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

Abstract

The invention provides a radiation-sensitive composition, a cured product, a display device, an imaging device, a method for producing the cured product, and a polymer, wherein the radiation-sensitive composition has a high refractive index and excellent solubility in a general-purpose solvent, and precipitation when the radiation-sensitive composition is diluted by the general-purpose solvent is not easy to occur. The invention also provides the cured product, the display device, the imaging device, the method for producing the cured product, and the polymer. A radiation-sensitive composition comprising a component (A) which is a polymer having a partial structure represented by formula (1), a component (B) which is a photopolymerization initiator, and a component (C) which is a polymerizable compound (in formula (1), Ar is a divalent organic group including either or both an aromatic ring and a heterocyclic ring, X1 and X2 are each independently S or NR (R is a hydrogen atom or a monovalent organic group), at least one of X1 and X2 is S, X2 is a hydrogen atom or a monovalent organic group, X3 is a monovalent organic group, X4 is a hydrogen atom or a monovalent organic group, and N4 is a hydrogen atom or a monovalent organic group). And * represents a bond). # imgabs0 #

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 Art

[0002] For example, a high refractive index is sometimes required for optical components such as high-function substrates for display devices, (interlayer) insulating films, protective films, planarizing films, optical adhesives, antireflection films, sealing materials, and microlenses for complementary metal oxide semiconductor (CMOS) or charge coupled device (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.

[0004] As such a composition containing a polymer having a high refractive index, for example, Patent Documents 1 and 2 disclose compositions containing a polymer containing a triazine ring.

[0005] [Prior art literature]

[0006] [Patent Document]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2018-107347

[0008] [Patent Document 2] International Publication No. 2017 / 138547 Summary of the invention

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

[0010] The optical member is often formed of the radiation-sensitive composition because the optical member can be easily formed into a desired shape.

[0011] In view of the handling properties during production of optical members, uniform optical member formation, safety, etc., such radiation-sensitive compositions often use general-purpose organic solvents (hereinafter also referred to as "general-purpose solvents") such as propylene glycol monomethyl ether acetate.

[0012] However, it is known that the 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 universal solvent.

[0013] In addition, when manufacturing the optical member, the radiation-sensitive composition (including the radiation-sensitive composition already containing the solvent) may be diluted with the universal solvent before use. However, it is known that when the radiation-sensitive composition containing a high-refractive index polymer is diluted with the universal solvent, the components (especially the high-refractive index polymer) contained in the radiation-sensitive composition are likely to precipitate during the dilution (hereinafter also referred to as "precipitation during dilution with the universal solvent").

[0014] The present invention has been made in view of the above, and one object of the present invention is to provide a polymer and a radiation sensitive composition which have a high refractive index, are excellent in solubility in a universal solvent, and are unlikely to precipitate when diluted with a universal solvent.

[0015] [Technical means to solve the problem]

[0016] The present inventors have found that the above-mentioned problems can be solved by the following structural examples. That is, according to the present invention, the following radiation-sensitive composition, cured product, display device, imaging device, method for producing a cured product, and polymer can be provided.

[0017] The following shows a configuration example of the present disclosure.

[0018] [1] A radiation sensitive composition comprising (A) a polymer having a partial structure represented by the following formula (1),

[0019] (B) Component: photopolymerization initiator, and

[0020] (C) Component: polymerizable compound.

[0021] [Chemistry 1]

[0022]

[0023] [In formula (1), Ar is a divalent organic group containing either or both of an aromatic ring and a heterocyclic ring,

[0024] X 1 and X 2 are independently S or NR (R is a hydrogen atom or a monovalent organic group), X 1 and X 2 At least one of is S,

[0025] * indicates a bonding bond〕

[0026] [2] The radiation sensitive composition according to [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).

[0027] [Chemistry 2]

[0028]

[0029] 〔In the 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,

[0030] R 13 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a branched structure,

[0031] W 1 and W 2 are independently single bonds, CR 14 R 15 (R 14 and R 15 are independently a hydrogen atom or a monovalent organic group (wherein R 14 and R 15 Can bond 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),

[0032] 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);

[0033] * indicates a bonding bond〕

[0034] [Chemistry 3]

[0035]

[0036] 〔In the 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,

[0037] Y 1 and Y 2 Each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms and may have a branched structure;

[0038] * indicates a bonding bond〕

[0039] [3] The radiation sensitive composition according to [1] or [2], wherein in the formula (1), X 1 and X 2One of them is S, and the other is NR (R is a hydrogen atom or a monovalent organic group).

[0040] [4] The radiation sensitive composition according to any one of [1] to [3], wherein the weight average molecular weight of the polymer having the partial structure represented by the formula (1) is 500 to 5,000.

[0041] [5] The radiation sensitive composition according to any one of [1] to [4], wherein the partial structure represented by the formula (1) is a partial structure represented by the following formula (2).

[0042] [Chemistry 4]

[0043]

[0044] [In formula (2), Ar, X 1 and X 2 The same symbols as in formula (1) have the same meanings,

[0045] X 3 is S, O or NR' (R' is a hydrogen atom or a monovalent organic group),

[0046] 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,

[0047] * indicates a bonding bond〕

[0048] [6] The radiation sensitive composition according to any one of [1] to [5], wherein the polymer having the partial structure represented by the formula (1) has a refractive index of 1.63 or more at a wavelength of 550 nm.

[0049] [7] The radiation sensitive composition according to any one of [1] to [6], wherein the polymer having the partial structure represented by the formula (1) is dissolved in propylene glycol monomethyl ether acetate (PGMEA) at 25° C. at a concentration of 10% by mass or more.

[0050] [8] The radiation sensitive composition according to any one of [1] to [7], which is used for producing a microlens by a heat flow method.

[0051] [9] A cured product obtained by curing the radiation sensitive composition according to any one of [1] to [8].

[0052]

[10] The cured product according to [9], wherein the refractive index of the cured product under light having a wavelength of 550 nm is 1.60 or more.

[0053]

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

[10] , which is used for optical components.

[0054]

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

[11] .

[0055]

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

[11] .

[0056]

[14] A method for producing a cured product, comprising: applying the radiation-sensitive composition according to any one of [1] to [8] onto a substrate;

[0057] a step of irradiating the radiation-sensitive composition coated on the substrate with radiation; and

[0058] A step of developing the radiation-sensitive composition after irradiation with radiation.

[0059]

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

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

[0060]

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

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

[0061]

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

[15] or

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

[0062]

[18] A polymer having a partial structure represented by the following formula (1).

[0063] [Chemistry 5]

[0064]

[0065] [In formula (1), Ar is a divalent organic group containing either or both of an aromatic ring and a heterocyclic ring,

[0066] X 1 and X 2 are independently S or NR (R is a hydrogen atom or a monovalent organic group), X 1 and X 2 One of them is S,

[0067] * indicates a bonding bond〕

[0068]

[19] The polymer according to

[18] , wherein the refractive index of the polymer under light having a wavelength of 550 nm is 1.63 or more.

