aromatic hydrocarbon ring, a condensed polycyclic aromatic hydrocarbon ring, or an aliphatic hydrocarbon ring, or a group having one or more heteroatoms selected from the group consisting of a sulfur atom, a nitrogen atom, and a phosphorus atom. Here, examples of the aliphatic hydrocarbon ring include the saturated alicyclic hydrocarbons and unsaturated alicyclic hydrocarbons exemplified in the description of the r-valent saturated or unsaturated alicyclic hydrocarbon group. From the viewpoint of increasing the refractive index of the cured product, R 7 is particularly preferably a group having a monocyclic aromatic hydrocarbon ring or a condensed polycyclic aromatic hydrocarbon ring, or a group having one or more heteroatoms selected from the group consisting of a sulfur atom, a nitrogen atom, and a phosphorus atom.

[0038] From the viewpoint of increasing the refractive index of the cured product, a compound represented by the following formula (2-1) can be preferably used as the compound (N). [ka] (In formula (2-1), R 7A is an r-valent group having a monocyclic aromatic hydrocarbon ring, a condensed polycyclic aromatic hydrocarbon ring, a monocyclic heterocycle, or a condensed polycyclic heterocycle. r is an integer from 1 to 4. However, in the formula, r "-S(=O)2-NCO"s are bonded to the monocyclic aromatic hydrocarbon ring, the condensed polycyclic aromatic hydrocarbon ring, the monocyclic heterocycle, or the condensed polycyclic heterocycle.

[0039] R 7A Examples of the monocyclic aromatic hydrocarbon ring contained in R include a benzene ring, and examples of the condensed polycyclic aromatic hydrocarbon ring contained in R include a naphthalene ring, an anthracene ring, and a phenanthrene ring. Of these, a benzene ring or a naphthalene ring is preferable. Specific examples of the monocyclic heterocycle and the condensed polycyclic heterocycle include R 7 When is an r-valent group having a heterocyclic structure, specific examples thereof include the same heterocycles as those in the heterocyclic structures exemplified above.

[0040] R7A The monocyclic aromatic hydrocarbon ring, condensed polycyclic aromatic hydrocarbon ring, monocyclic heterocycle or condensed polycyclic heterocycle may have one or more substituents. In addition, two or more substituents of the monocyclic aromatic hydrocarbon ring, condensed polycyclic aromatic hydrocarbon ring, monocyclic heterocycle or condensed polycyclic heterocycle may be combined with each other to form a condensed ring structure together with the monocyclic aromatic hydrocarbon ring, condensed polycyclic aromatic hydrocarbon ring, monocyclic heterocycle or condensed polycyclic heterocycle. Specific examples of the substituent include the same groups as the specific examples of the monovalent heteroatom-containing group described above.

[0041] Specific examples of the compound (N) include compounds represented by the following formulas (N-1) to (N-31): In the following formula (N-25), q is an integer of 1 to 6. [ka]

[0042] The reaction between compound (M) and compound (N) can be preferably carried out in a solvent. The amount of compound (N) used is, for example, 0.2 to 2.0 moles, and preferably 0.5 to 1.0 moles, relative to 1 mole of the hydroxy group of compound (M). Examples of the solvent include esters, ethers, amides, ketones, hydrocarbons, and halogens. The reaction temperature is, for example, -20 to 50°C, and preferably 0 to 30°C. The reaction time is, for example, 0.2 to 36 hours.

[0043] In the above reaction, the hydroxyl group of compound (M) reacts with the isocyanate group of compound (N) to form a urethane bond, thereby obtaining a compound having a fluorene skeleton, a sulfonamide structure, and a polymerizable carbon-carbon unsaturated bond (i.e., compound (A)). Compound (A) exhibits good alkali solubility due to the presence of a sulfonamide structure. In other words, the reaction between compound (M) and compound (N) can impart alkali developability to compound (M). In addition, compound (A) is useful as a component for forming a high refractive index material that is applied to various display elements such as organic electroluminescence elements and liquid crystal display elements, solid-state imaging elements, etc., in that it is unlikely to generate decomposition products.

[0044] Compound (A) may be a relatively low molecular weight compound produced by using a monofunctional compound (N), or an oligomer produced by using a polyfunctional compound (N). For example, when synthesizing compound (A), a compound represented by the following formula (A1) can be obtained as compound (A) by using a monofunctional compound in which r in the above formula (2) is 1 as compound (N). In addition, R in the following formula (1y) 7 represents a partial structure of the compound (N) (i.e., R 7 ) [ka] (In formula (A1), Ar 1 , Ar 2 , R 1 ~R 4 , m1, m2, k1, k2, n1 and n2 are the same as those in formula (1). 3 and X 4 are each independently a group represented by the following formula (1y): [ka] (In formula (1y), Y 1 is a hydrogen atom or "-C(=O)-NH-SO2-R 7 " is a group represented by the formula (A1) . 1At least one of the groups is "-C(=O)-NH-SO2-R 7 " R 5 , R 6 and p are the same as those in formula (1x), R 7 is the same as the above formula (2).

[0045] In addition, when compound (A) is synthesized, an oligomer having compound (M) and compound (N) as monomers can be obtained by using a polyfunctional compound in which r in the above formula (2) is 2 or more as compound (N). From the viewpoint of increasing the refractive index of the cured product obtained by using compound (A) and from the viewpoint of obtaining a cured product having a good pattern shape, a compound represented by the above formula (A1) can be preferably used as compound (A).

[0046] The molecular weight of compound (A) is preferably 600 or more. A molecular weight of 600 or more is preferable in that an organic film exhibiting good alkali developability can be formed, and a cured product having sufficiently high heat resistance and chemical resistance can be obtained. The molecular weight of compound (A) is more preferably 700 or more, and even more preferably 750 or more. From the viewpoint of melting by low-temperature heating and suppressing the viscosity of the composition from becoming too high, the molecular weight of compound (A) is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,200 or less. When compound (A) is an oligomer, the molecular weight of compound (A) is the weight average molecular weight (Mw) calculated in terms of polystyrene by gel permeation chromatography (GPC).

[0047] In the present composition, the content of compound (A) is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, based on 100 parts by mass of the solid content (i.e., components other than the solvent in the radiation-sensitive composition) contained in the present composition. The content of compound (A) is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, based on 100 parts by mass of the solid content contained in the present composition. When the content of compound (A) is within the above range, a cured product with a high refractive index can be obtained, and the cured product can be melted at a relatively low temperature (e.g., 100°C or less) during lens production, and a microlens with a good lens shape can be obtained.

[0048] In this specification, the term "solid content" refers to components other than the solvent that are optionally blended into the radiation-sensitive composition. In other words, the term "solid content contained in the present composition" refers to the components obtained by adding components other than (A) to (C) and other than the solvent to the compound (A), photopolymerization initiator, and compound (C). Therefore, even if an additive component is in a liquid state (e.g., a surfactant, etc.), the additive component is considered to be included in the solid content.

[0049] <Component (B): Photopolymerization initiator> The photopolymerization initiator is preferably a photoradical polymerization initiator that generates radicals in response to radiation and initiates polymerization. The photopolymerization initiator used is not particularly limited. Examples of the photopolymerization initiator include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and acylphosphine oxide compounds.

