Radiation-sensitive composition, cured material, display device, imaging device, producing method of cured material and polymer

Abstract

To provide a polymer that is, while having a high refraction index, excellent in solubility into a general-purpose solvent and difficult to cause deposition during dilution with the general-purpose solvent and a radiation-sensitive composition.SOLUTION: A radiation-sensitive composition comprising (A) Component: A polymer having a partial structure represented by the following formula (1), and (B) Component: A photopolymerization initiator, and (C) Component: A polymerizable compound, [In formula (1), Ar is a divalent organic group includes either or both an aromatic ring and a heterocyclic ring, and X1 and X2 are each independently S or NR (R being a hydrogen atom or a monovalent organic group), with at least one of X1 and X2 being S, and * representing a bonding hand.]SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] For example, high refractive indexes are sometimes required for optical components such as high-performance substrates for display devices, (interlayer) insulating films, protective films, planarizing films, optical adhesives, anti-reflection films, sealing materials, and microlenses for CMOS and CCD image sensors.

[0003] The high refractive index optical member is formed using, for example, a high refractive index polymer or a composition containing the polymer. As a composition containing such a high refractive index polymer, for example, Patent Documents 1 and 2 disclose a composition containing a triazine ring-containing polymer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-107347 [Patent Document 2] International Publication No. 2017 / 138547 Summary of the Invention [Problem to be solved by the invention]

[0005] The optical members are often formed from radiation-sensitive compositions because they can be easily formed into optical members having desired shapes. Such radiation-sensitive compositions are often prepared using general-purpose organic solvents (hereinafter also referred to as "general-purpose solvents"), such as propylene glycol monomethyl ether acetate, from the viewpoints of ease of handling during the production of optical members, the ability to form uniform optical members, safety, and the like.

[0006] However, it has been found that high refractive index polymers such as the triazine ring-containing polymers described in Patent Documents 1 and 2 have room for improvement in terms of solubility in the general-purpose solvents. Furthermore, when producing the optical member, the radiation-sensitive composition (including a radiation-sensitive composition that already contains a solvent) may be further diluted with the general-purpose solvent before use. However, it has been found that when a conventional radiation-sensitive composition containing a high refractive index polymer is diluted with the general-purpose solvent, precipitation of components contained in the radiation-sensitive composition (particularly the high refractive index polymer) is likely to occur during the dilution (hereinafter also referred to as "precipitation during dilution with a general-purpose solvent").

[0007] The present invention has been made in view of the above, and an object of the present invention is to provide a polymer and a radiation-sensitive composition that have a high refractive index, yet have excellent solubility in general-purpose solvents, and are less likely to precipitate when diluted with a general-purpose solvent. [Means for solving the problem]

[0008] The present inventors have found that the above-mentioned problems can be solved by the following configuration examples. That is, the present invention provides the following radiation-sensitive composition, cured product, display device, imaging device, method for producing the cured product, and polymer. A configuration example of the present disclosure is shown below. [1] Component (A): a polymer having a partial structure represented by the following formula (1), (B) component: a photopolymerization initiator; Component (C): a polymerizable compound A radiation-sensitive composition comprising: [ka] [In formula (1), Ar represents a divalent organic group containing either an aromatic ring or a heterocyclic ring, or both, X 1 and X 2 are each independently S or NR (R is a hydrogen atom or a monovalent organic group), and X 1 and X 2 At least one of these is S, * represents a bond. [2] The radiation-sensitive composition according to [1] above, wherein Ar in the formula (1) is at least one selected from the group represented by the following formulae (Ar-1) to (Ar-20): [ka] [In the formula, R 1 ~R 12 each independently represents a hydrogen atom, a halogen atom, an acidic group, an alkyl group having 1 to 10 carbon atoms which may have a branched structure, or an alkoxy group having 1 to 10 carbon atoms which may have a branched structure, R 13 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and which may have a branched structure, W 1 and W 2 are each independently a single bond, CR 14 R 15 (R 14 and R 15 are each independently a hydrogen atom or a monovalent organic group (provided that R 14 and R 15 may be bonded to each other to form a ring. ) ), C=O, O, S, SO, SO2, or NR 16 (R 16 is a hydrogen atom or a monovalent organic group; Z 1 and Z 2 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms which may have a branched structure, or a group represented by the following formula (Z-1). * represents a bond. [ka] [In the formula, R 21 ~R 24 each independently represents a hydrogen atom, a halogen atom, an acidic group, an alkyl group having 1 to 10 carbon atoms which may have a branched structure, or an alkoxy group having 1 to 10 carbon atoms which may have a branched structure, Y 1 and Y 2are each independently a single bond or an alkylene group having 1 to 10 carbon atoms which may have a branched structure. * represents a bond. [3] In the formula (1), X 1 and X 2 The radiation-sensitive composition according to the above [1] or [2], wherein one of the groups is S and the other is NR (R is a hydrogen atom or a monovalent organic group). [4] The radiation-sensitive composition according to any one of the above [1] to [3], wherein the polymer having the partial structure represented by the formula (1) has a weight-average molecular weight of 500 to 5,000. [5] The radiation-sensitive composition according to any one of [1] to [4] above, wherein the partial structure represented by formula (1) above is a partial structure represented by formula (2) below: [ka] [In formula (2), Ar, X 1 and X 2 has the same meaning as the same symbol in the formula (1), X 3 is S, O, or NR' (R' is a hydrogen atom or a monovalent organic group), A is an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group containing either an aromatic ring or a heterocyclic ring, or both; * represents a bond. [6] The radiation-sensitive composition according to any one of [1] to [5] above, wherein the polymer having the partial structure represented by formula (1) has a refractive index of 1.63 or more at a wavelength of 550 nm. [7] The radiation-sensitive composition according to any one of [1] to [6] above, wherein the polymer having the partial structure represented by formula (1) is soluble in propylene glycol monomethyl ether acetate (PGMEA) at 25°C in an amount of 10% by mass or more. [8] The radiation-sensitive composition according to any one of [1] to [7] above, which is used for producing a microlens by a thermal flow method. [9] A cured product obtained by curing the radiation-sensitive composition according to any one of the above [1] to [8].

[10] The cured product according to [9] above, having a refractive index of 1.60 or more at a wavelength of 550 nm.

[11] The cured product according to [9] or

[10] above, which is for use in optical components.

[12] A display device comprising the cured product according to any one of [9] to

[11] above.

[13] An imaging device comprising the cured product according to any one of [9] to

[11] above.

[14] A step of applying the radiation-sensitive composition according to any one of the above [1] to [8] onto a substrate; a step of irradiating the radiation-sensitive composition coated on the substrate with radiation; developing the radiation-sensitive composition after irradiation; A method for producing a cured product, comprising:

[15] The method for producing a cured product according to

[14] above, further comprising a step of heating the radiation-sensitive composition after development.

[16] The method for producing a cured product according to

[15] above, wherein the heating temperature in the step of heating the radiation-sensitive composition after development is 100°C or less.

[17] The method for producing a cured product according to

[15] or

[16] above, wherein the pattern is melted by a step of heating the radiation-sensitive composition after the development to form microlenses.

[18] A polymer having a partial structure represented by the following formula (1): [ka] [In formula (1), Ar represents a divalent organic group containing either an aromatic ring or a heterocyclic ring, or both, X 1 and X 2 are each independently S or NR (R is a hydrogen atom or a monovalent organic group), and X 1 or X 2 One of them is S, * represents a bond.

[19] The polymer according to

[18] above, which has a refractive index of 1.63 or more at a wavelength of 550 nm.

[20] The polymer according to

[18] or

[19] above, which is soluble in propylene glycol monomethyl ether acetate (PGMEA) at 25°C to a concentration of 10% by mass or more. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a polymer and a radiation-sensitive composition that have a high refractive index, yet have excellent solubility in general-purpose solvents (particularly PGMEA), and are less likely to precipitate when diluted with a general-purpose solvent (particularly PGMEA). Examples of the general-purpose solvent include PGMEA, propylene glycol monomethyl ether (PGME), methyl 3-methoxypropanoate, propylene glycol-n-propyl ether, butyl acetate, ethyl lactate, ethyl 3-methoxypropanoate, methoxybutyl acetate, ethylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether acetate, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether. Polymers and radiation-sensitive compositions that have excellent solubility in PGMEA tend to also have excellent solubility in general-purpose solvents other than PGMEA.