[0069]

[20] The polymer according to

[18] or

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

[0070] [Effects of the Invention]

[0071] The present invention provides a polymer and a radiation sensitive composition which have a high refractive index, are excellent in solubility in a general-purpose solvent (particularly PGMEA), and are unlikely to precipitate when diluted with a general-purpose solvent (particularly PGMEA).

[0072] In addition, as the general solvent, for example, PGMEA, propylene glycol monomethyl ether (PGME), 3-methoxypropionic acid methyl ester, propylene glycol n-propyl ether, butyl acetate, ethyl lactate, 3-methoxypropionic acid ethyl ester, methoxybutyl acetate, ethylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether can be listed. It can be said that the polymer and radiation-sensitive composition with excellent solubility for PGMEA have a tendency to also have excellent solubility for general solvents other than these PGMEA.

[0073] According to the radiation-sensitive composition of one embodiment of the present invention, a high-refractive-index cured product (e.g., microlens and planarized film), particularly a microlens, can be easily formed into a desired shape by fluidization (heat flow) caused by heating at a low temperature. Such a radiation-sensitive composition of one embodiment of the present invention is suitable for use in microlens manufacturing or planarized film formation.

[0074] Furthermore, the radiation sensitive composition according to one embodiment of the present invention can be made developer-soluble, particularly alkali-soluble, and the developer-soluble radiation sensitive composition can be excellent in pattern forming properties and in forming a cured product of a desired shape such as a microlens. BRIEF DESCRIPTION OF THE DRAWINGS

[0075] Figure 1 (a) and (b) are magnified photographs of microlens patterns obtained in the patterning test of the following example observed from the front. Figure 1 (a) is the state before post-baking, Figure 1 (b) shows the state after post-baking. DETAILED DESCRIPTION

[0076] Hereinafter, matters related to the embodiment will be described in detail. In addition, in this specification, the numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower limit and the upper limit.

[0077] In the present specification, the term "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

[0078] The term "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and / or a branched hydrocarbon group that does not include a cyclic structure in the main chain but consists only of a chain structure, and may be saturated or unsaturated.

[0079] The so-called "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only the structure of an alicyclic hydrocarbon as a ring structure and does not contain an aromatic ring structure. It is not necessary to be composed only of the structure of an alicyclic hydrocarbon, and a group having a chain structure in a part thereof is also included. In addition, the structure of the alicyclic hydrocarbon may be a single ring or a condensed ring.

[0080] The so-called "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. It is not necessary to be composed of only an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may be contained in part thereof. In addition, the aromatic ring structure may be a monocyclic ring or a condensed ring. In addition, the ring structure possessed by the alicyclic hydrocarbon group and the aromatic hydrocarbon group may also have a hydrocarbon group as a substituent.

[0081] In addition, in this specification, "(meth)acrylic acid" includes "acrylic acid" and "methacrylic acid". "(Meth)acryloyl" includes "acryloyl" and "methacryloyl". The so-called "alkali soluble" means that it can be dissolved or swelled in a 2.38 mass% concentration of tetramethylammonium hydroxide aqueous solution at 25°C.

[0082] 《Radiosensitive composite material》

[0083] The radiation sensitive composition of the present disclosure (hereinafter also referred to as "the present composition") contains the following components (A), (B) and (C). In addition, each component may be used alone or in combination of two or more unless otherwise specified.

[0084] Component (A): A polymer having a partial structure represented by the following formula (1)

[0085] Component (B): Photopolymerization initiator

[0086] (C) Component: polymerizable compound

[0087] "polymer"

[0088] The polymer disclosed in the present invention is a polymer having a partial structure represented by the following formula (1).

[0089] Hereinafter, a polymer having a partial structure represented by the following formula (1) is also referred to as "polymer (1)".

[0090] [Chemistry 6]

[0091]

[0092] [In formula (1), Ar is a divalent organic group containing either or both of an aromatic ring and a heterocyclic ring, and X 1 and X 2 are independently S or NR (R is a hydrogen atom or a monovalent organic group), X 1 and X 2 At least one of them is S, * represents a bonding bond]

[0093] [Polymer (1)]

[0094] The polymer (1) is a polymer having a partial structure represented by formula (1), and is a polymer containing a repeating unit having a triazine ring structure.

[0095] Such a polymer (1) has a high refractive index and excellent solubility in a general-purpose solvent (particularly PGMEA). Furthermore, by using such a polymer (1), it is possible to easily obtain the present composition which is less likely to precipitate when diluted with a general-purpose solvent.

[0096] In the above formula (1), the aromatic ring and heterocyclic ring possessed by Ar may be a monocyclic ring or a condensed ring.

[0097] As Ar, in terms of achieving a high refractive index and improving solubility in general solvents (especially PGMEA), it is preferably at least one selected from the group represented by the following formulas (Ar-1) to (Ar-20), and more preferably at least one selected from the group represented by the following formulas (Ar-1), (Ar-4), (Ar-19) and (Ar-20). Considering the ease of obtaining the raw material compounds or the ease of synthesis of the polymer (1), it is further preferably at least one selected from the group represented by the following formulas (Ar-1) and (Ar-19).

[0098] [Chemistry 7]

[0099]

[0100] In the formula, R 1 ~R 12 Each of them is 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.

[0101] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0102] Examples of the acidic group include a carboxyl group, a carboxyalkoxy group, a sulfonic acid group, a phenolic hydroxyl group, a thiol group, an imidazole group, a triazole group, a tetrazolyl group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfonamide group, a maleimide group, a silanol group, and a hydroxyalkyl group in which a hydrogen atom bonded to a carbon atom is substituted with an electron withdrawing group.

[0103] Examples of the alkyl group having 1 to 10 carbon atoms 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, a sec-butyl group, a tert-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-n-butyl group, a Methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1 -ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-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, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, and the like.

[0104] The number of carbon atoms in the alkyl group is preferably 1 to 8, and more preferably 1 to 3, from the viewpoint of achieving both refractive index and solubility. The structure may be a chain structure or may have a branched structure.

[0105] Examples of the alkoxy group having 1 to 10 carbon atoms and which may have a branched structure include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy and the like.

[0106] The number of carbon atoms in the alkoxy group is preferably 1 to 8, and more preferably 1 to 3, from the viewpoint of achieving both refractive index and solubility. The structure may be a chain structure or may have a branched structure.

[0107] R 13 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a branched structure. Examples of the alkyl group include the same groups as those exemplified above.

[0108] W 1 and W 2 are independently single bonds, CR 14 R 15 , C=O, O, S, SO, SO2 or NR 16 , R 14 ~R 16 are independently a hydrogen atom or a monovalent organic group. 14 and R 15 They may bond with each other to form a ring.

[0109] Specific examples of the monovalent organic group include an alkyl group, an alkoxy group, an aryl group, and an aralkyl group which may have a substituent. Examples of the alkyl group and the alkoxy group include the same groups as those described above.

[0110] 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.

[0111] The carbon number of 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.