[0050] Examples of the O-acyloxime compound include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1-(9-ethyl-6-benzoyl-9H-carbazol-3-yl)-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, ethanone- 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime), and the like.

[0051] Examples of the acetophenone compound include α-aminoketone compounds and α-hydroxyketone compounds. Specific examples of these include α-aminoketone compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenylketone.

[0052] 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.

[0053] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and the like.

[0054] The content of the photopolymerization initiator in the present composition is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the total amount of the polymerizable compounds (compound (A) and compound (C)) contained in the present composition. The content of the photopolymerization initiator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less, based on 100 parts by mass of the total amount of the polymerizable compounds contained in the present composition. By setting the content of the photopolymerization initiator within the above range, a radiation-sensitive composition exhibiting good curability and transparency can be obtained.

[0055] <Component (C): Compound having a polymerizable carbon-carbon unsaturated bond> The compound having a polymerizable carbon-carbon unsaturated bond, which is component (C) (hereinafter also referred to as "compound (C)"), is a component copolymerizable with compound (A) and is a compound capable of forming a polymer together with compound (A) upon irradiation with radiation. Note that compound (C) is a compound different from compound (A). Compound (C) is preferably a compound not having a fluorene skeleton.

[0056] Here, while compound (A) exhibits a high refractive index, there is a concern that if compound (A) alone is used as a polymerizable compound to melt the pattern by heating to form an appropriate lens shape, a high-temperature process of, for example, 120°C or higher is required. In addition, if compound (A) alone is used as a polymerizable compound, a high exposure dose is required to obtain sufficient curability. In contrast, by using compound (A) and compound (C) in combination, the pattern can be melted by a low-temperature process at, for example, 100°C or less, and an appropriate lens shape can be obtained. In addition, the curing speed is improved, and curing by a relatively low exposure dose is possible.

[0057] From the viewpoint of lowering the temperature during melting by heating as much as possible, the molecular weight of the compound (C) is preferably smaller than that of the compound (A). Specifically, the molecular weight of the compound (C) is preferably less than 600, more preferably 550 or less, even more preferably 500 or less, and particularly preferably 450 or less. In addition, from the viewpoint of obtaining a cured product having a high refractive index and excellent reliability in terms of solvent resistance and low volatility, the molecular weight of the compound (C) is preferably 100 or more.

[0058] Examples of the compound (C) include a (meth)acryloyl group-containing compound, a chain vinyl compound, an aromatic vinyl compound, a maleimide compound, etc. These compounds are preferably used because they have good copolymerizability with the compound (A) and relatively high plasticity.

[0059] Compound (C) may be either a monofunctional compound or a polyfunctional compound. In addition, a monofunctional compound and a polyfunctional compound may be used in combination as compound (C). Specific examples of compound (C) that is a monofunctional compound include (meth)acrylic acid esters having a chain structure, (meth)acrylic acid esters having an alicyclic structure, (meth)acrylic acid esters having an aromatic ring structure, (meth)acrylamide compounds, chain vinyl compounds, aromatic vinyl compounds, maleimide compounds, and the like. When compound (C) is a monofunctional compound, a (meth)acryloyl group-containing compound can be preferably used as compound (C), and a (meth)acrylic acid ester compound that is at least one selected from the group consisting of (meth)acrylic acid esters having a chain structure, (meth)acrylic acid esters having an alicyclic structure, and (meth)acrylic acid esters having an aromatic ring structure can be more preferably used.

[0060] Specific examples of the above compounds include (meth)acrylic acid esters having a chain structure, such as (meth)acrylic acid alkyl esters, (meth)acrylic acid hydroxyalkyl esters, (meth)acrylic acid alkoxyalkyl esters, and (meth)acrylic acid polyoxyalkylene esters. Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate. Examples of (meth)acrylic acid hydroxyalkyl esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples of (meth)acrylic acid alkoxyalkyl esters include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and propoxyethyl (meth)acrylate. Examples of (meth)acrylic acid polyoxyalkylene esters include methoxydiethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, ethoxydipropylene glycol (meth)acrylate, and 2-ethylhexyloxydiethylene glycol (meth)acrylate.

[0061] Examples of (meth)acrylic acid esters having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, 4-hydroxymethylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate, and the like. 2,6 ]decan-8-yl, (meth)acrylic acid tricyclo[5.2.1.0 2,5]decan-8-yloxyethyl, isobornyl (meth)acrylate, etc. Examples of (meth)acrylic acid esters having an aromatic ring structure include phenyl (meth)acrylate, benzyl (meth)acrylate, naphthylmethyl (meth)acrylate, naphthylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, m-phenoxyphenylmethyl (meth)acrylate, p-phenoxyphenylmethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, polyethyleneoxynonylphenyl (meth)acrylate, (1-naphthyl)methyl (meth)acrylate, (2-naphthyl)methyl (meth)acrylate, (1,1'-biphenyl-4-yl)methyl (meth)acrylate, etc.

[0062] Examples of (meth)acrylamide compounds include (meth)acryloylmorpholine, N-(2-hydroxyethyl)(meth)acrylamide, N-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactam. Examples of chain vinyl compounds include propene, butene, pentene, and hexene. Examples of aromatic vinyl compounds include styrene, methylstyrene, α-methylstyrene, t-butoxystyrene, and vinylnaphthalene. Examples of maleimide compounds include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-(p-methylphenyl)maleimide.

[0063] Specific examples of compounds (C) that are polyfunctional compounds include polyfunctional (meth)acrylic acid esters, aromatic vinyl compounds, and chain vinyl compounds. Examples of polyfunctional (meth)acrylic acid esters include bifunctional (meth)acrylic acid esters and trifunctional or higher (meth)acrylic acid esters. Specific examples of these include bifunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate.

[0064] Examples of the trifunctional or higher (meth)acrylic acid ester include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, tri(2-(meth)acryloyloxyethyl)phosphate, succinic acid-modified pentaerythritol tri(meth)acrylate, and the like. Examples of the compound include (meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, and carboxy group-containing polybasic acid-modified (meth)acrylic oligomer, as well as polyfunctional urethane acrylate compounds obtained by reacting a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups with a compound having one or more hydroxyl groups in the molecule and having three, four or five (meth)acryloyloxy groups.

[0065] Examples of the polyfunctional aromatic vinyl compound include 1,3-divinylbenzene, 1,4-divinylbenzene, etc. Examples of the polyfunctional chain vinyl compound include 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, etc.

[0066] Preferred specific examples of the compound (C) include the compounds represented by the following formulas (C1-1) to (C1-47). [ka] [ka]

[0067] [ka] (In formulas (C1-1) to (C1-47), R 20 is a hydrogen atom or a methyl group. 20 If there are multiple R 20 are the same or different. m and n are each independently an integer of 0 to 3. x, y and z are each independently an integer of 0 to 3, provided that 1≦x+y+z≦3 is satisfied.

[0068] The content of the compound (C) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more, based on 100 parts by mass of the total amount of the fluorene skeleton-containing compounds contained in the composition (specifically, the total amount of the compound (A) and the compound (α) shown below), from the viewpoint of obtaining a cured product with high heat resistance while enabling the formation of an appropriate lens shape by heating at a low temperature. Also, from the viewpoint of suppressing a decrease in the refractive index of the obtained cured product, the content of the compound (C) is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass of the total amount of the fluorene skeleton-containing compounds contained in the composition.