[0010] The radiation-sensitive composition according to one embodiment of the present invention can be fluidized by heating at low temperature (thermal flow) to easily form a cured product (e.g., a microlens or planarizing film) with a desired shape and a high refractive index, particularly a microlens. Such a radiation-sensitive composition according to one embodiment of the present invention is suitable for producing microlenses or forming planarizing films. Furthermore, the radiation-sensitive composition according to one embodiment of the present invention can be a developer-soluble, particularly alkali-soluble, radiation-sensitive composition, and the developer-soluble radiation-sensitive composition is excellent in pattern-forming properties and in the ability to form a cured product having a desired shape, such as a microlens. [Brief explanation of the drawings]

[0011] [Figure 1]1A and 1B are enlarged photographs of a microlens pattern obtained in a patterning test in the following example, viewed from the front, showing the state before post-baking and the state after post-baking. DETAILED DESCRIPTION OF THE INVENTION

[0012] Matters related to the embodiments will be described in detail below. In this specification, a numerical range indicated using "to" means that the numerical values ​​before and after "to" are included as the lower and upper limits.

[0013] In this specification, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and / or a branched hydrocarbon group that does not contain a cyclic structure in the main chain and is composed solely of a chain structure, and may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, it does not necessarily have to be composed solely of an alicyclic hydrocarbon structure, and also includes groups that have a chain structure as part of it. Furthermore, the alicyclic hydrocarbon structure may be a single ring or a fused ring. The term "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary for the group to be composed solely of an aromatic ring structure, and it may also contain a chain structure or an alicyclic hydrocarbon structure as part of the aromatic ring structure. The aromatic ring structure may be a single ring or a condensed ring. The ring structures of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a hydrocarbon group as a substituent.

[0014] In this specification, "(meth)acrylic" encompasses "acrylic" and "methacrylic." "(meth)acryloyl group" encompasses "acryloyl group" and "methacryloyl group." "Alkali-soluble" means that the compound is soluble or swellable in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C.

[0015] ≪Radiation-sensitive composition≫ The radiation-sensitive composition of the present disclosure (hereinafter also referred to as "the composition") contains the following components (A), (B), and (C). Unless otherwise specified, each component may be used alone or in combination of two or more. Component (A): a polymer having a partial structure represented by the following formula (1): Component (B): Photopolymerization initiator (C) Component: Polymerizable compound

[0016] <Polymer> The polymer of the present disclosure is a polymer having a partial structure represented by the following formula (1): Hereinafter, a polymer having a partial structure represented by the following formula (1) will also be referred to as "polymer (1)".

[0017] [ka] [In formula (1), Ar is a divalent organic group containing either an aromatic ring or a heterocyclic ring, or both, and X 1 and X 2 are each independently S or NR (R is a hydrogen atom or a monovalent organic group), and X 1 and X 2 At least one of the groups is S, and * represents a bond.

[0018] [Polymer (1)] The polymer (1) is a polymer having a partial structure represented by formula (1) and containing a repeating unit having a triazine ring structure. Such polymer (1) has a high refractive index and excellent solubility in general-purpose solvents (particularly PGMEA). Furthermore, by using such polymer (1), it is possible to easily obtain the present composition, which is less likely to precipitate when diluted with a general-purpose solvent.

[0019] In the formula (1), the aromatic ring and heterocyclic ring contained in Ar may be a single ring or a fused ring. As Ar, from the viewpoints of achieving a high refractive index and increasing solubility in general-purpose solvents (particularly PGMEA), it is preferably at least one selected from the group represented by the following formulas (Ar-1) to (Ar-20), more preferably at least one selected from the group represented by the following formulas (Ar-1), (Ar-4), (Ar-19), and (Ar-20), and in consideration of the ease of availability of raw material compounds and the ease of synthesis of polymer (1), it is even more preferably at least one selected from the group represented by the following formulas (Ar-1) and (Ar-19).

[0020] [ka]

[0021] In the above formula, R 1 ~R 12 are each independently a hydrogen atom, a halogen atom, an acidic group, an alkyl group having 1 to 10 carbon atoms which may have a branched structure, or an alkoxy group having 1 to 10 carbon atoms which may have a branched structure.

[0022] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0023] Examples of the acidic group include a carboxy group, a carboxyalkoxy group, a sulfonic acid group, a phenolic hydroxyl group, a thiol group, an imidazole group, a triazole group, a tetrazole group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfonamide group, a maleimide group, a silanol group, and a hydroxyalkyl group in which a hydrogen atom bonded to a carbon atom is substituted with an electron-withdrawing group.

[0024] Examples of the alkyl group having 1 to 10 carbon atoms and which may have a branched structure include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl -n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,Examples include a 3-trimethyl-cyclopropyl group, a 1-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-1-methyl-cyclopropyl group, a 2-ethyl-2-methyl-cyclopropyl group, and a 2-ethyl-3-methyl-cyclopropyl group. From the viewpoint of achieving both a good refractive index and solubility, the number of carbon atoms in the alkyl group is preferably 1 to 8, and more preferably 1 to 3. The structure may be a chain structure or a branched structure.

[0025] Examples of the alkoxy group having 1 to 10 carbon atoms and which may have a branched structure include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, and a 2-methyl-n-pentyloxy group. Examples of such groups include a 3-methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, and a 1-ethyl-2-methyl-n-propoxy group. From the viewpoint of achieving both a good refractive index and solubility, the number of carbon atoms in the alkoxy group is preferably 1 to 8, and more preferably 1 to 3. The structure may be a chain structure or a branched structure.

[0026] R 13 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a branched structure, and examples of the alkyl group include the same groups as those exemplified above.

[0027] W 1 and W 2 are each independently a single bond, CR 14 R 15 , C=O, O, S, SO, SO2, or NR 16 and R 14 ~R 16 are each independently a hydrogen atom or a monovalent organic group. 14 and R 15 may be bonded to each other to form a ring. Specific examples of the monovalent organic group include an alkyl group, an alkoxy group, an aryl group, and an aralkyl group, each of which may have a substituent. Examples of the alkyl group and alkoxy group include the same groups as those specifically mentioned above. Examples of the substituent include a halogen atom, an acidic group, a cyano group, an alkyl group having 1 to 10 carbon atoms which may have a branched structure, and an alkoxy group having 1 to 10 carbon atoms which may have a branched structure.

[0028] The number of carbon atoms in the aryl group is not particularly limited, but is preferably 6 to 40, more preferably 6 to 16, and even more preferably 6 to 13, in order to further increase the refractive index of the polymer. Specific examples of the aryl group include a phenyl group, an o-chlorophenyl group, a m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-hydroxyphenyl group, a m-hydroxyphenyl group, a p-hydroxyphenyl group, an o-carboxyphenyl group, a m-carboxyphenyl group, a p-carboxyphenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-nitrophenyl group, a p-cyanophenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

[0029] The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 7 to 20. The alkyl portion of the aralkyl group may be linear, branched, or cyclic. Specific examples of the aralkyl group include a benzyl group, a p-methylphenylmethyl group, a m-methylphenylmethyl group, an o-ethylphenylmethyl group, a m-ethylphenylmethyl group, a p-ethylphenylmethyl group, a 2-propylphenylmethyl group, a 4-isopropylphenylmethyl group, a 4-isobutylphenylmethyl group, and an α-naphthylmethyl group.

[0030] Z 1 and Z 2 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms which may have a branched structure, or a group represented by the following formula (Z-1). Examples of the alkylene group having 1 to 10 carbon atoms and which may have a branched structure include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.

[0031] [ka]

[0032] In the above formula, R 21 ~R 24 are each independently a hydrogen atom, a halogen atom, an acidic group, an alkyl group having 1 to 10 carbon atoms which may have a branched structure, or an alkoxy group having 1 to 10 carbon atoms which may have a branched structure, and examples of the halogen atom, acidic group, alkyl group, and alkoxy group include the same atoms and groups as those exemplified above.

[0033] Y 1 and Y 2 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms which may have a branched structure, and examples of the alkylene group include the same groups as those exemplified above.