[0112] Specific examples of the aryl group include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-hydroxyphenyl, m-hydroxyphenyl, p-hydroxyphenyl, o-carboxyphenyl, m-carboxyphenyl, p-carboxyphenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl.

[0113] The carbon number of 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.

[0114] Specific examples of the aralkyl group include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, and α-naphthylmethyl.

[0115] Z 1 and Z 2 Each of them is 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).

[0116] 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.

[0117] [Chemistry 8]

[0118]

[0119] In the formula, R 21 ~R 24 Each of them is 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. Examples of the halogen atom, the acidic group, the alkyl group, and the alkoxy group include the same atoms or groups as those mentioned above.

[0120] Y 1 and Y 2 Each of them is independently a single bond or an alkylene group having 1 to 10 carbon atoms and optionally having a branched structure, and examples of the alkylene group include the same groups as those exemplified above.

[0121] In the above formula (Ar-1) to (Ar-20), * represents1 or X 2 The bond key.

[0122] About Ar and X 1 and X 2 The two bonding bonds are bonded to the same ring (for example, the formula (Ar-1), formula (Ar-5), formula (Ar-7), formula (Ar-9), formula (Ar-13) to formula (Ar-20)). The positional relationship of the two bonding bonds can be any of the so-called ortho, meta, and para positions. When they are located at the ortho position, there is a tendency that a polymer with excellent solubility in a general solvent can be easily obtained, so it is preferred.

[0123] Specific examples of Ar include groups represented by the following formulae, but are not limited to these.

[0124] [Chemistry 9]

[0125]

[0126] In the formula (1), X 1 and X 2 Each independently represents S or NR (R represents a hydrogen atom or a monovalent organic group). Examples of the monovalent organic group include the same groups as those exemplified above.

[0127] In the above formula (1), X is preferably selected from the following aspects: a polymer having excellent solubility in a general solvent (particularly PGMEA) can be easily obtained; and a composition which is less likely to precipitate when diluted with a general solvent (particularly PGMEA) can be easily obtained by using the above polymer. 1 and X 2 At least one of is S, preferably X 1 and X 2 One of them is S and the other is NR.

[0128] The partial structure represented by the formula (1) is preferably a partial structure represented by the following formula (2).

[0129] The polymer having the partial structure represented by the following formula (2) can be made into a chain polymer, rather than a so-called hyperbranched polymer like the polymer described in Patent Document 2.

[0130] [Chemistry 10]

[0131]

[0132] In the formula (2), Ar, X 1 and X 2The same symbols as in the above formula (1) have the same meanings, and * represents a bonding bond.

[0133] 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 mentioned above.

[0134] X 3 It is preferably NR', and more preferably NH.

[0135] In order to obtain the present composition being soluble in developer, particularly alkali-soluble, R' is preferably a group having an acidic group. Examples of the group having an acidic group include o-hydroxyphenyl, m-hydroxyphenyl, p-hydroxyphenyl, o-carboxyphenyl, m-carboxyphenyl and p-carboxyphenyl.

[0136] 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.

[0137] In consideration of further improving the solubility in a general-purpose solvent (particularly PGMEA), the alkyl group having 1 to 20 carbon atoms in A preferably has 3 to 18 carbon atoms, and more preferably has 6 to 16 carbon atoms.

[0138] Specific examples of the alkyl group having 1 to 20 carbon atoms include the same groups as those described above for the alkyl group having 1 to 10 carbon atoms which may have a branched structure.

[0139] Examples of the monovalent organic group containing either or both of an aromatic ring and a heterocyclic ring in A include a group in which one of the two bonding bonds in Ar is replaced by a substituent R 30 The basis formed.

[0140] R 30 is a hydrogen atom, a halogen atom, an acidic group, a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms and optionally having a branched structure, or a group in which a part of the hydrocarbon group is substituted with at least one selected from an oxygen atom, a nitrogen atom and a sulfur atom. 30 For example, a substituent obtained by reacting a hydroxyl group with 2-isocyanatoethyl (meth)acrylate or the like, or a reactive group such as a (meth)acryloyl group may be introduced via the substituent group (eg, hydroxyl group, acidic group).

[0141] As R 30 Specific examples include R 1 ~R 12 The specific examples of are the same atoms or groups.

[0142] As A, it is preferred that one of the two bonding bonds in the formula (Ar-1) is substituted with the substituent R 30 The base represented by the base formed by .

[0143] In terms of obtaining developer-soluble, particularly alkali-soluble, compositions 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 o-hydroxyphenyl, m-hydroxyphenyl, p-hydroxyphenyl, o-carboxyphenyl, m-carboxyphenyl, and p-carboxyphenyl.

[0144] Preferred specific examples of the partial structure represented by the formula (1) include structures represented by the following formulae, but the present invention is not limited to these.

[0145] [Chemistry 11]

[0146]

[0147] The polymer (1) is preferably a polymer represented by the following formula (3) because it is easy to form a polymer having a high refractive index and excellent solubility in a general solvent. The polymer represented by the following formula (3) can be said to be a chain polymer, not a hyperbranched polymer.

[0148] [Chemistry 12]

[0149]

[0150] In the formula (3), A, Ar, X 1 ~X 3 The same symbols as in the above formula (2) have the same meanings.

[0151] Y in the formula (3) is a terminal structure, and examples thereof include the same groups as those for A. Specifically, examples thereof include structures derived from the following terminal blocking monomers.

[0152] In the formula (3), X is S or NR (R is a hydrogen atom or a monovalent organic group), preferably NR. Examples of R include the same groups as those mentioned above as specific examples.

[0153] In terms of obtaining the present composition soluble in developer, particularly alkali soluble, A, Ar, X, X 1 ~X 3 At least one of Y is preferably a group having an acidic group.

[0154] In the formula (3), n is the number of repeating units, and is preferably a number that allows the weight average molecular weight (Mw) of the polymer represented by the formula (3) to be within the following range.

[0155] The weight average molecular weight (Mw) of the polymer (1) in terms of polystyrene obtained by gel permeation chromatography (GPC) is preferably 500 to 5,000, more preferably 700 to 4,800, and even more preferably 1,000 to 4,600.

[0156] The polymer having an Mw within the above range can be said to be substantially an oligomer, and can easily form a cured product having excellent solubility in a general solvent (particularly PGMEA) and excellent heat resistance and chemical resistance.

[0157] The polymer having 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) and the following monomer (II).

[0158] Specifically, the Mw can be measured by the method described in the following Examples.

[0159] The refractive index of the polymer (1) at a wavelength of 550 nm is preferably 1.63 or more, more preferably 1.69 or more, further preferably 1.70 or more, particularly preferably 1.73 or more, and most preferably 1.75 or more.

[0160] 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 members and the like.

[0161] Specifically, the refractive index can be measured by the method described in the following Examples.

[0162] The polymer (1) is preferably soluble in PGMEA at 25° C. at 10% by mass or more, more preferably soluble in PGMEA at 20% by mass or more, and even more preferably soluble in PGMEA at 30% by mass or more.