[0069] From the viewpoint of obtaining a cured product having high heat resistance and enabling the formation of an appropriate lens shape by heating at a low temperature, the content of compound (C) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more, relative to 100 parts by mass of the total amount of compound (A) contained in the composition. From the viewpoint of suppressing a decrease in the refractive index of the obtained cured product, the content of compound (C) is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, relative to 100 parts by mass of the total amount of compound (A) contained in the composition.

[0070] From the viewpoint of obtaining a radiation-sensitive composition having more excellent patterning properties, the compound (C) preferably contains a compound having three or more polymerizable carbon-carbon unsaturated bonds in one molecule (hereinafter also referred to as "compound (C2)"). Specifically, the compound (C) is preferably compound (C2) or a mixture of a compound having one or two polymerizable carbon-carbon unsaturated bonds in one molecule (hereinafter also referred to as "compound (C1)") and compound (C2).

[0071] The content of compound (C2) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total amount (100% by mass) of compound (C) contained in the composition, from the viewpoint of improving the patterning properties of the radiation-sensitive composition. Also, the content of compound (C2) is preferably 95% by mass or less, more preferably 90% by mass or less, based on the total amount of compound (C) contained in the composition, from the viewpoint of obtaining a cured product having an appropriate lens shape by melting by heating at a low temperature.

[0072] <Other ingredients> In addition to the above-mentioned compound (A), photopolymerization initiator, and compound (C), the present composition may further contain other components (hereinafter also referred to as "other components"). Examples of the other components include a compound having a fluorene skeleton and a molecular weight of 1,500 or less that is different from compound (A) (hereinafter also referred to as "compound (α)"), a polymer having a molecular weight of 2,000 to 100,000 (hereinafter also referred to as "polymer (D)"), a solvent, etc.

[0073] ·Compound (α) For the purpose of improving the performance such as the patterning property of the present composition, the present composition may further contain a compound (α) having a molecular weight of 1,500 or less as a fluorene skeleton-containing compound different from the compound (A). The molecular weight of the compound (α) is preferably 1,000 or less, more preferably 800 or less, and even more preferably 600 or less.

[0074] Specific examples of the compound (α) include the compound represented by the above formula (1) and the compound represented by the following formula (3). [ka] (In formula (3), Ar 11 and Ar 12 R is each independently an aromatic ring group. 11 and R 12 are each independently a monovalent substituent, or R 11 and R 12 and are combined together to form Ar 11 and Ar 12 The fused ring structure is a fused ring structure in which two aromatic rings are bonded together with a single bond, -O-, -S-, -NR 18 -, methylene group or ethylene group. 18 R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 13 and R 14 Each of m3 and m4 is independently an integer of 0 to 6. Each of k3 and k4 is independently an integer of 0 to 4. In the formula, R 11 ~R 14If there are multiple R 11 ~R 14 are the same or different.)

[0075] In the above formula (3), Ar 11 Or Ar 12 The aromatic ring group represented by the formula (1) is 1 Or Ar 2 The aromatic ring group represented by R 11 or R 12 The monovalent substituent represented by the formula: R 1 or R 2 In addition to the groups exemplified as the monovalent substituent represented by the formula (I), examples thereof include an alkali-soluble group, a primary amino group, a secondary amino group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group, an alkoxyalkylalkoxy group, a cycloalkyloxyalkyl group, a hydroxyalkyl group, a hydroxyalkoxy group, a dihydroalkyl group, a dihydroalkoxy group, a hydroxycycloalkyl group, and a hydroxycycloalkoxy group. Here, the term "alkali-soluble group" refers to a functional group that increases the solubility in an alkaline solution by interacting or reacting with an alkali. Examples of the alkali-soluble group include an acidic group, and specific examples thereof include a carboxy group, a phenolic hydroxyl group, a sulfonic acid group, and a phosphoric acid group.

[0076] R 13 or R 14 The monovalent substituent represented by the formula: R 3 or R 4 Examples of the monovalent substituent represented by the following formula include the same groups as those exemplified above. m3 and m4 each preferably represent an integer of 1 to 3, more preferably 1 or 2, and further preferably represent an integer of 1. k3 and k4 each are preferably 0 to 2, more preferably 0 or 1, and further preferably 0.

[0077] The compound (α) preferably has an alkali-soluble group in addition to a fluorene skeleton, and more preferably has a carboxy group or a phenolic hydroxyl group, in that this can improve the alkali developability of the composition while maintaining good reliability of the cured product.

[0078] Specific examples of compound (α) include the compounds represented by the above formulas (M-1) to (M-6) and the compounds represented by the following formulas (a1-1) to (a1-13). [ka]

[0079] When compound (α) is blended in the present composition, the content of compound (α) is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, relative to 100 parts by mass of the total amount of the fluorene skeleton-containing compounds (compound (A) and optional compound (α)) contained in the present composition. The content of compound (α) is preferably 60 parts by mass or less, and more preferably 55 parts by mass or less, relative to 100 parts by mass of the total amount of the fluorene skeleton-containing compounds contained in the present composition.

[0080] Component (D): Polymer (D) The composition may further contain, as an additive component, a polymer (D) having a molecular weight of 2,000 to 100,000. By blending the polymer (D) in the composition, the heat resistance of the resulting cured product can be improved, and a high refractive index material with excellent reliability can be obtained.

[0081] Examples of the polymer (D) include an alkali-soluble polymer, a fluorene skeleton-containing photosensitive polymer, a carboxy group-containing photosensitive polymer, etc. Examples of the alkali-soluble polymer include a (meth)acrylic acid / methyl (meth)acrylate copolymer, a (meth)acrylic acid / benzyl (meth)acrylate copolymer, a (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate copolymer, a (meth)acrylic acid / styrene / isoprene / tricyclodecanyl (meth)acrylate / 2-mono(hexahydroxyphthaloyloxy)ethyl (meth)acrylate copolymer, a methacrylic-modified acrylic resin, and an acid anhydride-modified acrylic resin.

[0082] Examples of the fluorene skeleton-containing photosensitive polymer include those described in International Publication No. 2009 / 119622. Examples of the carboxy group-containing photosensitive polymer include acid-modified epoxy acrylates such as bisphenol A type epoxy acrylate, bisphenol F type epoxy acrylate, cresol novolac type epoxy acrylate, and biphenyl type epoxy acrylate. Specific examples of the carboxy group-containing photosensitive polymer 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.).

[0083] When polymer (D) is blended in the composition, the content of polymer (D) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less, relative to 100 parts by mass of compound (A) contained in the composition. By setting the content of polymer (D) within the above range, it is possible to obtain an appropriate lens shape by heating at a low temperature, while obtaining an effect of improving heat resistance.

[0084] Component (E): Solvent The present composition is a liquid composition in which the compound (A), the photopolymerization initiator, the compound (C), and other components blended as necessary are preferably dissolved or dispersed in a solvent. The solvent is preferably an organic solvent that dissolves each component blended in the present composition and does not react with each component.