[0034] * in the formulae (Ar-1) to (Ar-20) represents X1 or X 2 Represents a bond with . Ar and X 1 and X 2 When the two bonds connecting the two groups are bonded to the same ring (e.g., the above formulae (Ar-1), (Ar-5), (Ar-7), (Ar-9), and (Ar-13) to (Ar-20)), the positional relationship of these two bonds may be any of the so-called ortho-, meta-, and para-positions, but being at the ortho-position is preferred because it tends to be easier to obtain a polymer that has excellent solubility in commonly used solvents.

[0035] Specific examples of Ar include, but are not limited to, groups represented by the following formulae:

[0036] [ka]

[0037] In the formula (1), X 1 and X 2 are each independently S or NR (R is a hydrogen atom or a monovalent organic group). Examples of the monovalent organic group include the same groups as those exemplified above. In the formula (1), a polymer having excellent solubility in a general-purpose solvent (particularly PGMEA) tends to be easily obtained, and further, by using the polymer, the present composition which is unlikely to precipitate when diluted with a general-purpose solvent (particularly PGMEA) tends to be easily obtained. Therefore, X 1 and X 2 At least one of is S, and preferably X 1 and X 2 One of them is S and the other is NR.

[0038] The partial structure represented by the formula (1) is preferably a partial structure represented by the following formula (2). The polymer having the partial structure represented by the following formula (2) can be a chain polymer, rather than a so-called hyperbranched polymer such as the polymer described in Patent Document 2.

[0039] [ka]

[0040] In the formula (2), Ar, X 1 and X 2 has the same meaning as the same symbol in the formula (1), and * represents a bond. X 3 is S, O, or NR', and R' is a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include the same groups as those exemplified above.

[0041] X 3 is preferably NR', more preferably NH, in order to provide a polymer with excellent solubility in common solvents. R' is preferably a group having an acidic group, from the viewpoint that the present composition can be obtained as a developer-soluble, particularly alkali-soluble, composition. Examples of the group having an acidic group include an o-hydroxyphenyl group, an m-hydroxyphenyl group, a p-hydroxyphenyl group, an o-carboxyphenyl group, an m-carboxyphenyl group, and a p-carboxyphenyl group.

[0042] A is an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group containing either or both of an aromatic ring and a heterocyclic ring. The number of carbon atoms in the alkyl group having 1 to 20 carbon atoms in A is preferably 3 to 18, and more preferably 6 to 16, in order to further increase the solubility in general-purpose solvents (particularly PGMEA). Specific examples of the alkyl group having 1 to 20 carbon atoms include the same groups as the alkyl group having 1 to 10 carbon atoms which may have a branched structure.

[0043] The monovalent organic group containing either or both of an aromatic ring and a heterocyclic ring in A is a group in which one of the two bonds in Ar is substituted with a substituent R 30 Examples of the groups include those substituted with: R 30 is a hydrogen atom, a halogen atom, an acidic group, a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms which may have a branched structure, or a group in which the hydrocarbon group is partially substituted with at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom. 30 may be a substituent into which a reactive group such as a (meth)acryloyl group is introduced via the substituent (e.g., hydroxyl group, acidic group), obtained by, for example, reacting a hydroxyl group with 2-isocyanatoethyl (meth)acrylate or the like. R 30 A specific example of this is R 1 ~R 12 Specific examples of the atoms or groups mentioned above include the same as those mentioned above. As A, one of the two bonds in the formula (Ar-1) is preferably substituted by the substituent R 30 It is preferable that the group is a group represented by the following formula:

[0044] In terms of being able to obtain a developer-soluble, particularly alkali-soluble, composition of the present invention, A in the formula (2) is preferably a group having an acidic group. Examples of the group having an acidic group include an o-hydroxyphenyl group, a m-hydroxyphenyl group, a p-hydroxyphenyl group, an o-carboxyphenyl group, a m-carboxyphenyl group, and a p-carboxyphenyl group.

[0045] Preferred specific examples of the partial structure represented by the formula (1) include, but are not limited to, structures represented by the following formulas:

[0046] [ka]

[0047] The polymer (1) is preferably a polymer represented by the following formula (3), because it is likely to be a polymer that has a high refractive index and excellent solubility in common solvents. The polymer represented by the following formula (3) can be said to be a chain polymer, not a hyperbranched polymer.

[0048] [ka]

[0049] In the formula (3), A, Ar, X 1 ~X 3 has the same meaning as the same symbol in the formula (2). Y in the formula (3) is a terminal structure, and examples thereof include the same groups as those of A, and specific examples thereof include structures derived from the terminal-capping monomers shown below. X in the formula (3) is S or NR (R is a hydrogen atom or a monovalent organic group), and is preferably NR. Examples of R include the same groups as those exemplified above. A, Ar, X, X 1 ~X 3 At least one of A and Y is preferably a group having an acidic group, from the viewpoint that the present composition can be obtained which is soluble in a developer, particularly an alkali-soluble composition. In the formula (3), n is the number of repeating units, and is preferably a number such that the weight average molecular weight (Mw) of the polymer represented by the formula (3) falls within the following range.

[0050] The weight average molecular weight (Mw) of the polymer (1) in terms of polystyrene determined by gel permeation chromatography (GPC) is preferably from 500 to 5,000, more preferably from 700 to 4,800, and even more preferably from 1,000 to 4,600. A polymer having an Mw within the above range can be said to be essentially an oligomer, and can easily form a cured product that has excellent solubility in general-purpose solvents (particularly PGMEA) and excellent heat resistance and chemical resistance. A polymer having an Mw within the above range can be synthesized, for example, by adjusting the equivalent ratio of the dihalogenated triazine compound obtained in the following step (I) to the following monomer (II). Specifically, the Mw can be measured by the method described in the examples below.

[0051] The refractive index of polymer (1) at a wavelength of 550 nm is preferably 1.63 or more, more preferably 1.69 or more, even more preferably 1.70 or more, particularly preferably 1.73 or more, and most preferably 1.75 or more. A polymer having a refractive index within the above range can be said to have a high refractive index, and can be suitably used as a raw material for optical components and the like. Specifically, the refractive index can be measured by the method described in the examples below.

[0052] The polymer (1) dissolves in PGMEA at 25° C. in an amount of preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. When the solubility in PGMEA is equal to or greater than the lower limit, the polymer can be said to have excellent solubility in general-purpose solvents, and by using the polymer, it is possible to easily obtain the present composition which is less likely to precipitate when diluted with a general-purpose solvent (particularly PGMEA). Specifically, the solubility can be measured by the method described in the examples below.

[0053] The polymer (1) can be synthesized, for example, by a method including the following steps (I) and (II). Step (I): A trihalogenated triazine compound such as cyanuric chloride is reacted with a compound having one group selected from an amino group (-NR'2 [the R' has the same meaning as the same symbol in formula (2)]), a thiol group, and a hydroxy group (hereinafter also referred to as "monomer (I)") in an organic solvent. Step (II): The obtained dihalogenated triazine compound is reacted with a compound (hereinafter also referred to as "monomer (II)") having two groups selected from an amino group (-NR2) and a thiol group (provided that at least one of the groups is a thiol group) in an organic solvent, and then a terminal-capping agent (hereinafter also referred to as "terminal-capping monomer") is reacted to terminate the polymerization reaction.

[0054] Examples of the monomer (I) include aniline, N-methylaniline, o-aminophenol, m-aminophenol, p-aminophenol, 4-hydroxydiphenylamine, o-aminobenzoic acid, thiosalicylic acid, diphenylamine, m-aminobenzoic acid, phenol, salicylic acid, methyl salicylate, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 8-aminoquinoline, thiophenol, p-toluenethiol, 1-naphthol, and 2-naphthol.

[0055] The amount of the monomer (I) used is preferably 0.2 to 1.8 equivalents, more preferably 0.5 to 1.5 equivalents, and even more preferably 0.9 to 1.1 equivalents relative to 1 equivalent of the trihalogenated triazine compound.

[0056] The step (I) can be carried out preferably at -10 to 30°C, more preferably at 0 to 5°C.

[0057] Examples of the monomer (II) include o-aminobenzenethiol, p-aminobenzenethiol, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 4,4'-thiobisbenzenethiol, bismuthiol, and 1,5-naphthalenedithiol.

[0058] The amount of the monomer (II) used is preferably 0.3 to 3 equivalents, more preferably 0.5 to 1.5 equivalents, and even more preferably 0.67 to 0.85 equivalents relative to 1 equivalent of the trihalogenated triazine compound.