[0163] When the solubility in PGMEA is at least the above lower limit, the solubility in a general-purpose solvent can be said to be excellent, and by using such a polymer, the present composition which is unlikely to cause precipitation when diluted with a general-purpose solvent (particularly PGMEA) can be easily obtained.

[0164] Specifically, the solubility can be measured by the method described in the following Examples.

[0165] The polymer (1) can be synthesized, for example, by a method comprising the following step (I) and step (II).

[0166] Step (I): A trihalogenated triazine compound such as cyanuric chloride is reacted with a compound having a group selected from an amino group (-NR'2 [the same symbol as in formula (2) has the same meaning]), a thiol group and a hydroxyl group (hereinafter also referred to as "monomer (I)") in an organic solvent.

[0167] Step (II): After reacting the obtained dihalogenated triazine compound with a compound having two groups selected from an amino group (-NR2) and a thiol group (wherein at least one of the groups is a thiol group) (hereinafter also referred to as "monomer (II)") in an organic solvent, it is reacted with a capping agent (hereinafter also referred to as "capping monomer") to stop the polymerization reaction.

[0168] 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.

[0169] 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.

[0170] The step (I) can be performed at preferably -10°C to 30°C, more preferably 0°C to 5°C.

[0171] 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, bismuthiothiol, and 1,5-naphthalenedithiol.

[0172] 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.

[0173] Examples of the terminal blocking monomer include aniline, 2,5-dimethoxyaniline, o-aminophenol, m-aminophenol, 2-(4-aminophenyl)ethanol, hexylamine, hexylmercaptan, benzenemercaptan, and p-toluenemercaptan.

[0174] 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.

[0175] The steps (I) and (II) are preferably performed in the presence of a base.

[0176] Examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, 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.

[0177] The step (II) can be performed preferably at 0°C to 130°C, and more preferably at 40°C to 80°C from an industrial viewpoint.

[0178] The organic solvent used in the step (I) and the step (II) is not particularly limited, and examples thereof include the same organic solvents as exemplified as the solvent (E) described below.

[0179] The organic solvent used in the step (I) may be the same as or different from the organic solvent used in the step (II), but they are preferably the same.

[0180] The following is a reaction scheme in the case where aniline is used as the monomer (I), p-aminobenzenethiol is used as the monomer (II), and aniline is used as the end-capping monomer.

[0181] [Chemistry 13]

[0182]

[0183] (wherein X represents a halogen atom)

[0184] 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, relative to 100% by mass of the solid content of the present composition (i.e., components other than the solvent in the present composition).

[0185] When the content of the component (A) is within the above range, a composition that is less likely to precipitate when diluted with a general 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 less). Even when the cured product is fluidized by heating at a low temperature, the wetting and extension of the portion (bottom hem) in contact with the substrate (adherend) can be suppressed, and a cured product of a desired shape can be easily obtained.

[0186] [Component (B): photopolymerization initiator]

[0187] The component (B) is not particularly limited, but is preferably a photoradical polymerization initiator that generates radicals in response to radiation and initiates polymerization. Examples of the component (B) include O-acyl oxime compounds, acetophenone compounds, biimidazole compounds, and acylphosphine oxide compounds.

[0188] Examples of the O-acyl oxime compound include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), 1-(9-ethyl-6-benzoyl-9H-carbazole-3-yl)-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, ethyl ketone, -1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyl oxime).

[0189] Examples of the acetophenone compound include α-aminoketone compounds and α-hydroxyketone compounds.

[0190] Specific examples of the α-amino ketone compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0191] Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenylketone.

[0192] 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.

[0193] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0194] The content of the component (B) in the present composition is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, based on 100 parts by mass of the component (A).

[0195] 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.

[0196] [Component (C): polymerizable compound]

[0197] In order to form a cured product of the present composition, a polymerizable compound as the component (C) is essential, and is preferably a compound having a polymerizable carbon-carbon unsaturated bond.

[0198] By using the component (C) as a polymerizable compound, the pattern can be fluidized by a low-temperature process of, for example, 100° C. or less, and a cured product having a desired shape (particularly a microlens shape) can be easily formed.

[0199] The molecular weight of the component (C) is preferably 1,200 or less, more preferably 800 or less, and further preferably 600 or less, from the viewpoint of being able to reduce the temperature of the heat treatment for forming a cured product of a desired shape as much as possible. In addition, the molecular weight of the component (C) is preferably 100 or more, from the viewpoint of being able to easily form a cured product having a high refractive index and excellent solvent resistance, low volatility, and other characteristics and having excellent reliability.

[0200] Component (C) includes, for example, (meth)acryloyl group-containing compounds, chain vinyl compounds, aromatic vinyl compounds, and maleimide compounds, and among these, (meth)acryloyl group-containing compounds are preferred. These compounds are preferred because of their relatively high plasticity.

[0201] (C) Component may be any of a monofunctional compound and a polyfunctional compound. In addition, as (C) component, a monofunctional compound and a polyfunctional compound may be used in combination.

[0202] Specific examples of the monofunctional compound of component (C) include: (meth)acrylates containing a chain structure, (meth)acrylates having an alicyclic structure, (meth)acrylates having an aromatic ring structure, (meth)acrylamide compounds, chain vinyl compounds, aromatic vinyl compounds, and maleimide compounds. Among these, a compound containing a (meth)acryloyl group is preferred, and a compound containing a (meth)acryloyl group is more preferred, wherein the compound containing a (meth)acryloyl group is at least one selected from the group consisting of (meth)acrylates containing a chain structure, (meth)acrylates having an alicyclic structure, and (meth)acrylates having an aromatic ring structure.

[0203] Specific examples of the compound include (meth)acrylates having a chain structure, such as alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, and polyoxyalkylene (meth)acrylates.

[0204] Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate.

[0205] Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0206] As an alkoxyalkyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, etc. are mentioned.

[0207] Examples of the polyoxyalkylene (meth)acrylate include methoxydiethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, ethoxydipropylene glycol (meth)acrylate, and 2-ethylhexyloxydiethylene glycol (meth)acrylate.

[0208] Examples of the (meth)acrylate having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, 4-hydroxymethylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ] decane-8-yl ester, (meth) acrylic acid tricyclo[5.2.1.0 2,5 ]Decan-8-yloxyethyl ester, isobornyl (meth)acrylate, and the like.

[0209] Examples of the (meth)acrylate having an aromatic ring structure include phenyl (meth)acrylate, benzyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate, naphthyl methyl (meth)acrylate, naphthyl ethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, m-phenoxyphenyl methyl (meth)acrylate, p-phenoxyphenyl methyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, polyethyleneoxynonylphenyl (meth)acrylate, (1-naphthyl)methyl (meth)acrylate, (2-naphthyl)methyl (meth)acrylate, and (1,1'-biphenyl-4-yl)methyl (meth)acrylate.

[0210] Examples of the (meth)acrylamide compound include (meth)acryloylmorpholine, N-(2-hydroxyethyl) (meth)acrylamide, N-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactam.