[0085] Specific examples of the solvent 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 diglycol monomethyl ether, ethylene diglycol ethyl methyl ether, dimethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Of these, the solvent preferably contains at least one selected from the group consisting of ethers, esters, and ketones.

[0086] Examples of other components include, in addition to the above, polymerization inhibitors, surfactants, antioxidants, sensitizers, softeners, plasticizers, adhesive assistants, ultraviolet absorbers, etc. The blending ratio of these components is appropriately selected according to each component within a range that does not impair the effects of the present disclosure.

[0087] For example, a surfactant can be used to improve the coating properties of the composition (wetting and spreading properties and reduction of coating unevenness). Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

[0088] Specific examples of surfactants include fluorine-based surfactants under the trade names below, such as Megafac F-171, F-172, F-173, F-251, F-430, F-554, and F-563 (manufactured by DIC Corporation); Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited); Asahiguard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106, and S-611 (manufactured by AGC Seimi Chemical Co., Ltd.); Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.); FTX-218 (manufactured by Neos Corporation); F-top EF301, EF303, and EF352 (manufactured by Shin-Akita Chemical Co., Ltd.).

[0089] Examples of silicone surfactants include, under the trade names below, SH200-100cs, SH-28PA, SH-30PA, SH-89PA, SH-190, SH-8400, FLUID, SH-193, SZ-6032, SF-8428, DC-57, DC-190, PAINTAD19, FZ-2101, FZ-77, FZ-2118, L-7001, and L-7002 (manufactured by Toray Dow Corning Silicone Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); and BYK-300, 306, 310, 330, 335, 341, 344, 370, 340, and 345 (manufactured by BYK Japan).

[0090] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate.

[0091] When a surfactant is blended in the present composition, the content of the surfactant is preferably 0.01 to 1.5 parts by mass, more preferably 0.02 to 1.2 parts by mass, and even more preferably 0.05 to 1.0 part by mass, relative to 100 parts by mass of the total amount of compound (A) contained in the present composition.

[0092] The adhesive aid is a component that improves the adhesion between the cured product formed using the present composition and the substrate, and suppresses peeling of the cured product during the development process. As the adhesive aid, a functional silane coupling agent having a reactive functional group can be preferably used. Examples of the reactive functional group of the functional silane coupling agent include a carboxy group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

[0093] Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0094] When the composition contains an adhesive aid, the content thereof is preferably from 0.01 to 4 parts by mass, and more preferably from 0.1 to 2 parts by mass, per 100 parts by mass of compound (A) contained in the composition.

[0095] The composition can be obtained by mixing the compound (A), the photopolymerization initiator, the compound (C), and other components that are optionally added in a predetermined ratio. The composition obtained by mixing the components may be filtered, for example, through a filter having a pore size of 0.5 μm or less.

[0096] The solid content concentration of the present composition (i.e., the ratio of the total mass of the components other than the solvent in the radiation-sensitive composition to the total mass of the radiation-sensitive composition) is appropriately selected in consideration of viscosity, volatility, etc. The solid content concentration of the present composition is preferably in the range of 1 to 60 mass %. A solid content concentration of 1 mass % or more is preferable in that a sufficient thickness of the coating film can be ensured when the present composition is applied onto a substrate. In addition, a solid content concentration of 60 mass % or less is preferable in that the thickness of the coating film does not become too large, and furthermore, the viscosity of the present composition can be appropriately increased, and good coatability can be ensured. The solid content concentration in the present composition is more preferably 2 to 50 mass %, and further preferably 5 to 40 mass %.

[0097] The content of the polymerizable compounds in the composition (i.e., the total amount of compound (A) and compound (C)) is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and even more preferably 85 parts by mass or more, relative to 100 parts by mass of the total amount of solids (components other than the solvent) contained in the composition, from the viewpoint of improving the sensitivity and achieving a good lens shape by low-temperature heating.

[0098] <Lens manufacturing method> The manufacturing method of the present disclosure is a method for manufacturing a minute light collector (hereinafter also referred to as a "microlens") provided in a solid-state imaging device (e.g., a CCD image sensor, a CMOS image sensor) or a display device (e.g., an organic EL device or a liquid crystal display device) using the radiation-sensitive composition of the present disclosure. The first lens manufacturing method of the present disclosure includes the following steps (I) to (IV). (I) A step of applying the radiation-sensitive composition onto a substrate to form a coating film. (II) A step of exposing a part of the coating film to radiation. (III) A step of developing the irradiated coating to form a pattern on the substrate. (IV) Heating the pattern

[0099] The second method of producing a lens according to the present disclosure includes a step of ink-jet coating a radiation-sensitive composition onto a substrate to form a pattern.

[0100] [First lens manufacturing method] The radiation-sensitive composition of the present disclosure described above is suitable as a negative pattern-forming material in which a part of an organic film formed from the radiation-sensitive composition is exposed to light, and the unexposed part of the exposed organic film is dissolved in an alkali developer to form a pattern (i.e., a cured product formed from the radiation-sensitive composition), which is then melted by heat treatment to form a lens shape. Hereinafter, each step (steps (I) to (IV)) in the first lens manufacturing method of the present disclosure will be described.

[0101] <Process (I): Coating process> Step (I) is a step of forming a coating film on a substrate by applying the composition onto the substrate. Examples of the substrate include glass substrates, silicon wafers, plastic substrates, plastic films, and substrates having colored resists, overcoats, anti-reflection films, various metal thin films, sealing films, etc. formed on the surfaces thereof. Examples of the plastic substrates and plastic films include resin substrates and films made of plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, and polyimide. These substrates may be provided in advance with various elements (for example, light receiving elements such as photodiodes, light emitting elements such as organic light emitting diodes).

[0102] The composition can be applied by any suitable method, such as spraying, roll coating, rotary coating (spin coating), slit die coating, bar coating, inkjet coating, etc. Of these, spin coating, bar coating, and slit die coating are preferred.

[0103] After the composition is applied onto a substrate, the composition may be preheated (prebaked) for the purpose of preventing dripping. The prebaking conditions can be appropriately set depending on the type and use ratio of each component. The prebaking conditions can be, for example, 60 to 130°C for about 30 seconds to 10 minutes. The thickness of the coating film formed after prebaking is preferably 0.1 to 20 μm, more preferably 0.2 to 15 μm.

[0104] <Process (II): Exposure process> Step (II) is a step of irradiating a part of the coating film formed in step (I) with radiation. This radiation irradiation causes a curing reaction in the exposed part, and a cured product is obtained in which the exposed part is cured. In step (II), the coating film is irradiated with radiation through a mask having a pattern (e.g., a dot pattern) for obtaining a microlens having a desired shape. The mask may be a multi-tone mask such as a halftone mask or a graytone mask.

[0105] Examples of the radiation to be irradiated to the coating film include ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, etc. Examples of ultraviolet rays include g-rays (wavelength 436 nm), i-rays (wavelength 365 nm), KrF excimer laser light (wavelength 248 nm), etc. Examples of X-rays include synchrotron radiation, etc. Examples of charged particle beams include electron beams, etc. Among these, the radiation to be irradiated to the coating film is preferably ultraviolet rays, and more preferably ultraviolet rays with a wavelength of 200 nm or more and 380 nm or less. Examples of the light source to be used include low pressure mercury lamps, high pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, LED lamps, etc. The radiation exposure is 500 J / m 2 ~50,000J / m 2 (50~500mJ / cm 2 ) is preferred.