[0059] Examples of the end-capping monomer include aniline, 2,5-dimethoxyaniline, o-aminophenol, m-aminophenol, 2-(4-aminophenyl)ethanol, hexylamine, hexyl mercaptan, benzenethiol, and p-toluenethiol.

[0060] The amount of the end-capping monomer used is preferably 0.05 to 0.9 equivalents, more preferably 0.2 to 0.6 equivalents, and even more preferably 0.3 to 0.5 equivalents relative to 1 equivalent of the trihalogenated triazine compound.

[0061] The steps (I) and (II) are preferably carried out in the presence of a base. Examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, calcium oxide, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, n-propylamine, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, diethylisopropylamine, N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, and N-methylmorpholine.

[0062] The step (II) can be carried out at a temperature of preferably 0 to 130°C, more preferably 40 to 80°C from an industrial viewpoint.

[0063] The organic solvent used in the steps (I) and (II) is not particularly limited, and examples thereof include the same solvents as those exemplified as solvent (E) below. The organic solvent used in the step (I) and the organic solvent used in the step (II) may be the same or different, but it is preferable that they are the same.

[0064] The reaction scheme when aniline is used as the monomer (I), p-aminobenzenethiol is used as the monomer (II), and aniline is used as the end-capping monomer is shown below.

[0065] [ka] (wherein X represents a halogen atom).

[0066] The content of component (A) in the present composition is preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, based on 100% by mass of the solid content of the present composition (i.e., the components other than the solvent in the present composition). When the content of component (A) is within the above range, a composition that is less likely to precipitate when diluted with a general-purpose solvent (particularly PGMEA) can be easily obtained, a cured product with a high refractive index can be easily formed, and the cured product can be fluidized at a relatively low temperature (for example, 100°C or lower).Even when fluidized by heating at a low temperature, wetting and spreading of the part (hem) that comes into contact with the substrate (adherend) is suppressed, and a cured product with the desired shape can be easily obtained.

[0067] [Component (B): Photopolymerization initiator] Although there are no particular limitations on component (B), a photoradical polymerization initiator that generates radicals in response to radiation and can initiate polymerization is preferred. Examples of component (B) include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and acylphosphine oxide compounds.

[0068] 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-9.H.-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)-9.H.-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, ethanone-1-one oxime-O-acet ... 1-[9-n-butyl-6-(2-ethylbenzoyl)-9.H.-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9.H.-carbazol-3-yl]-ethan-1-one oxime-O- -[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9.H.-carbazol-3-yl]-1-(O-acetyloxime).

[0069] Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound. Specific examples of α-aminoketone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. Specific examples of α-hydroxyketone compounds include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenyl ketone.

[0070] Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0071] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0072] The content of component (B) in the present composition is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, per 100 parts by mass of component (A). When the content of the component (B) is within the above range, a radiation-sensitive composition exhibiting good curability and transparency can be easily obtained.

[0073] [Component (C): Polymerizable compound] The polymerizable compound as component (C) is essential for forming a cured product of the present composition, and is preferably a compound having a polymerizable carbon-carbon unsaturated bond. By using component (C) as the polymerizable compound, it is possible to achieve fluidization of the pattern through a low-temperature process at, for example, 100°C or less, and to easily form a cured product in the desired shape (particularly a microlens shape).

[0074] From the viewpoint of being able to keep the temperature of the heat treatment for forming a cured product of the desired shape as low as possible, the molecular weight of component (C) is preferably 1,200 or less, more preferably 800 or less, and even more preferably 600 or less. Furthermore, from the viewpoint of being able to easily form a cured product that has a high refractive index, excellent solvent resistance, and excellent reliability such as low volatility, the molecular weight of component (C) is preferably 100 or more.

[0075] Examples of component (C) include (meth)acryloyl group-containing compounds, linear vinyl compounds, aromatic vinyl compounds, and maleimide compounds, and among these, (meth)acryloyl group-containing compounds are preferred because of their relatively high plasticity.

[0076] The component (C) may be either a monofunctional compound or a polyfunctional compound, and a monofunctional compound and a polyfunctional compound may be used in combination as the component (C).

[0077] Specific examples of when component (C) 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, and maleimide compounds. Among these, (meth)acryloyl group-containing compounds are preferred, and (meth)acryloyl group-containing compounds that are at least one selected from the group consisting of (meth)acrylic acid esters having a chain structure, (meth)acrylic acid esters having an alicyclic structure, and (meth)acrylic acid esters having an aromatic ring structure are more preferred.

[0078] Specific examples of the compound include (meth)acrylic acid esters having a chain structure, such as (meth)acrylic acid alkyl esters, (meth)acrylic acid hydroxyalkyl esters, (meth)acrylic acid alkoxyalkyl esters, and (meth)acrylic acid polyoxyalkylene esters. Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate. Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples of the alkoxyalkyl (meth)acrylate 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.

[0079] Examples of (meth)acrylic acid esters having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, 4-hydroxymethylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate, and the like. 2,6 ] decan-8-yl, (meth)acrylic acid tricyclo[5.2.1.0 2,5 ] decan-8-yloxyethyl, isobornyl (meth)acrylate, and the like.

[0080] Examples of (meth)acrylic acid esters having an aromatic ring structure include phenyl (meth)acrylate, benzyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate, naphthylmethyl (meth)acrylate, naphthylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, m-phenoxyphenylmethyl (meth)acrylate, p-phenoxyphenylmethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, polyethyleneoxynonylphenyl (meth)acrylate, (1-naphthyl)methyl (meth)acrylate, (2-naphthyl)methyl (meth)acrylate, and (1,1'-biphenyl-4-yl)methyl (meth)acrylate.

[0081] Examples of the (meth)acrylamide compound include (meth)acryloylmorpholine, N-(2-hydroxyethyl)(meth)acrylamide, N-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactam.

[0082] Examples of the chain vinyl compound include propene, butene, pentene, and hexene.

[0083] Examples of aromatic vinyl compounds include styrene, methylstyrene, α-methylstyrene, t-butoxystyrene, and vinylnaphthalene.

[0084] Examples of the maleimide compound include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-(p-methylphenyl)maleimide.

[0085] Specific examples of when component (C) is a polyfunctional compound include polyfunctional (meth)acrylic acid esters, polyfunctional aromatic vinyl compounds, and polyfunctional chain vinyl compounds. Examples of polyfunctional (meth)acrylic acid esters include bifunctional (meth)acrylic acid esters, trifunctional or higher functional (meth)acrylic acid esters, etc. Specific examples of these include bifunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenol A ethoxylate di(meth)acrylate, bisphenol F ethoxylate di(meth)acrylate, cresol novolac ethoxylate di(meth)acrylate, and biphenyl ethoxylate di(meth)acrylate.

[0086] Examples of trifunctional or higher (meth)acrylic acid esters include trimethylolpropane tri(meth)acrylate, trimethylolpropane polypropylene glycol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, and ethylene oxide-modified dipentaerythritol poly(meth)acrylate (e.g., A-DPH-12E Examples of the acrylic acid-modified dipentaerythritol oligomer include those manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene oxide oligomer-modified dipentaerythritol hexa(meth)acrylate (e.g., diethylene glycol-modified dipentaerythritol hexa(meth)acrylate), tri(2-(meth)acryloyloxyethyl)phosphate, succinic acid-modified pentaerythritol tri(meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, carboxy group-containing polybasic acid-modified (meth)acrylic oligomer, and polyfunctional urethane acrylate compounds obtained using a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and a compound having one or more hydroxy groups in the molecule and having three, four, or five (meth)acryloyloxy groups.

[0087] Examples of the polyfunctional aromatic vinyl compound include 1,3-divinylbenzene and 1,4-divinylbenzene.

[0088] Examples of the polyfunctional chain vinyl compound include 1,5-hexadiene, 1,6-heptadiene, and 1,7-octadiene.

[0089] Preferred specific examples of the component (C) include compounds represented by the following formulas (C1-1) to (C1-50).

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] In formulas (C1-1) to (C1-50), R 20 is a hydrogen atom or a methyl group. m and n are each independently an integer of 0 to 10. x, y, and z are each independently an integer of 0 to 10. In addition, R in formula (C1-48) is R in formula (C1-48). a or R b and a number of R out of 6 R are R a and b Rs out of 6 Rs are Rs b where a+b=6 and a is an integer of 1 or greater.