[0211] Examples of the chain vinyl compound include propylene, butene, pentene, and hexene.

[0212] Examples of the aromatic vinyl compound include styrene, methylstyrene, α-methylstyrene, tert-butoxystyrene, and vinylnaphthalene.

[0213] Examples of the maleimide compound include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-(p-methylphenyl)maleimide.

[0214] Specific examples of the component (C) when it is a polyfunctional compound include polyfunctional (meth)acrylates, polyfunctional aromatic vinyl compounds, and polyfunctional chain vinyl compounds.

[0215] Examples of the multifunctional (meth)acrylate include difunctional (meth)acrylates, trifunctional or higher (meth)acrylates, etc. Specific examples of these difunctional (meth)acrylates include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenol A ethoxylate di(meth)acrylate, bisphenol F ethoxylate di(meth)acrylate, cresol novolac ethoxylate di(meth)acrylate, and biphenyl ethoxylate di(meth)acrylate.

[0216] Examples of trifunctional or higher-functional (meth)acrylates include trimethylolpropane tri(meth)acrylate, trimethylolpropane polypropylene glycol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol poly(meth)acrylate (e.g., A-DPH-12E manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene oxide oligomer-modified dipentaerythritol hexa(meth)acrylate (e.g., dipentaerythritol tetra(meth)acrylate), dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol poly(meth)acrylate (e.g., A-DPH-12E manufactured by Shin-Nakamura Chemical Co., Ltd.), Ethylene glycol-modified dipentaerythritol hexa(meth)acrylate), tris(2-(meth)acryloyloxyethyl)phosphate, succinic acid-modified pentaerythritol tri(meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate, isocyanuric acid tris(2-(meth)acryloyloxyethyl) ester, carboxyl-containing polyacid-modified (meth)acrylic acid oligomer, a compound having a linear alkylene and alicyclic structure and having two or more isocyanate groups, and a compound having one or more hydroxyl groups and three, four or five (meth)acryloyloxy groups in the molecule.

[0217] Examples of the polyfunctional aromatic vinyl compound include 1,3-divinylbenzene and 1,4-divinylbenzene.

[0218] Examples of the polyfunctional chain vinyl compound include 1,5-hexadiene, 1,6-heptadiene, and 1,7-octadiene.

[0219] Preferred specific examples of the component (C) include compounds represented by the following formula (C1-1) to formula (C1-50).

[0220] [Chemistry 14]

[0221]

[0222] [Chemistry 15]

[0223]

[0224] [Chemistry 16]

[0225]

[0226] [Chemistry 17]

[0227]

[0228] [Chemistry 18]

[0229]

[0230] In formula (C1-1) to formula (C1-50), R 20 is a hydrogen atom or a methyl group. m and n are each independently an integer of 0 to 10. x, y and z are each independently an integer of 0 to 10.

[0231] In addition, R in formula (C1-48) is a or R b , and it means that a of the six Rs is R a , b of the six Rs are R b . Wherein, a+b=6, and a is an integer greater than or equal to 1.

[0232] In terms of being able to easily form a hardened product of a desired shape by heat treatment at a low temperature and being able to easily form a hardened product with high heat resistance, the content of component (C) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of component (A).

[0233] The component (C) is preferably a compound containing one or two polymerizable carbon-carbon unsaturated bonds in one molecule (hereinafter also referred to as "compound (C1)").

[0234] In terms of the fact that the pattern can be fluidized by heat treatment at a low temperature (for example, a temperature below 100° C.) and a hardened product of a desired shape can be easily formed, the content of the compound (C1) is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more, relative to 100% by mass of the component (C).

[0235] [Other ingredients]

[0236] In addition to the above-mentioned components (A) to (C), the present composition may also contain components other than these (hereinafter also referred to as "other components") within the range that does not impair the effects of the present invention. Examples of other components include polymers, solvents, polymerization inhibitors, surfactants, antioxidants, sensitizers, softeners, plasticizers, adhesion aids, and ultraviolet absorbers.

[0237] The blending ratio of these other components can be appropriately selected according to each component within a range that does not impair the effects of the present invention.

[0238] ·polymer

[0239] The present composition may also contain a polymer other than the above-mentioned components (A) and (C) (hereinafter also referred to as "polymer (D)") as an additive component. By adding the polymer (D) to the present composition, the heat resistance of the obtained cured product can be improved, and a cured product with a high refractive index and better reliability can be easily formed.

[0240] Examples of the polymer (D) include alkali-soluble polymers, fluorene skeleton-containing radiation-sensitive polymers, and carboxyl group-containing radiation-sensitive polymers.

[0241] The molecular weight of the polymer (D) is preferably 2,000 or more and 100,000 or less.

[0242] Examples of the alkali-soluble polymer include (meth)acrylic acid / methyl (meth)acrylate copolymers, (meth)acrylic acid / benzyl (meth)acrylate copolymers, (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate copolymers, (meth)acrylic acid / styrene / isoprene / tricyclodecyl (meth)acrylate / 2-mono(hexahydroxyphthalyloxy)ethyl (meth)acrylate copolymers, (meth)acrylic acid-modified (meth)acrylic acid resins, and acid anhydride-modified (meth)acrylic acid resins.

[0243] Examples of the radiation-sensitive polymer containing a fluorene skeleton include polymers described in International Publication No. 2009 / 119622.

[0244] As specific examples of the carboxyl group-containing radiation-sensitive polymer, commercially available products may be used, and examples of the commercially available products include CCR-1235, CCR-1291H, ZAR-1035, ZAR-2000, ZFR-1401H, ZFR-1491H, ZCR-1569H, and ZCR-1798H (all manufactured by Nippon Kayaku Co., Ltd.).

[0245] When a polymer (D) is added to the present composition, the amount of the polymer (D) is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of component (A). When the amount of the polymer (D) is within the above range, a cured product having excellent heat resistance can be easily formed into a desired shape by heat treatment at a low temperature.

[0246] Solvent

[0247] The present composition is preferably a liquid composition obtained by dissolving or dispersing the components (A) to (C) and other components prepared as necessary in a solvent (hereinafter also referred to as “solvent (E)”).

[0248] The solvent (E) is preferably an organic solvent that dissolves the components formulated in the present composition and does not react with the components.

[0249] Specific examples of the solvent (E) include, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diglycol monomethyl ether, ethylene diglycol ethyl methyl ether, 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.

[0250] Surfactants

[0251] For example, the coating properties of the present composition can be improved (wetting and spreading properties or coating unevenness can be reduced) by using a surfactant.