[0106] <Step (III): Development step> Step (III) is a step of forming a pattern on the substrate by developing the coating film irradiated with radiation in step (II). This development step removes the unexposed parts of the coating film formed on the substrate, and a pattern (more specifically, a concave-convex pattern formed by a large number of regularly arranged micro-cured products) in which the exposed parts remain can be formed on the substrate. The micro-cured products have, for example, a substantially rectangular cross section.

[0107] The developer may be an aqueous solution of an alkali (basic compound). Examples of the aqueous solution of an alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonane, etc. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution of an alkali, or adding a small amount of various organic solvents capable of dissolving the present composition, may be used as the developer.

[0108] As the developing method, for example, a suitable method such as a puddle method, a dipping method, a swing immersion method, a shower method, etc. can be adopted. The developing time may be appropriately adjusted depending on the composition of the present composition. The developing time is, for example, 20 seconds to 120 seconds.

[0109] <Process (IV): Heating process> Step (IV) is a step of heating the developed pattern. In the first lens manufacturing method, the developed pattern is heated in step (IV) to form the micro-cured material on the substrate into a lens shape. In addition, the composition may be further cured while melting the micro-cured material having a substantially rectangular cross section by the heat treatment in step (IV). This makes it possible to obtain a microlens array in which hemispherical micro-cured materials are regularly arranged on the substrate. The heat treatment can be performed using a heating device such as an oven or a hot plate.

[0110] The heating temperature in step (IV) is preferably 100° C. or lower, more preferably 95° C. or lower, and even more preferably 90° C. or lower, from the viewpoint of being applicable to high refractive index materials for organic EL devices. Moreover, from the viewpoint of obtaining microlenses having high heat resistance and chemical resistance and good shape, the heating temperature in step (IV) is preferably 60° C. or higher, and more preferably 70° C. or higher. The heating time can be appropriately set depending on the type of heating device, etc. For example, when heating is performed using a hot plate, the heating time is, for example, 5 to 60 minutes. Moreover, when heating is performed using an oven, the heating time is, for example, 10 to 90 minutes. In step (IV), a step bake method in which heating is performed multiple times can also be used.

[0111] The production method of the present disclosure may further include the following step (V) as an optional step. (V) A step of irradiating the lens obtained by the above step (IV) with radiation (hereinafter also referred to as the "post-exposure step").

[0112] <Step (V): Post-exposure step> Step (V) is a step of further irradiating at least a part of the coating film after development with radiation. By irradiating with radiation in step (V) (hereinafter also referred to as "post-exposure"), it is possible to further improve heat resistance, chemical resistance, etc., and obtain a highly reliable cured product. Specific examples of post-exposure include (1) a method of irradiating radiation to the coating film after the development step and before the heating step (i.e., the pattern before melting), and (2) a method of irradiating radiation to the coating film after the heating step (i.e., the pattern after melting). Of these, from the viewpoint of suitably realizing melting at low temperature, the method (2), that is, irradiating radiation to the lens formed by heating the pattern, is preferred. The type of radiation and exposure conditions in post-exposure can be the same as those in step (II). Note that the conditions such as the wavelength and dose of irradiation light and the light source in post-exposure may be the same as or different from those in step (II).

[0113] The microlenses thus obtained have a good lens shape. The diameter of the microlenses is, for example, 1 μm or more and 100 μm or less. In addition, the microlenses obtained from the present composition have excellent heat resistance and chemical resistance, and also have high transparency and refractive index. Therefore, the microlenses of the present disclosure can be suitably used as microlenses for solid-state imaging elements provided in imaging devices such as cameras, and microlenses for various display elements such as organic EL elements and liquid crystal display elements. In particular, the present composition can form a lens shape even when heating for melting is performed at a low temperature of 100° C. or less. Therefore, it is particularly suitable for microlenses for the production of organic EL elements, which require the application of low-temperature processes.

[0114] [Second lens manufacturing method] The method for producing the second lens includes a step of ink-jet-coating a radiation-sensitive composition on a substrate to form a pattern. In the method for producing the second lens, a pattern having a spherical lens shape may be formed directly on the substrate by ink-jet coating. Alternatively, a pattern may be formed on the substrate by ink-jet coating, and then the pattern may be heated and melted to form a lens shape in the same manner as in the method for producing the first lens. Specifically, the latter method includes a step of forming a pattern by ink-jet coating instead of the steps (I), (II), and (III) in the method for producing the first lens, and the pattern formed by this step is made hemispherical by applying the step (IV) in the method for producing the first lens to the pattern, thereby producing a lens. That is, the method for producing the second lens may include a step of ink-jet-coating a radiation-sensitive composition on a substrate to form a pattern, and a step of heating the pattern formed by ink-jet coating to form a lens.

[0115] <Radiation-sensitive composition for forming planarizing film and method for producing planarizing film> The radiation-sensitive composition for forming a flattening film of the present disclosure is a curable composition containing the above-mentioned components (A), (B), and (C). As described above, the cured product formed by the curable composition has a high refractive index and is highly reliable. Furthermore, by heating the developed pattern at a low temperature, the composition melts sufficiently, and a cured film with excellent surface flatness can be obtained. Therefore, the radiation-sensitive composition of the present disclosure is suitable as a material for forming a flattening film provided on an organic EL device or a liquid crystal display device. The above explanation applies to the types and contents of the components (A), (B), and (C) and each component that is optionally blended, contained in the radiation-sensitive composition for forming a flattening film of the present disclosure. The flattening film can be produced by a method including steps (I) to (IV) in the same manner as the above-mentioned method for producing the first lens. The method may further include the above-mentioned step (V). The flattening film can also be produced by a method similar to the above-mentioned method for producing the second lens.

[0116] The radiation-sensitive composition of the present disclosure described above was applied onto a substrate and pre-heated (pre-baked) at 85° C. for 2 minutes to obtain a coating film having a thickness of 5.0 μm. This coating film was then exposed to an i-line equivalent of 200 mJ / cm 2 A cured product having a refractive index of 1.59 or more can be obtained by heating (post-baking) at 100° C. for 40 minutes after irradiation. According to the radiation-sensitive composition of the present disclosure, a cured film having a high refractive index, preferably 1.61 or more, more preferably 1.64 or more, can be obtained under the above conditions.

[0117] According to the present disclosure described above, the following means are provided.