[0096] The content of component (C) is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of component (A), from the viewpoints that a cured product of the desired shape can be easily formed by heat treatment at low temperature and that a cured product with high heat resistance can be easily formed.

[0097] The component (C) preferably contains a compound having one or two polymerizable carbon-carbon unsaturated bonds in one molecule (hereinafter also referred to as "compound (C1)"). The content of compound (C1) is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, relative to 100% by mass of component (C), because this allows the pattern to be fluidized at low temperatures (for example, a temperature of 100°C or less) and makes it easy to form a cured product in the desired shape.

[0098] [Other ingredients] In addition to the components (A) to (C) described above, the present composition may further contain other components (hereinafter also referred to as "other components") within the scope of the present invention, such as polymers, solvents, polymerization inhibitors, surfactants, antioxidants, sensitizers, softeners, plasticizers, adhesion aids, and ultraviolet absorbers. The blending ratio of these other components is appropriately selected depending on each component within a range that does not impair the effects of the present invention.

[0099] Polymers The present composition may further contain, as an additive component, a polymer other than the aforementioned components (A) and (C) (hereinafter also referred to as "polymer (D)"). By blending polymer (D) into the present composition, the heat resistance of the resulting cured product can be improved, and a cured product with a high refractive index and excellent reliability can be easily formed.

[0100] Examples of the polymer (D) include an alkali-soluble polymer, a fluorene skeleton-containing radiation-sensitive polymer, and a carboxy group-containing radiation-sensitive polymer. The molecular weight of the polymer (D) is preferably 2,000 or more and 100,000 or less.

[0101] Examples of alkali-soluble polymers include (meth)acrylic acid / methyl (meth)acrylate copolymer, (meth)acrylic acid / benzyl (meth)acrylate copolymer, (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate copolymer, (meth)acrylic acid / styrene / isoprene / tricyclodecanyl (meth)acrylate / 2-mono(hexahydroxyphthaloyloxy)ethyl (meth)acrylate copolymer, (meth)acrylic acid-modified (meth)acrylic resin, and acid anhydride-modified (meth)acrylic resin.

[0102] Examples of the radiation-sensitive polymer containing a fluorene skeleton include the polymers described in WO 2009 / 119622.

[0103] Specific examples of the carboxy group-containing radiation-sensitive polymer may include commercially available products such as CCR-1235, CCR-1291H, ZAR-1035, ZAR-2000, ZFR-1401H, ZFR-1491H, ZCR-1569H, and ZCR-1798H (all manufactured by Nippon Kayaku Co., Ltd.).

[0104] When polymer (D) is blended into the present composition, the blending amount of polymer (D) is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, per 100 parts by mass of component (A). When the blending amount of polymer (D) is within this range, a cured product with a desired shape and excellent heat resistance can be easily formed by heat treatment at a low temperature.

[0105] ·solvent The present composition is preferably a liquid composition in which components (A) to (C) and other components that are blended as necessary are dissolved or dispersed in a solvent (hereinafter also referred to as "solvent (E)"). The solvent (E) is preferably an organic solvent that dissolves each component blended in the present composition but does not react with each component.

[0106] Specific examples of the solvent (E) 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. Among these, the solvent (E) preferably contains at least one selected from the group consisting of ethers, esters, and ketones.

[0107] Surfactants For example, the use of a surfactant can improve the coating properties of the present composition (wetting and spreading properties and reduction of coating unevenness). Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

[0108] As the fluorine-based surfactant, commercially available products may be used, and examples of such commercially available products include Megafac F-171, F-172, F-173, F-251, F-430, F-554, and F-563 (manufactured by DIC Corporation); Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited); Asahiguard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106, and S-611 (manufactured by AGC Seimi Chemical Co., Ltd.); Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.); FTX-218 (manufactured by Neos Corporation); and F-top EF301, EF303, and EF352 (manufactured by Shin-Akita Chemical Co., Ltd.).

[0109] As the silicone surfactant, commercially available products may be used, and examples of commercially available products include SH200-100cs, SH-28PA, SH-30PA, SH-89PA, SH-190, SH-8400, FLUID, SH-193, SZ-6032, SF-8428, DC-57, DC-190, PAINTAD19, FZ-2101, FZ-77, FZ-2118, L-7001, and L-7002 (manufactured by Dow-Toray Industries, Inc.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); and BYK-300, BYK-306, BYK-310, BYK-330, BYK-335, BYK-341, BYK-344, BYK-370, BYK-340, and BYK-345 (manufactured by BYK Japan Co., Ltd.).

[0110] 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.

[0111] When a surfactant is added to the present composition, the amount of surfactant added is preferably 0.01 to 1.5 parts by mass, more preferably 0.02 to 1.2 parts by mass, and even more preferably 0.05 to 1.0 part by mass, per 100 parts by mass of component (A).

[0112] Antioxidants For example, by using an antioxidant, degradation due to cleavage of polymer molecules in the composition can be suppressed, and durability and the like can be improved. Examples of antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, and thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].

[0113] When an antioxidant is blended in the present composition, the blending amount of the antioxidant is preferably 0.01 to 1.5 parts by mass, more preferably 0.02 to 1.2 parts by mass, and even more preferably 0.05 to 1.0 part by mass per 100 parts by mass of component (A).

[0114] Adhesion aid By using the present composition containing an adhesion aid, the adhesion between the formed cured product and the substrate (adherend) can be improved, and peeling of the cured product from the substrate during a development process or the like can be suppressed. As the adhesion aid, a functional silane coupling agent having a reactive functional group is preferred. Examples of the reactive functional group possessed by the functional silane coupling agent include a carboxy group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

[0115] Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0116] When an adhesion aid is blended into the present composition, the blend amount is preferably 0.01 to 4 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of component (A).

[0117] [Method for preparing the present composition] The present composition can be prepared by mixing components (A) to (C) and any other components that may be added. After mixing the components, the resulting mixture may be filtered, for example, through a filter having a pore size of 0.5 μm or less, if necessary.

[0118] The solids concentration of the composition (i.e., the ratio of the total mass of the components other than the solvent in the composition to the total mass of the composition) is appropriately selected taking into consideration viscosity, volatility, and the like. The solids concentration of the composition is preferably 1 to 60 mass%, more preferably 2 to 50 mass%, and even more preferably 5 to 40 mass%. A solids concentration of at least the lower limit is preferred in that a sufficient coating thickness can be ensured when the composition is applied to a substrate (adherend). On the other hand, a solids concentration of at most the upper limit is preferred in that the viscosity of the composition can be appropriately increased, ensuring good coatability.

[0119] The present composition is suitable for use in optical members used in at least a part of imaging devices such as cameras, and various display elements such as organic EL elements and liquid crystal display elements. In particular, when a cured product is formed using the present composition through heat treatment, a cured product having a desired microlens shape or planarizing film shape can be easily formed. Therefore, the composition is suitable for use as a radiation-sensitive composition for producing microlenses or planarizing films, particularly as a radiation-sensitive composition for producing microlenses by a thermal flow method.

[0120] ≪Cured product≫ The cured product of the present disclosure (hereinafter also referred to as the "present cured product") is a cured product of the present composition, and specifically, is formed by irradiating the present composition with radiation.

[0121] The shape of the cured product is not particularly limited, but is preferably a microlens or a planarizing film, more preferably a microlens, in order to better demonstrate the effects of the present invention. The present cured product is suitable for use as an optical component used in at least a portion of an imaging device such as a camera, or various display elements such as an organic electroluminescence (EL) element or a liquid crystal display element. That is, the present cured product is suitable for use as a material for optical components. Specifically, the present cured product can be suitable for use as an optical component such as a microlens for a solid-state imaging element included in an imaging device such as a camera, or as a microlens for various display elements such as an organic electroluminescence (OLED) element, a liquid crystal display element (LCD), or a μLED included in a display device. The present cured product can also be suitable for use as a planarizing film provided in an organic electroluminescence (EL) element, a liquid crystal display element, or the like.

[0122] The refractive index of the cured product at a wavelength of 550 nm is preferably 1.60 or more, more preferably 1.64 or more. A cured product having a refractive index within this range can be said to have a high refractive index, and is suitable for use as an optical component. Specifically, the refractive index can be measured by the method described in the examples below.

[0123] [Method of manufacturing the cured product] The method for producing the present cured product includes a step of irradiating the present composition with radiation. When irradiating with radiation, a mask having a predetermined pattern may be used, if necessary. After irradiation with radiation using the mask, development may be carried out, and after irradiation with radiation, a heat treatment may be carried out.