[0252] Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

[0253] As the fluorine-based surfactant, a commercially available product can be used, and examples of the commercially available product include: Megafac F-171, Megafac F-172, Megafac F-173, Megafac F-251, Megafac F-430, Megafac F-554, Megafac F-563 (manufactured by DIC Corporation); Fluorad FC430, Fluorad FC431, Fluorad FC432, Fluorad FC433, Fluorad FC434, Fluorad FC435, Fluorad FC436, Fluorad FC437, Fluorad FC438, Fluorad FC439, Fluorad FC440, Fluorad FC441, Fluorad FC443, Fluorad FC444, Fluorad FC445, Fluorad FC446, Fluorad FC447, Fluorad FC448, Fluorad FC449, Fluorad FC448, Fluorad FC449, Fluorad FC441, Fluorad FC443 ...2, Fluorad FC443, Fluorad FC444, Fluorad FC445, Fluorad FC446, Fluorad FC447, Fluorad FC448, Fluorad )FC431 (manufactured by Sumitomo 3M Co., Ltd.); AsahiGuard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106, Surflon S-611 (AGC Qingmei Chemical Co., Ltd. (manufactured by SEIMI Chemical); Polyflow No.75, Polyflow No.95 (manufactured by Kyoeisha Chemical); FTX-218 (manufactured by NEOS); Eftop EF301, Eftop EF303, Eftop EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), etc.

[0254] As the silicone surfactant, commercially available products can be used, and examples of the commercially available products include SH200-100cs, SH-28PA, SH-30PA, SH-89PA, SH-190, SH-8400, FLUID, SH-193, SZ-6032, SF-8428, DC-57, DC-190, PAINTAD 19, FZ-2101, FZ-77, FZ-2118, L-7001, L-7002 (Dow Toray), ray)(manufactured by Shin-Etsu Chemical Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-300, BYK-306, BYK-310, BYK-330, BYK-335, BYK-341, BYK-344, BYK-370, BYK-340, BYK-345 (manufactured by BYK-Chemie Japan)(manufactured by BYK-Chemie Japan Co., Ltd.), etc.

[0255] Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate.

[0256] When a surfactant is blended in the present composition, the amount of the surfactant blended is preferably 0.01 to 1.5 parts by mass, more preferably 0.02 to 1.2 parts by mass, and still more preferably 0.05 to 1.0 parts by mass, relative to 100 parts by mass of component (A).

[0257] Antioxidants

[0258] For example, by using an antioxidant, decomposition and degradation of polymer molecules in the present composition can be suppressed, and durability can be improved.

[0259] Examples of the antioxidant include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, and diethylenethiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0260] When an antioxidant is blended in the present composition, the amount of the antioxidant is preferably 0.01 to 1.5 parts by mass, more preferably 0.02 to 1.2 parts by mass, and still more preferably 0.05 to 1.0 parts by mass, based on 100 parts by mass of the component (A).

[0261] ·Sealing agent

[0262] By using the present composition containing the adhesion aid, the adhesion between the formed cured product and the substrate (adherend) can be improved, and the peeling of the cured product from the substrate in the development step or the like can be suppressed.

[0263] As the adhesion aid, a functional silane coupling agent having a reactive functional group is preferred.

[0264] Examples of the reactive functional group possessed by the functional silane coupling agent include a carboxyl group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

[0265] Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0266] When the adhesion aid is mix|blended in this composition, the mixing|blending amount is preferably 0.01 mass part - 4 mass parts, and more preferably 0.1 mass part - 2 mass parts, based on 100 mass parts of (A) components.

[0267] [Method for preparing the present composition]

[0268] The present composition can be prepared by mixing the components (A) to (C) and any other components.

[0269] Alternatively, after mixing the components, the obtained mixture may be filtered using a filter having a pore size of 0.5 μm or less, as necessary.

[0270] The solid content concentration of this composition (that is, the total mass of the composition other than the solvent in this composition, the ratio shared in the total mass of this composition) can consider viscosity or volatility etc. to suitably select.The solid content concentration of this composition is preferably 1 mass %~60 mass %, more preferably 2 mass %~50 mass %, and then preferably 5 mass %~40 mass %.If solid content concentration is more than the lower limit, then when this composition is applied on substrate (adherend), the film thickness of coating can be fully ensured, etc. is preferred.In addition, if solid content concentration is below the upper limit, then the viscosity of this composition can be appropriately improved and good coating properties can be ensured, etc. are preferred.

[0271] The present composition can be suitably used for optical components used in at least a part of imaging devices such as cameras, organic EL elements, or various display elements such as liquid crystal display elements. In particular, when the present composition is used to form a cured product by heat treatment, it can be suitably used as a radiation-sensitive composition for microlens production or flattening film production, especially a radiation-sensitive composition for microlens production based on a heat flow method, in terms of being able to easily form a cured product having a desired microlens shape or flattening film shape.

[0272] Hardened

[0273] The cured product of the present disclosure (hereinafter also referred to as “the present cured product”) is a cured product of the present composition, and specifically, can be formed by irradiating the present composition with radiation.

[0274] The shape of the cured product is not particularly limited, but is preferably a microlens or a planarized film, and more preferably a microlens, from the viewpoint of further exerting the effects of the present invention.

[0275] This hardened material can be suitably used as an optical component used in at least a part of an imaging device such as a camera, an organic EL element, or various display elements such as a liquid crystal display element. That is, this hardened material can be suitably used as a material for an optical component. Specifically, it can be suitably used as an optical component such as a microlens of a solid imaging element included in an imaging device such as a camera, or an organic EL element (organic light emitting diode (OLED)) or liquid crystal display element (liquid crystal display (LCD)), μLED, etc. included in a display device. In addition, it can also be suitably used as a flattening film provided in an organic EL element or a liquid crystal display element.

[0276] The refractive index of the present cured product under light of a wavelength of 550 nm is preferably 1.60 or more, and more preferably 1.64 or more. A cured product having a refractive index within the above range can be said to have a high refractive index and can be suitably used for optical components.

[0277] Specifically, the refractive index can be measured by the method described in the following Examples.

[0278] [Method for producing the present hardened product]

[0279] The method for producing the present cured product includes the step of irradiating the present composition with radiation. When irradiating with radiation, a mask having a predetermined pattern may be used as necessary, and development may be performed after irradiating with radiation using the mask. Furthermore, heat treatment may be performed after irradiating with radiation.

[0280] The present composition is particularly suitable as a negative pattern forming material, which is used to make the following pattern (i.e., a hardened material formed by the present composition) fluidized by heat treatment, thereby forming a desired shape (e.g., a microlens shape, a flattened film shape), that is, a pattern formed by exposing a portion of an organic film formed by the present composition and dissolving the unexposed portion of the exposed organic film in an alkaline developer.

[0281] As suitable examples of the method for producing the present cured product, the following first production method and second production method can be mentioned.

[0282] <First Manufacturing Method>

[0283] The first production method is a method comprising the following steps (I) to (III), and may further comprise the following step (IV) and / or step (V).

[0284] (Step (I): coating step)

[0285] Step (I) is a step of forming a coating film (organic film) on a substrate by applying the present composition on the substrate.

[0286] Examples of the substrate include glass substrates, silicon wafers, plastic substrates, and substrates having a color resist, an overcoat layer, an antireflection film, various metal thin films, a sealing film, and the like formed on the surface thereof.

[0287] Examples of the plastic substrate include resin substrates (resin films) made of plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyether sulfone, polycarbonate, and polyimide.