[0118] [Means 1] A radiation-sensitive composition comprising: component (A): a reaction product of a compound represented by the above formula (1) and a compound represented by the above formula (2); component (B): a photopolymerization initiator; and component (C): a compound having a polymerizable carbon-carbon unsaturated bond (excluding the above component (A)). [Means 2] R in the above formula (2) 7 is a group having a monocyclic aromatic hydrocarbon ring, a condensed polycyclic aromatic hydrocarbon ring or an aliphatic hydrocarbon ring, or is a group having one or more hetero atoms selected from the group consisting of a sulfur atom, a nitrogen atom and a phosphorus atom. [Means 3] The radiation-sensitive composition according to [Means 1] or [Means 2], wherein the component (C) is a compound (C2) having three or more polymerizable carbon-carbon unsaturated bonds in one molecule, or a combination of a compound (C1) having one or two polymerizable carbon-carbon unsaturated bonds in one molecule and the compound (C2). [Measure 4] The radiation-sensitive composition according to any one of [Measure 1] to [Measure 3], wherein the component (C) is a compound having a molecular weight of less than 600. [Means 5] The component (A) is represented by the formula (1) Ar 1 and Ar 2 has a condensed polycyclic aromatic hydrocarbon ring, or R 1 and R 2 and are combined together to form Ar 1 and Ar 2The radiation-sensitive composition according to any one of [Measures 1] to [Measures 4], which has a condensed ring structure constituted by the above. [Measure 6] The component (A) is represented by the above formula (A1), and is the radiation-sensitive composition according to any one of measures 1 to 5. [Measures 7] The radiation-sensitive composition according to any one of [Measures 1] to [Measures 6], further comprising a compound having a fluorene skeleton and a molecular weight of 1,500 or less (excluding the component (A)). [Means 8] The radiation-sensitive composition according to any of [Means 1] to [Means 7], comprising, as an optional component, a compound having a fluorene skeleton and a molecular weight of 1,500 or less (excluding the component (A)), in which the content of the component (C) is 5 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the total of the component (A) and the compound having a fluorene skeleton and a molecular weight of 1,500 or less. [Measures 9] The radiation-sensitive composition according to any one of [Measures 1] to [Measures 8], further comprising a component (D): a polymer having a molecular weight of 2,000 or more and 100,000 or less (excluding the component (A)). [Measure 10] The radiation-sensitive composition according to [Measure 9], wherein the content of the component (D) is 50 parts by mass or less per 100 parts by mass of the component (A). [Means 11] The radiation-sensitive composition according to any one of [Means 1] to [Means 10], which is used for producing lenses. [Measure 12] The radiation-sensitive composition according to any one of [Measure 1] to [Measure 10], which is for forming a flattening film. [Means 13] A method for producing a lens, comprising the steps of: applying the radiation-sensitive composition according to any one of [Means 1] to [Means 10] onto a substrate to form a coating film; irradiating a part of the coating film with radiation; developing the irradiated coating film to form a pattern on the substrate; and heating the pattern. [Means 14] The method for manufacturing a lens according to [Means 13], wherein the temperature to which the pattern is heated is 100°C or lower. [Measure 15] A method for producing a lens, comprising a step of applying the radiation-sensitive composition according to any one of measures 1 to 10 onto a substrate by inkjet coating to form a pattern. [Measurement 16] A display device comprising a lens formed using the radiation-sensitive composition according to any one of measures 1 to 10. [Measure 17] A display device comprising one or both of the display element of [Measure 16] and a planarizing film formed using any one of the radiation-sensitive compositions of [Measure 1] to [Measure 10]. [Measurement 18] A solid-state imaging device comprising a lens formed using the radiation-sensitive composition according to any one of measures 1 to 10. [Means 19] An imaging device comprising the solid-state imaging element according to [Means 18]. [Means 20] A compound which is a reaction product of a compound represented by the above formula (1) and a compound represented by the above formula (2). EXAMPLES

[0119] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the examples and comparative examples, "parts" and "%" are by weight unless otherwise specified.

[0120] The abbreviations of the compounds used in the examples and comparative examples are as follows. BNFGA: acrylic acid adduct of 9,9-bis[6-(glycidyloxy)-2-naphthyl]-9H-fluorene, a compound obtained by synthesis according to the description in Japanese Patent No. 6175259 (molecular weight = 706.79) BPFGA: 9,9-bis(4-glycidyloxyphenyl)fluorene acrylic acid adduct PGMEA: Propylene glycol monomethyl ether acetate CPN: Cyclopentanone Compounds (A-4) to (A-11): Compounds represented by the following formulas (A-4) to (A-11), respectively. [ka] [ka]

[0121] 1. Synthesis of fluorene compounds (compounds [A]) [Synthesis Example 1] In a 100 mL three-neck flask equipped with a reflux condenser and a thermometer, 12 g (16.9 mmol) of BNFGA was dissolved in 28 g of PGMEA and cooled on ice. Then, 6.66 g (33.8 mmol) of p-toluenesulfonyl isocyanate was slowly added so that the internal temperature did not exceed 20°C, and the mixture was allowed to react at room temperature for 1 hour, thereby obtaining 46.7 g of a PGMEA solution of compound (A-1) with a solid content concentration of 40%. [ka]

[0122] [Synthesis Example 2] A reaction was carried out in the same manner as in Synthesis Example 1, except that the amounts of the raw materials were changed as shown in Table 1, to obtain a PGMEA solution of compound (A-2). PGMEA was added so that the solid concentration became 40%, and the solution was used to prepare the radiation-sensitive composition shown below.

[0123] [Synthesis Example 3] A reaction was carried out in the same manner as in Synthesis Example 1, except that the types and amounts of raw materials were changed as shown in Table 1, to obtain a PGMEA solution of compound (A-3). PGMEA was added so that the solid concentration became 40%, and the solution was used in the preparation of the radiation-sensitive composition shown below. [ka]

[0124] [Table 1]

[0125] In Table 1, the abbreviations for the compounds are as follows. N-1: p-Toluenesulfonyl isocyanate

[0126] [Comparative Synthesis Example 1] According to Example 1 of Japanese Patent No. 6726050, BNFGA was reacted with succinic anhydride to obtain a PGMEA solution containing an acid-modified (meth)acrylate (hereinafter referred to as "compound (R-1)") at a solid concentration of 40%.

[0127] 2. Preparation of Radiation-Sensitive Composition A radiation-sensitive composition was prepared by mixing the compound [A], the photopolymerization initiator [B], the compound [C], the additive [D], and the solvent [E]. The compound [A], the photopolymerization initiator [B], the compound [C], the additive [D], and the solvent [E] used in the preparation of the radiation-sensitive composition are shown below. For the compounds (A-1) to (A-3) and (R-1) among the compounds [A], a PGMEA solution having a solid content concentration of 40% was used in the preparation of the radiation-sensitive composition.

[0128] [A] Compound A-1 to A-3: Compounds obtained in Synthesis Examples 1 to 3 A-4 to A-11: Compounds represented by the above formulas (A-4) to (A-11), respectively R-1: Compound obtained by Comparative Synthesis Example 1

[0129] [B] Photopolymerization initiator B-1: 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)] (Irgacure OXE01, manufactured by BASF) B-2: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Irgacure 907, manufactured by BASF) B-3: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[0130] [C] Compound C-1: 2-hydroxy-3-phenoxypropyl acrylate C-2: Polyethylene glycol diacrylate (product name "M-240", manufactured by Toagosei Co., Ltd.) C-3: Dipentaerythritol hexaacrylate C-4: Pentaerythritol tetraacrylate C-5: Diethylene glycol modified dipentaerythritol hexaacrylate C-6: Trimethylolpropane polypropylene glycol triacrylate

[0131] [D] Additives (polymer additives) D-1: Fluorene resin (photosensitive resin described in Example 2 (paragraph 0071) of WO 2009 / 119622) [ka] D-2: Cresol novolac epoxy acrylate resin "CCR-1235" (manufactured by Nippon Kayaku Co., Ltd.)