[0124] The present composition is particularly suitable as a negative pattern-forming material in which a pattern (i.e., a cured product formed from the present composition) is formed by exposing a portion of an organic film formed from the present composition to light and dissolving the unexposed portion of the exposed organic film in an alkaline developer, and then the pattern is fluidized by heat treatment to form a desired shape (e.g., a microlens shape, a planarized film shape).

[0125] Suitable examples of the method for producing the present cured product include the following first and second production methods.

[0126] <First manufacturing method> The first production method is a method including the following steps (I) to (III), and may further include the following steps (IV) and / or (V).

[0127] (Process (I): Coating process) Step (I) is a step of forming a coating film (organic film) on a substrate by applying the present composition onto the substrate.

[0128] Examples of the substrate include glass substrates, silicon wafers, plastic substrates, and substrates having colored resists, overcoats, anti-reflection films, various metal thin films, sealing films, etc. formed on their surfaces. Examples of plastic substrates include resin substrates (resin films) made of plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, and polyimide. The substrate may be provided with various elements (for example, a light receiving element such as a photodiode, or a light emitting element such as an organic light emitting diode) in advance.

[0129] The composition can be applied by any suitable method, such as spraying, roll coating, rotary coating (spin coating), slit die coating, bar coating, ink jetting, etc. Of these, spin coating, bar coating, and slit die coating are preferred.

[0130] After the composition is applied to a substrate, it may be preheated (prebaked) to prevent dripping, etc. The prebaking conditions can be appropriately set depending on the types and proportions of the components used in the composition, but can be, for example, at 60 to 130°C for about 30 seconds to 10 minutes.

[0131] The thickness of the coating film formed after pre-baking is preferably 0.1 to 20 μm, more preferably 0.2 to 15 μm.

[0132] (Step (II): Exposure step) Step (II) is a step of irradiating a part of the coating film formed in step (I) with radiation. This radiation 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 cured product having a desired shape (e.g., a microlens). The mask may be a multi-tone mask such as a halftone mask or a graytone mask.

[0133] Examples of radiation to be irradiated onto the coating film include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. Examples of ultraviolet rays include g-rays (wavelength 436 nm), i-rays (wavelength 365 nm), and KrF excimer laser light (wavelength 248 nm). X-rays include, for example, synchrotron radiation. An example of the charged particle beam is an electron beam. Of these, ultraviolet light is preferred, and ultraviolet light with a wavelength of 200 nm or more and 380 nm or less is more preferred. Examples of light sources used for irradiation include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, and excimer lasers. The radiation exposure is 500 to 50,000 J / m 2 (50-5,000mJ / cm 2 ) is preferred.

[0134] (Step (III): Development step) Step (III) is a step of forming a pattern on the substrate by developing the coating film and cured product obtained in step (II). This development step removes the coating film formed on the substrate in the unexposed areas, and a pattern (e.g., a relief pattern formed by a large number of regularly arranged micro-cured products) in which the cured product (micro-cured product) in the exposed areas remains can be formed on the substrate.

[0135] The developer may be an aqueous solution of an alkali (basic compound). Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane. The aqueous alkali solution may contain an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant, or may contain a small amount of any of various organic solvents capable of dissolving the present composition.

[0136] The concentration of the developer can be appropriately determined depending on the composition of the composition, but is usually from 0.01 to 10% by mass, and preferably from 0.5 to 5% by mass.

[0137] As the developing method, for example, a puddle method, a dipping method, a swing immersion method, a shower method, or the like can be used appropriately. The developing time may be adjusted appropriately depending on the composition of the present composition, but is, for example, 20 to 120 seconds.

[0138] After the development step, if necessary, a step of washing the developed patterned substrate with pure water or the like may be carried out. Furthermore, a step of drying the patterned substrate after development or after the cleaning may be carried out. The drying conditions are not particularly limited, but may be, for example, the same conditions as those for the pre-baking.

[0139] (Step (IV): heating step) Step (IV) is a step in which the developed pattern is heated and melted, and the pattern on the substrate is formed into a desired shape (for example, a microlens shape, a planarizing film shape) by a thermal flow method. The heat treatment in step (IV) allows the pattern formed in step (III) to undergo thermal flow while further curing the composition. In step (IV), for example, the minute cured product formed in step (III) can be formed into a lens (microlens) shape, thereby obtaining a microlens (array) in which minute hemispherical cured products are (regularly) arranged on a substrate.

[0140] The heat treatment can be carried out using a heating device such as an oven or a hot plate. The heating temperature in step (IV) may be appropriately selected depending on the substrate and the present composition used, but from the viewpoint of being applicable to high refractive index materials for organic electroluminescence devices, it is preferably 100° C. or lower, more preferably 95° C. or lower, and even more preferably 90° C. or lower. Furthermore, from the viewpoint of achieving high heat resistance and chemical resistance and being able to easily form a cured product in a desired shape, the heating temperature in step (IV) is preferably 60° C. or higher, more preferably 80° C. or higher. This composition can form a cured product in a desired shape even when heat treatment is carried out at a low temperature of 100° C. or less. By carrying out heat treatment at a low temperature of 100° C. or less, the composition can be used as a substrate for organic EL devices and the like that require low-temperature processing. The heating time can be set appropriately depending on the type of heating device, etc. For example, when heating is performed using a hot plate, the heating time is, for example, 5 to 60 minutes. When heating is performed using an oven, the heating time is, for example, 10 to 90 minutes. In the step (IV), a step bake method in which heat treatment is performed multiple times can also be used.

[0141] (Step (V): Post-exposure step) Step (V) is a step of further irradiating the cured product (e.g., microcured product) obtained after development in step (III) and / or the cured product (e.g., microlens) obtained in step (IV) with radiation. Among these, the step of further irradiating the cured product (e.g., microlens) obtained in step (IV) with radiation is preferred because it allows for easy formation of a cured product, particularly a microlens, in a desired shape by low-temperature thermal flow. By irradiating with radiation in step (V) (hereinafter also referred to as "post-exposure"), the heat resistance, chemical resistance, etc. can be further improved, and a highly reliable cured product, in particular a microlens, can be easily formed. The type of radiation and exposure conditions in the post-exposure can be the same as those in step (II), and the conditions for the wavelength, dose, and light source of the irradiated light in the post-exposure may be the same as or different from those in step (II).

[0142] <Second manufacturing method> The second manufacturing method includes a step of inkjet-coating the present composition on a substrate to form a pattern. In the second manufacturing method, a pattern of a desired shape (e.g., a spherical lens shape) may be formed directly on the substrate by inkjet coating. Alternatively, a pattern (e.g., a dot pattern) may be formed on the substrate by inkjet coating, and then step (IV) similar to that of the first manufacturing method may be performed to form a desired cured product. The second production method may also include a step similar to step (V) in the first production method.

[0143] The planarization film, which is one embodiment of the present cured product, can be produced by a method similar to that of the first production method, except that, for example, in step (II) of the first production method, a mask is not used or, for example, a pattern other than a dot pattern is used.

[0144] ≪Display device≫ The display device of the present disclosure is not particularly limited as long as it contains the present cured product, and may have any conventionally known configuration other than the inclusion of the present cured product. Examples of such display devices include liquid crystal displays (LCDs), organic light emitting diode (OLED)-based organic EL displays, μLED displays, electrochromic displays (ECDs), electroluminescent displays (ELDs), and quantum dot-organic EL (QD-OLED) displays.

[0145] <Imaging device> The imaging device of the present disclosure is not particularly limited as long as it includes the present cured product, and may have any conventionally known configuration other than the inclusion of the present cured product. Examples of such imaging devices include video cameras, digital cameras, mobile phones with camera functions, endoscopic cameras, capsule-type endoscopic cameras, microscopes, medical or healthcare cameras (e.g., cameras for taking images of blood vessels by receiving infrared light), in-vehicle cameras (e.g., cameras for taking images of the surroundings and interior of a vehicle, cameras for detecting the distance between vehicles), surveillance cameras, cameras for person authentication, and industrial cameras. [Example]

[0146] 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.