[0288] Various elements (for example, a light receiving element such as a photodiode or a light emitting element such as an organic light emitting diode) may be provided in advance in the substrate.

[0289] As a coating method of the present composition, for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slot die coating method, a bar coating method, an ink jet method, etc. can be used. As a coating method, spin coating method, a bar coating method, and a slot die coating method are preferable among these.

[0290] After the composition is applied to the substrate, the composition may be preheated (prebaked) for the purpose of preventing dripping. The prebaking conditions may be appropriately set according to the type or proportion of each component used in the composition, for example, at 60°C to 130°C for 30 seconds to 10 minutes.

[0291] The film thickness of the formed coating film is preferably 0.1 μm to 20 μm, more preferably 0.2 μm to 15 μm, as the film thickness after prebaking.

[0292] (Step (II): Exposure Step)

[0293] Step (II) is a step of irradiating a portion of the coating film formed in step (I) with radiation. By the irradiation with radiation, a curing reaction proceeds in the exposed portion, and a cured product is obtained in which the exposed portion is cured.

[0294] In step (II), the radiation irradiation to the coating film is performed through a mask having a pattern (e.g., a dot pattern) for obtaining a cured product (e.g., a microlens) having a desired shape. The mask may be a multi-tone mask such as a halftone mask or a gray tone mask.

[0295] As a radiation irradiated to a coating film, ultraviolet rays, extreme ultraviolet rays, X-rays, and charged particle beams are mentioned, for example.

[0296] Examples of ultraviolet rays include g-rays (wavelength: 436 nm), i-rays (wavelength: 365 nm), and KrF excimer laser light (wavelength: 248 nm).

[0297] Examples of X-rays include synchrotron radiation.

[0298] As a charged particle beam, an electron beam is mentioned, for example.

[0299] Among these, ultraviolet rays are preferred, and ultraviolet rays having a wavelength of 200 nm to 380 nm are more preferred.

[0300] Examples of the light source used for radiation irradiation include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and an excimer laser.

[0301] The radiation exposure dose is preferably 500 J / m 2 ~50,000J / m 2 (50mJ / cm 2 ~5,000mJ / cm 2 ).

[0302] (Step (III): Development Step)

[0303] Step (III) is a step of forming a pattern on the substrate by developing the coating film and the cured product obtained in step (II). The development step can remove the coating film formed on the substrate in the unexposed portion, thereby forming a pattern (for example, a concave-convex pattern formed by a plurality of regularly arranged fine cured products) in which the cured products (fine cured products) in the exposed portion remain on the substrate.

[0304] As the developer, an aqueous solution of an alkali (alkaline compound) can be mentioned.

[0305] Examples of the aqueous solution 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.

[0306] Alternatively, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous alkali solution, or a small amount of various organic solvents capable of dissolving the present composition may be added.

[0307] The concentration of the developer can be appropriately determined depending on the composition of the composition, and is usually 0.01% by mass to 10% by mass, and preferably 0.5% by mass to 5% by mass.

[0308] As the developing method, for example, an appropriate method such as a coating method, a dipping method, a shaking dipping method, a shower method, or the like can be adopted.

[0309] The development time may be appropriately adjusted according to the composition of the present composition, and is, for example, 20 seconds to 120 seconds.

[0310] After the development step, a step of washing the developed patterned substrate with pure water or the like may be performed as necessary.

[0311] In addition, a step of drying the patterned substrate after development or the cleaning may be performed. The drying conditions are not particularly limited, and for example, the same conditions as those for the pre-baking may be mentioned.

[0312] (Step (IV): Heating Step)

[0313] Step (IV) is a step of heating and melting the developed pattern to form the pattern on the substrate into a desired shape (eg, microlens shape, planarized film shape) by heat flow.

[0314] By the heat treatment in step (IV), the present composition can be further cured while heat-fluxing the pattern formed in step (III).

[0315] By performing step (IV), for example, the fine hardened objects formed in step (III) can be formed into a lens (microlens) shape, thereby obtaining a microlens (array) in which hemispherical fine hardened objects are (regularly) arranged on a substrate.

[0316] The heat treatment can be performed using a heating device such as an oven or a hot plate.

[0317] The heating temperature in step (IV) can be appropriately selected according to the substrate or the present composition used, and is preferably 100° C. or less, more preferably 95° C. or less, and further preferably 90° C. or less, from the perspective of being applicable to high-refractive-index materials for organic electroluminescent elements. In addition, from the perspective of being able to easily form a cured product having high heat resistance and chemical resistance and a desired shape, the heating temperature in step (IV) is preferably 60° C. or more, more preferably 80° C. or more.

[0318] According to the present composition, a cured product of a desired shape can be formed even when heat-treated at a low temperature of 100° C. or lower. As described above, by heat-treating at a low temperature of 100° C. or lower, an organic EL element or the like requiring application of a low temperature process can be used as a substrate.

[0319] The heating time can be appropriately set according to the type of heating device, etc. For example, when a hot plate is used for heating, the heating time is, for example, 5 minutes to 60 minutes. In addition, when an oven is used for heating, the heating time is, for example, 10 minutes to 90 minutes.

[0320] In step (IV), a step baking method in which the heating treatment is performed multiple times may be used.

[0321] (Step (V): Post-exposure step)

[0322] Step (V) is a step of further irradiating the hardened product (e.g., micro-hardened product) obtained in step (III) after development and / or the hardened product (e.g., microlens) obtained in step (IV) with radiation. Among these, the step of further irradiating the hardened product obtained in step (IV), especially the microlens, with radiation is preferred because a hardened product of a desired shape, especially the microlens, can be easily formed by low-temperature heat flow.

[0323] By irradiating with radiation in the step (V) (hereinafter also referred to as “post-exposure”), heat resistance and chemical resistance can be further improved, and a highly reliable cured product, particularly a microlens, can be easily formed.

[0324] Among these, the type of radiation or exposure conditions in the post-exposure may be the same as those in step (II). In addition, the wavelength or irradiation amount of the irradiation light, the light source and other conditions in the post-exposure may be the same as or different from those in step (II).

[0325] <Second Manufacturing Method>

[0326] The second manufacturing method includes a step of inkjet coating the 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) can be directly formed on the substrate by inkjet coating. Alternatively, a pattern (e.g., a dot pattern) can be formed on the substrate by inkjet coating, and then the same step (IV) as the first manufacturing method can be performed to form a desired hardened product.

[0327] In addition, the second manufacturing method may include the same step as the step (V) in the first manufacturing method.

[0328] The planarized film as one form of the present cured product can be produced by the same method as the first production method except that, in step (II) of the first production method, no mask is used or a pattern other than a dot pattern is used.

[0329] Display Device

[0330] The display device of the present disclosure is not particularly limited as long as it includes the present cured product, and may have any conventionally known structure other than including the present cured product.

[0331] Examples of the display device include a liquid crystal display (LCD), an organic EL using an organic light emitting diode (OLED), a μLED display, an electrochromic display (ECD), an electroluminescent display (ELD), and a display using a quantum dot-organic EL (QD-OLED).