[0132] [E] Solvent E-1: Propylene glycol monomethyl ether acetate (PGMEA) E-2: Cyclopentanone (CPN) E-3: Propylene glycol monomethyl ether (PGME)

[0133] [Example 1] [A] A solution containing 100 parts by mass (solid content) of (A-1) as a compound, [B] 5 parts by mass of (B-1) as a photopolymerization initiator, [C] 20 parts by mass of (C-1) and 10 parts by mass of (C-4) as compounds, [D] 10 parts by mass of (D-1) as an additive, 0.5 parts by mass of an adhesive assistant (3-glycidyloxypropyltrimethoxysilane), and 0.2 parts by mass of a surfactant (NEOS Co., Ltd.'s "FTX-218") were mixed to obtain a mixed liquid (hereinafter referred to as "mixed liquid Mx"). A mixed solvent with a ratio of (E-1) and (E-3) of 70:30 (mass ratio) was further added to the obtained mixed liquid Mx so that the solid content concentration was 35% by mass, and then the mixture was stirred and dissolved. Next, the mixture was filtered through a membrane filter with a pore size of 0.2 μm, thereby preparing the radiation-sensitive composition of Example 1.

[0134] [Examples 2 to 35 and Comparative Examples 1 and 2] The types and amounts (parts by mass) of the compound [A], the photopolymerization initiator [B], the compound [C], and the additive [D] were as shown in Table 2, and the same operation as in Example 1 was performed to prepare radiation-sensitive compositions of Examples 2 to 35 and Comparative Examples 1 and 2. Note that, in Examples 2 to 4, 28 to 35, and Comparative Examples 1 and 2, as in Example 1, a mixed solvent in which the ratio of (E-1) and (E-3) was 70:30 (mass ratio) was used as a solvent for diluting the mixed liquid Mx obtained by mixing the compound [A], the photopolymerization initiator [B], the compound [C], the additive [D], the adhesive aid, and the surfactant, and this mixed solvent was added to the mixed liquid Mx so that the solid content concentration was 35 mass%. In Examples 5 to 27, (E-2) was used as a solvent for diluting the mixed liquid Mx, and (E-2) was added to the mixed liquid Mx so that the solid content concentration was 35 mass%.

[0135] In Table 2, the amount of compound [A] (the total amount when two or more types are used) is 100 parts by mass. The numerical values ​​of the photopolymerization initiator [B], compound [C], and additive [D] indicate the mixing ratio (parts by mass) of each compound relative to 100 parts by mass of compound [A] used in the preparation of each radiation-sensitive composition. When preparing the radiation-sensitive composition of each example, solvent [E] was added so that the final solid content concentration of each radiation-sensitive composition was 35% by mass.

[0136] [Table 2]

[0137] 3. Evaluation of radiation-sensitive composition The properties of the radiation-sensitive compositions prepared in Examples 1 to 35 and Comparative Examples 1 and 2 were evaluated as follows. The evaluation results are shown in Table 3.

[0138] [Refractive index evaluation] Each radiation-sensitive composition was applied onto a non-alkali glass substrate using a spin coater, and then prebaked on a hot plate at 85° C. for 2 minutes to form a coating film with a thickness of 9.0 μm. The resulting coating film was then irradiated with 200 mJ / cm 2 using a high-pressure mercury lamp. 2The film was then post-baked in an oven at 85° C. for 40 minutes to form a cured film. The refractive index of the resulting cured film at 589 nm was measured using a Prism Coupler (manufactured by Metricon) and evaluated according to the following criteria. Good (◎): Refractive index ≧ 1.64 Fairly good (○): 1.64>Refractive index ≧ 1.61 Acceptable (△): 1.61 > refractive index ≧ 1.59 Poor (×): 1.59> Refractive index

[0139] [Evaluation of lens shape] Each radiation-sensitive composition was applied onto a non-alkali glass substrate using a spin coater, and then prebaked on a hot plate at 85° C. for 2 minutes to form a coating film with a thickness of 9.0 μm. The coating film was then exposed to light of 200 mJ / cm using a high-pressure mercury lamp through a photomask having a pattern with multiple circular shapes with a diameter of 25 μm. 2The substrate was irradiated with radiation at 25°C. Then, development was performed for 80 seconds at 25°C by puddle method using a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23°C as a developer, and then washed with pure water for 60 seconds. Then, the substrate was dried. If the unexposed area is dissolved in the developer by the development process, a pattern consisting of many micro-cured products formed by the radiation-sensitive composition is formed on the glass substrate (see FIG. 1(a)). Furthermore, the substrate was post-baked in an oven at 85°C for 60 minutes. The micro-cured products are melted by this post-baking, and a lens pattern in which many micro-lenses are regularly arranged is formed on the substrate. The substrate was observed with a scanning electron microscope (SEM) before and after post-baking. With this series of operations, if the micro-cured material was sufficiently melted by post-baking at 85°C to form a hemispherical lens as shown in Figure 1(b), it was rated as "good (◎)"; if a lens close to a hemispherical shape was formed, it was rated as "fair (○)"; if some of it melted but the lens shape was trapezoidal when viewed from the side, it was rated as "fair (△)"; if it was not sufficiently melted and the shape did not change (i.e., it remained rectangular when viewed from the side as shown in Figure 1(a)), if it melted excessively and a hemispherical lens could not be formed, or if residues were found on most of the substrate after development (i.e., if the micro-cured material of the shape shown in Figure 1(a) was not obtained), it was rated as "poor (×)".

[0140] [Reliability test evaluation] The substrate having the cured product (cured product after development) obtained in the above [Evaluation of lens shape] was stored in a thermo-hygrostat at a temperature of 85°C and a humidity of 85% for 120 hours. The transmittance of the lens pattern was quickly measured before and after storage, and the evaluation was performed as follows: if there was no change in the transmittance before and after storage, it was "good (◎)"; if the transmittance changed by more than 0% and less than 5%, it was "fair (○)"; if the transmittance changed by more than 5% and less than 10%, it was "fair (△)"; if the transmittance changed by 10% or more, it was "poor (×)". The transmittance was measured using a microscopic ultraviolet-visible-near infrared spectrophotometer (manufactured by JASCO Corporation).

[0141] [Table 3]

[0142] As shown in Table 3, the radiation-sensitive compositions of Examples 1 to 35 were evaluated as "◎", "◯" or "△" in the refractive index, lens shape and reliability tests, and the various properties were well-balanced. In contrast, in Comparative Example 1, in which an unmodified fluorene compound (BNFGA) not modified with compound (N) was used instead of the reaction product (compound (A)) of compound (M) represented by formula (1) above and compound (N) represented by formula (2) above, the refractive index was evaluated to be equivalent to that of the radiation-sensitive compositions of Examples 1 to 35, but residues were observed on most of the substrate after development treatment, and a good lens pattern could not be formed. In addition, in Comparative Example 2, in which an acid-modified fluorene compound modified with succinic anhydride instead of compound (N) was used, the refractive index was evaluated to be equivalent to that of the radiation-sensitive compositions of Examples 1 to 35, but melting proceeded excessively due to post-baking, and hemispherical lenses could not be obtained. In addition, the cured product formed by the radiation-sensitive composition of Comparative Example 2 had a large change in transmittance and was poor in reliability.