[0147] (Synthesis Example 1) Under a nitrogen atmosphere, cyanuric chloride (20 mmol) was added to a 300 mL two-necked flask, dissolved in N-methylpyrrolidone (NMP, 20 mL), and cooled to 0 °C in an ice bath. Next, a solution of aniline (monomer (I), 20 mmol) and N,N-diisopropylethylamine (60 mmol) in NMP (20 mL) was added dropwise to the cooled solution, ensuring that the internal temperature of the flask did not exceed 15 °C, and the mixture was stirred in the ice bath for an additional 15 minutes. Subsequently, a solution of p-aminobenzenethiol (monomer (II), 13.4 mmol) in NMP (10 mL) was added dropwise, ensuring that the internal temperature of the flask did not exceed 15 °C, and the mixture was stirred for 10 minutes. After stirring for 10 minutes, the flask was transferred to an oil bath, heated to 120 °C, and stirred for 3 hours. After stirring for 3 hours, a solution of aniline (end-capping monomer, 6.8 mmol) dissolved in NMP (8 mL) was added, and the mixture was heated and stirred for an additional 30 minutes. After stirring for 30 minutes, stirring and heating were stopped, and the resulting solution was added dropwise to ion-exchanged water (400 g) with stirring to cause reprecipitation. The resulting precipitate was filtered, washed with water and methanol, and dried in a vacuum dryer at 60°C for 6 hours to obtain the desired oligomer (polymer (A-1), 5.72 g).

[0148] [ka]

[0149] (Synthesis Examples 2 to 10, Synthesis Examples 12 to 26, and Comparative Synthesis Examples 1 to 3) The target oligomers (polymers (A-2) to (A-10), polymers (A-12) to (A-26), and comparative polymers (CA-1) to (CA-3)) were obtained in the same manner as in Synthesis Example 1, except that the types and amounts of the monomers used were changed to those shown in Table 1.

[0150] (Synthesis Example 11) An oligomer was obtained in the same manner as in Synthesis Example 6, except that 2-(4-aminophenyl)ethanol was used as the end-capping monomer instead of aniline. A 300 mL flask was charged with 5.81 g of the resulting oligomer, 2,4-di-tert-butylhydroquinone (0.0001 g), and THF (tetrahydrofuran, 40 mL). The atmosphere was replaced with nitrogen and the mixture was stirred to dissolve the oligomer. The internal temperature of the flask was then raised to 60°C, and 2-isocyanatoethyl acrylate (1.9 g) was added. After stirring for 3 hours, the reaction solution was added dropwise to ion-exchanged water (400 g) with stirring to reprecipitate. The resulting precipitate was filtered, washed with water and methanol, and dried in a vacuum dryer at 60°C for 6 hours to obtain the desired oligomer (polymer (A-11), 5.56 g).

[0151] [Polymer evaluation] The properties of the polymers prepared in Synthesis Examples 1 to 26 and Comparative Synthesis Examples 1 to 3 were evaluated as follows. The evaluation results are shown in Table 1.

[0152] <Evaluation of weight average molecular weight> The weight average molecular weight (Mw) of each prepared polymer is a polystyrene equivalent value measured by gel permeation chromatography (GPC) under the following conditions. Column: TSKgel GRCXLII, manufactured by Tosoh Corporation Solvent: tetrahydrofuran Temperature: 40℃ Pressure: 68kgf / cm 2

[0153] <Evaluation of refractive index> Each prepared polymer was dissolved in an appropriate amount of NMP, and the solution was applied to an alkali-free glass substrate using a spinner, followed by heating on a hot plate at 100°C for 3 minutes and then on a hot plate at 150°C for 30 minutes to obtain a polymer film. The refractive index of the obtained polymer film at a wavelength of 550 nm was measured using a rotational compensator spectroscopic ellipsometer SE-2000 (manufactured by emilab Semiconductor Physics Laboratory Co. Ltd.) and evaluated according to the following criteria. Evaluation criteria AA: Refractive index ≧ 1.69 BB:1.69>Refractive index≧1.63 CC: Refractive index <1.63

[0154] <Evaluation of solubility> Propylene glycol monomethyl ether acetate (PGMEA) was added to each prepared polymer so that the solid content concentration of the polymer became 10% by mass, and then the mixture was stirred at room temperature (25°C) for 6 hours. The mixture was then allowed to stand, and the solution was observed and evaluated according to the following evaluation criteria. Evaluation criteria AA: The solution was clear and no turbidity was observed. BB: The solution became cloudy.

[0155] [Table 1]

[0156] The "equivalent" in the column for each monomer in Table 1 indicates the amount (equivalent) of each monomer used when the amount of cyanuric chloride used in synthesizing each polymer is taken as 1 equivalent.

[0157] [Preparation of Radiation-Sensitive Composition] In the examples and comparative examples, the components (B), (C), and solvent (E) used in preparing the radiation-sensitive compositions are shown in detail below.

[0158] <Photopolymerization initiator (B)> B-1: 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)] (Irgacure OXE01, manufactured by BASF) B-2: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[0159] <Polymerizable compound (C)> C-1: Bisphenol A ethoxylate diacrylate C-2: 3-phenoxybenzyl acrylate C-3: Dipentaerythritol hexaacrylate C-4: Ethylene oxide-modified dipentaerythritol polyacrylate (A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.) C-5: 1,9-nonanediol diacrylate

[0160] <Solvent (E)> E-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0161] Example 1 A PGMEA solution (solids concentration 30% by mass) containing 100 parts by mass of polymer (A-1), 25 parts by mass of polymerizable compound (C-1), 15 parts by mass of polymerizable compound (C-2), 5 parts by mass of photopolymerization initiator (B-1), 0.5 parts by mass of adhesion promoter (3-methacryloyloxypropyltrimethoxysilane), 0.1 parts by mass of antioxidant (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]), and 0.2 parts by mass of surfactant ("FTX-218" manufactured by NEOS Co., Ltd.) was mixed, and solvent (E-1) was added to a solids concentration of 35% by mass, followed by stirring to dissolve each component. The resulting mixture was then filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[0162] (Examples 2 to 32 and Comparative Examples 1 to 3) Radiation-sensitive compositions were prepared in the same manner as in Example 1, except that the types and amounts of each component were changed as shown in Table 2.

[0163] [Evaluation of Radiation-Sensitive Composition] The properties of the radiation-sensitive compositions prepared in Examples 1 to 32 and Comparative Examples 1 to 3 were evaluated as follows. The evaluation results are shown in Table 2.

[0164] <Evaluation of solubility> The prepared radiation-sensitive composition was stirred at room temperature (25°C) for 1 hour, and then allowed to stand. The radiation-sensitive composition was observed and evaluated according to the following evaluation criteria.

[0165] Evaluation criteria AA: The radiation-sensitive composition was transparent and no turbidity was observed. BB: The radiation-sensitive composition was cloudy.

[0166] <Evaluation of precipitation upon dilution> The prepared radiation-sensitive composition was diluted 3 times, 10 times, or 50 times by mass with PGMEA and thoroughly stirred at room temperature (25°C). The diluted solution was visually observed, and the presence or absence of precipitation of the components constituting the radiation-sensitive composition due to dilution was evaluated according to the following evaluation criteria. AA: The diluted solution was transparent and no cloudiness was observed at any dilution ratio. BB: Any of the diluted solutions was cloudy.

[0167] <Patterning ability> Each of the prepared radiation-sensitive compositions was applied onto a non-alkali glass substrate using a spinner, and then pre-baked on a hot plate at 85°C for 3 minutes to form a coating film with a thickness of 9.0 µm. Next, the resulting coating film was exposed to light using a 1:1 projection exposure device (high-pressure mercury lamp; illuminance at 365 nm: approximately 500 mW / cm) through a photomask having a circular pattern with a diameter of 20 μm. 2 ) to 200-900mJ / cm 2 in the range of 100 mJ / cm 2 The radiation exposure was carried out by changing the exposure dose step by step. The substrate was then developed at 25°C using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C as the developer by the puddle method for 60 seconds, followed by rinsing with pure water for 60 seconds. The substrate was then dried, forming a pattern consisting of multiple microscopic bodies formed by the radiation-sensitive composition on the substrate (an enlarged photograph of the pattern is shown in Figure 1(a)). After development, the substrate was observed under an optical microscope, and the substrate with the least residue and pattern peeling among those obtained by irradiating with radiation at different exposure doses was evaluated for patterning ability according to the following evaluation criteria. Note that when the polymer (A) did not have an alkali-soluble group (was not soluble in an alkaline developer), evaluation of patterning ability was not performed. Thereafter, post-baking was carried out in an oven at 85°C for 40 minutes, and a pattern having a plurality of lens shapes formed by the radiation-sensitive composition was formed on the substrate (an enlarged photograph of the pattern at this stage is shown in Figure 1(b)). Evaluation criteria AA: No residue other than the pattern was observed on the substrate, and almost no pattern peeling was observed. BB: Residue other than the pattern or slight peeling of the pattern was observed on the substrate. CC: Residues other than the pattern were observed on most of the substrate, or the pattern was peeled off and almost no pattern remained on the substrate.