[0143] From the above results, it is clear that the radiation-sensitive composition containing the reaction product of the compound (M) represented by the above formula (1) and the compound (N) represented by the above formula (2), a photopolymerization initiator, and the compound (C) having a polymerizable carbon-carbon unsaturated bond has good patterning properties, can sufficiently melt a pattern by heating at 100°C or less, and can give a cured product with a high refractive index and high reliability.

Claims

1. Component (A): a reaction product of a compound represented by the following formula (1) and a compound represented by the following formula (2): Component (B): a photopolymerization initiator, and Component (C): A compound having a polymerizable carbon-carbon unsaturated bond (excluding the component (A)). A radiation-sensitive composition comprising: 【Chemistry 1】 (In formula (1), Ar １ and Ar ２ are each independently an aromatic ring group. １ and R ２ are each independently a monovalent substituent, or R １ and R ２ and are combined together to form Ar １ and Ar ２ The fused ring structure is a fused ring structure in which two aromatic rings are bonded together with a single bond, —O—, —S—, —NR ８ -, methylene group or ethylene group. ８ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ３ and R ４ are each independently a monovalent substituent. １ and X ２ are each independently a group represented by the following formula (1x): m1 and m2 are each independently an integer of 0 to 6; k1 and k2 are each independently an integer of 0 to 4; n1 and n2 are each independently an integer of 1 to 6. In the formula, R １ ~R ４ , X １ , X ２ When there are multiple R １ ~R ４ , X １ , X ２ are the same or different.) 【Chemistry 2】 (In formula (1x), R ５ is an alkanediyl group having 2 to 4 carbon atoms. ６ is a hydrogen atom or a methyl group. p is an integer of 0 to 4. When p is 2 or more, multiple R ５ are the same or different.) 【Chemistry 3】 (In formula (2), R ７ is an organic group having a valence of r. r is an integer from 1 to 4.

2. R in the above formula (2) ７ is a group having a monocyclic aromatic hydrocarbon ring, a condensed polycyclic aromatic hydrocarbon ring, or an aliphatic hydrocarbon ring, or is a group having one or more hetero atoms selected from the group consisting of a sulfur atom, a nitrogen atom, and a phosphorus atom.

3. 2. The radiation-sensitive composition according to claim 1, wherein the component (C) is a compound (C2) having three or more polymerizable carbon-carbon unsaturated bonds in one molecule, or a combination of a compound (C1) having one or two polymerizable carbon-carbon unsaturated bonds in one molecule and the compound (C2).

4. The radiation-sensitive composition according to claim 1 , wherein the component (C) is a compound having a molecular weight of less than 600.

5. The component (A) is Ar in the above formula (1). １ and Ar ２ has a condensed polycyclic aromatic hydrocarbon ring, or R １ and R ２ and are combined together to form Ar １ and Ar ２ The radiation-sensitive composition according to claim 1 , which has a condensed ring structure formed together with

6. The radiation-sensitive composition according to claim 1 , wherein the component (A) is represented by the following formula (A1): 【Chemistry 4】 (In formula (A1), Ar １ , Ar ２ , R １ ~R ４ , m1, m2, k1, k2, n1 and n2 are the same as those in formula (1). ３ and X ４ are each independently a group represented by the following formula (1y): 【Chemistry 5】 (In formula (1y), Y １ is a hydrogen atom or "-C(=O)-NH-SO ２ -R ７ " is a group represented by the formula (A1). １ At least one of the groups is "-C(=O)-NH-SO ２ -R ７ " is a group represented by R ５ , R ６ and p are the same as those in formula (1x), R ７ is defined as the above formula (2).

7. 2. The radiation-sensitive composition according to claim 1, further comprising a compound having a fluorene skeleton and a molecular weight of 1,500 or less (excluding the component (A)).

8. The composition contains, as an optional component, a compound having a fluorene skeleton and a molecular weight of 1,500 or less (excluding the component (A)), 2. The radiation-sensitive composition according to claim 1, wherein a content of the component (C) is 5 parts by mass or more and 100 parts by mass or less, relative to a total of 100 parts by mass of the component (A) and the compound having a fluorene skeleton and a molecular weight of 1,500 or less.

9. Furthermore, Component (D): a polymer having a molecular weight of 2,000 or more and 100,000 or less (excluding component (A)). The radiation-sensitive composition according to claim 1 , comprising:

10. The radiation-sensitive composition according to claim 9 , wherein the content of the component (D) is 50 parts by mass or less per 100 parts by mass of the component (A).

11. The radiation-sensitive composition according to any one of claims 1 to 10, which is used for producing a lens.

12. The radiation-sensitive composition according to any one of claims 1 to 10, which is used for forming a planarizing film.

13. A step of applying the radiation-sensitive composition according to any one of claims 1 to 10 onto a substrate to form a coating film; exposing a portion of the coating to radiation; developing the irradiated coating to form a pattern on the substrate; heating the pattern; A method for manufacturing a lens, comprising:

14. The method for manufacturing a lens according to claim 13, wherein the temperature at which the pattern is heated is 100° C. or less.

15. A method for producing a lens, comprising a step of ink-jet coating the radiation-sensitive composition according to any one of claims 1 to 10 onto a substrate to form a pattern.

16. A display device comprising a lens formed using the radiation-sensitive composition according to any one of claims 1 to 10.

17. A display device comprising one or both of the display element according to claim 16 and a planarizing film formed using the radiation-sensitive composition according to any one of claims 1 to 10.

18. A solid-state imaging device comprising a lens formed using the radiation-sensitive composition according to any one of claims 1 to 10.

19. An imaging device comprising the solid-state imaging device according to claim 18.

20. A compound which is a reaction product of a compound represented by the following formula (1) and a compound represented by the following formula (2): 【Chemistry 6】 (In formula (1), Ar １ and Ar ２ are each independently an aromatic ring group. １ and R ２ are each independently a monovalent substituent, or R １ and R ２ and are combined together to form Ar １ and Ar ２ The fused ring structure is a fused ring structure in which two aromatic rings are bonded together with a single bond, —O—, —S—, —NR ８ -, methylene group or ethylene group. ８ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ３ and R ４ are each independently a monovalent substituent. １ and X ２ are each independently a group represented by the following formula (1x): m1 and m2 are each independently an integer of 0 to 6; k1 and k2 are each independently an integer of 0 to 4; n1 and n2 are each independently an integer of 1 to 6. In the formula, R １ ~R ４ , X １ , X ２ When there are multiple R １ ~R ４ , X １ , X ２ are the same or different.) 【Chemistry 7】 (In formula (1x), R ５ is an alkanediyl group having 2 to 4 carbon atoms. ６ is a hydrogen atom or a methyl group. p is an integer of 0 to 4. When p is 2 or more, multiple R ５ are the same or different.) 【Chemistry 8】 (In formula (2), R ７ is an organic group having a valence of r. r is an integer from 1 to 4.

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