[0168] <Lens formation> Each of the prepared radiation-sensitive compositions was applied onto a non-alkali glass substrate using a spinner, and then pre-baked on a hot plate at 85°C for 3 minutes to form a coating film with a thickness of 9.0 µm. Next, the resulting coating film was exposed to light using a 1:1 projection exposure device (high-pressure mercury lamp; illuminance at 365 nm: approximately 500 mW / cm) through a photomask having a line pattern with a line width of 30 μm (space of 30 μm). 2 ) at 200, 300, 500, 700, 1,000, or 1,500 mJ / cm 2 The radiation exposure was carried out at each exposure dose. Thereafter, each of the substrates irradiated with radiation at each exposure dose was developed for 60 seconds by the puddle method at 25°C using a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23°C as a developer, followed by rinsing with pure water for 60 seconds. The substrates were then dried, thereby forming a plurality of line patterns formed on the substrates from the radiation-sensitive composition. Each substrate on which the line pattern was formed was then post-baked for 40 minutes in an oven at 85°C. The cross-section of the pattern on each substrate (a cross-section in a direction approximately perpendicular to the length of the line pattern) was then observed with an optical microscope, and the lens formability was evaluated according to the following evaluation criteria. Note that when the polymer (A) did not have an alkali-soluble group (was not soluble in an alkaline developer), evaluation of the lens formability was not performed. When the evaluation result is "AA", it is thought that the line pattern (especially the upper part of the line pattern on the opposite side from the substrate), which had a rectangular cross section, has reflowed due to post-baking, causing the cross section of the pattern to become semicircular. In this evaluation, a line pattern was formed, but when the evaluation result is "AA", it is highly likely that lenses (microlenses) can be formed by forming a dot pattern. Evaluation criteria AA: Among the patterns on the obtained substrates (substrates obtained after post-baking by irradiating with radiation at each exposure dose), the cross section of the pattern after post-baking on at least one substrate was semicircular. BB: Of the obtained substrates (post-baked substrates obtained by irradiating with radiation at each exposure dose), the cross section of the pattern after post-baking on all substrates was rectangular.

[0169] <Evaluation of refractive index> Each of the prepared radiation-sensitive compositions was applied to a non-alkali glass substrate using a spinner, and then prebaked on a hot plate at 100°C for 3 minutes to form a coating film with a thickness of 9.0 μm. The resulting coating film was then irradiated with a high-pressure mercury lamp (illuminance at 365 nm: approximately 500 mW / cm). 2 ) at 500mJ / cm 2The substrate was then exposed to radiation at an exposure dose of 1000 ppm. Development was then performed at 25°C using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C as the developer by the puddle method for 60 seconds, followed by rinsing with pure water for 60 seconds, and then drying the substrate. This was followed by post-baking in an oven at 85°C for 40 minutes to form a cured film. The refractive index of the resulting cured film at a wavelength of 550 nm was measured using a rotational compensator spectroscopic ellipsometer SE-2000 (manufactured by emilab Semiconductor Physics Laboratory Co. Ltd.), and evaluated according to the following criteria.

[0170] Evaluation criteria AA: Refractive index ≧ 1.64 BB:1.64>Refractive index≧1.60

[0171] [Table 2]

Claims

1. Component (A): a polymer having a partial structure represented by the following formula (1), Component (B): a photopolymerization initiator; Component (C): a polymerizable compound and A radiation-sensitive composition comprising: 【Chemistry 1】 In formula (1), Ar is a divalent organic group containing either one or both of an aromatic ring and a heterocyclic ring, X 1 and X 2 are each independently S or NR (R is a hydrogen atom or a monovalent organic group), and X 1 and X 2 At least one of is S, * represents a bond.

2. 2. The radiation-sensitive composition according to claim 1, wherein Ar in the formula (1) is at least one selected from the group represented by the following formulas (Ar-1) to (Ar-20): 【Chemistry 2】 [In the formula, R 1 ~R 12 each independently represents a hydrogen atom, a halogen atom, an acidic group, an alkyl group having 1 to 10 carbon atoms which may have a branched structure, or an alkoxy group having 1 to 10 carbon atoms which may have a branched structure, R 13 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a branched structure, W 1 and W. 2 each independently represents a single bond, CR 14 R 15 (R 14 and R 15 each independently represents a hydrogen atom or a monovalent organic group (wherein R 14 and R 15 may be bonded to each other to form a ring. ) C=O, O, S, SO, SO 2 , or N.R. 16 (R 16 is a hydrogen atom or a monovalent organic group; Z 1 and Z 2 each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms which may have a branched structure, or a group represented by the following formula (Z-1): * represents a bond. 【Chemistry 3】 [In the formula, R 21 ~R 24 each independently represents a hydrogen atom, a halogen atom, an acidic group, an alkyl group having 1 to 10 carbon atoms which may have a branched structure, or an alkoxy group having 1 to 10 carbon atoms which may have a branched structure, Y 1 and Y 2 each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms which may have a branched structure. * represents a bond.

3. In the formula (1), X 1 and X 2 2. The radiation-sensitive composition according to claim 1, wherein one of the above is S and the other is NR (R is a hydrogen atom or a monovalent organic group).

4. 2. The radiation-sensitive composition according to claim 1, wherein the polymer having the partial structure represented by formula (1) has a weight average molecular weight of 500 to 5,000.

5. The radiation-sensitive composition according to claim 1 , wherein the partial structure represented by formula (1) is a partial structure represented by formula (2): 【Chemistry 4】 [In formula (2), Ar, X 1 and X 2 has the same meaning as the same symbol in formula (1), X 3 is S, O, or NR' (R' is a hydrogen atom or a monovalent organic group); A is an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group containing either or both of an aromatic ring and a heterocyclic ring, * represents a bond.

6. 2. The radiation-sensitive composition according to claim 1, wherein the polymer having the partial structure represented by formula (1) has a refractive index of 1.63 or more at light having a wavelength of 550 nm.

7. 2. The radiation-sensitive composition according to claim 1, wherein the polymer having the partial structure represented by formula (1) is soluble in propylene glycol monomethyl ether acetate (PGMEA) at 25°C in an amount of 10% by mass or more.

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

9. A cured product obtained by curing the radiation-sensitive composition according to any one of claims 1 to 8.

10. The cured product according to claim 9, having a refractive index of 1.60 or more at a wavelength of 550 nm.

11. The cured product according to claim 9 , which is for use as an optical member.

12. A display device comprising the cured product according to claim 9.

13. An imaging device comprising the cured product according to claim 9.

14. A step of applying the radiation-sensitive composition according to any one of claims 1 to 8 onto a substrate; a step of exposing the radiation-sensitive composition applied onto the substrate to radiation; developing the radiation-sensitive composition after irradiation; A method for producing a cured product comprising the steps of:

15. The method for producing a cured product according to claim 14, further comprising a step of heating the radiation-sensitive composition after development.

16. The method for producing a cured product according to claim 15, wherein the heating temperature in the step of heating the radiation-sensitive composition after development is 100°C or lower.

17. The method for producing a cured product according to claim 15 , wherein the pattern is melted to form a microlens by a step of heating the developed radiation-sensitive composition.

18. A polymer having a partial structure represented by the following formula (1): 【Chemistry 5】 In formula (1), Ar is a divalent organic group containing either one or both of an aromatic ring and a heterocyclic ring, X 1 and X 2 are each independently S or NR (R is a hydrogen atom or a monovalent organic group), and X 1 or X 2 is S, * represents a bond.

19. The polymer according to claim 18, having a refractive index of 1.63 or more for light with a wavelength of 550 nm.

20. The polymer according to claim 18, which has a solubility of 10% by mass or more in propylene glycol monomethyl ether acetate (PGMEA) at 25°C.

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