[0332] Camera Device

[0333] The imaging device of the present disclosure is not particularly limited as long as it includes the present cured product, and may have any conventionally known structure other than including the present cured product.

[0334] Examples of the imaging device include: a video camera, a digital camera, a mobile phone with a camera function, an endoscopic camera, a capsule endoscopic camera, a microscope, a medical or health care camera (for example, a camera for photographing blood vessels based on infrared light reception), a vehicle-mounted camera (for example, a camera for photographing the surroundings and interior of a vehicle, a camera for detecting the distance between vehicles), a surveillance camera, a person authentication camera, and an industrial camera.

[0335] [Example]

[0336] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

[0337] (Synthesis example 1)

[0338] In a nitrogen atmosphere, cyanuric chloride (20 mmol) was added to a 300 mL two-necked flask and dissolved in N-methylpyrrolidone (NMP, 20 mL), and then cooled to 0°C in an ice bath. Then, while confirming that the internal temperature of the flask did not reach 15°C or higher, a solution in which aniline (monomer (I), 20 mmol) and N,N-diisopropylethylamine (60 mmol) were dissolved in NMP (20 mL) was added dropwise to the cooled solution, and the mixture was further stirred for 15 minutes in an ice bath. Then, while confirming that the internal temperature of the flask did not reach 15°C or higher, a solution in which p-aminobenzenethiol (monomer (II), 13.4 mmol) was dissolved in NMP (10 mL) was added dropwise, and the mixture was stirred for 10 minutes. After stirring for 10 minutes, the flask was moved to an oil bath, heated to 120°C, and stirred for 3 hours. After stirring for 3 hours, a solution obtained by dissolving aniline (end-capping monomer, 6.8 mmol) in NMP (8 mL) was added, and the mixture was heated and stirred for 30 minutes. After stirring for 30 minutes, stirring and heating were stopped, and the obtained solution was added dropwise to ion exchange water (400 g) while stirring to reprecipitate. The obtained precipitate was separated by filtration, washed with water and methanol, and dried at 60° C. for 6 hours using a reduced pressure dryer to obtain the target oligomer (polymer (A-1), 5.72 g).

[0339] [Chemistry 19]

[0340]

[0341] (Synthesis Examples 2 to 10, Synthesis Examples 12 to 26, and Comparative Synthesis Examples 1 to 3)

[0342] The target oligomers (polymers (A-2) to (A-10), (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 monomers used were changed to the types and amounts described in Table 1.

[0343] (Synthesis Example 11)

[0344] 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.

[0345] In a 300 mL flask, 5.81 g of the obtained oligomer, 2,4-di-tert-butylhydroquinone (0.0001 g) and tetrahydrofuran (THF, 40 mL) were added, and after nitrogen substitution, the oligomer was dissolved by stirring. Then, the temperature was raised until the internal temperature of the flask reached 60°C, and 2-isocyanatoethyl acrylate (1.9 g) was added. After stirring for 3 hours, the reaction solution was added dropwise to ion exchange water (400 g) while stirring for reprecipitation. The obtained precipitate was filtered and separated, washed with water and methanol, and dried at 60°C for 6 hours using a reduced pressure dryer to obtain the target oligomer (polymer (A-11), 5.56 g).

[0346] [Evaluation of polymer]

[0347] 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.

[0348] <Evaluation of weight average molecular weight>

[0349] 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.

[0350] Column: Made by Tosoh Corporation, TSKgelGRCXLII

[0351] Solvent: Tetrahydrofuran

[0352] Temperature: 40℃

[0353] Pressure: 68kgf / cm 2

[0354] <Evaluation of refractive index>

[0355] After applying a solution obtained by dissolving each prepared polymer in an appropriate amount of NMP on an alkali-free glass substrate using a spinner, the solution was heated on a hot plate at 100° C. for 3 minutes, and then heated on a hot plate at 150° C. for 30 minutes to obtain a polymer film. The refractive index of the obtained polymer film under light of a wavelength of 550 nm was measured using a rotary compensator type spectroscopic ellipsometer SE-2000 (manufactured by Semilab Semiconductor Physics Laboratory Co. Ltd.), and the evaluation was performed according to the following evaluation criteria.

[0356] Evaluation benchmark

[0357] AA: Refractive index ≥ 1.69

[0358] BB: 1.69>Refractive index ≧1.63

[0359] CC: Refractive index <1.63

[0360] <Evaluation of solubility>

[0361] Propylene glycol monomethyl ether acetate (PGMEA) was added to each prepared polymer so that the solid content concentration of the polymer became 10 mass %, and then stirred at room temperature (25° C.) for 6 hours. The solution was then left to stand and observed, and evaluated based on the following evaluation criteria.

[0362] Evaluation benchmark

[0363] AA: The solution is transparent and no turbidity is observed.

[0364] BB: White turbidity is seen in the solution.

[0365] [Table 1]

[0366]

[0367] In addition, the "equivalent weight" in the column of each monomer in Table 1 is the usage amount (equivalent weight) of each monomer when the usage amount of cyanuric chloride for synthesizing each polymer is set to 1 equivalent.

[0368] [Preparation of radiation-sensitive composition]

[0369] The details of the component (B), the component (C), and the solvent (E) used for preparing the radiation-sensitive composition in the Examples and Comparative Examples are shown below.

[0370] <Photopolymerization initiator (B)>

[0371] B-1: 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)] (Irgacure OXE01, manufactured by BASF)

[0372] B-2: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[0373] <Polymerizable compound (C)>

[0374] C-1: Bisphenol A ethoxylate diacrylate

[0375] C-2: 3-Phenoxybenzyl acrylate

[0376] C-3: Dipentaerythritol hexaacrylate

[0377] C-4: Ethylene oxide-modified dipentaerythritol polyacrylate (A-DPH-12E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0378] C-5: 1,9-nonanediol diacrylate

[0379] <Solvent (E)>

[0380] E-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0381] (Example 1)

[0382] A PGMEA solution (solid content concentration of 30% by mass) containing 100 parts by mass (solid content) of the polymer (A-1), 25 parts by mass of the polymerizable compound (C-1), 15 parts by mass of the polymerizable compound (C-2), 5 parts by mass of the photopolymerization initiator (B-1), 0.5 parts by mass of an adhesion aid (3-methacryloyloxypropyltrimethoxysilane), 0.1 parts by mass of an antioxidant (pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), and 0.2 parts by mass of a surfactant ("FTX-218" manufactured by NEOS Co., Ltd.) were mixed, and a solvent (E-1) was added so that the solid content concentration became 35% by mass, followed by stirring to dissolve the components. The obtained mixture was then filtered using a membrane filter having a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[0383] (Example 2 to Example 32 and Comparative Example 1 to Comparative Example 3)

[0384] Except having changed the kind and the usage-amount of each component as described in Table 2, it carried out similarly to Example 1, and prepared the radiation sensitive composition.

[0385] [Evaluation of radiation sensitive composition]

[0386] The properties of the radiation-sensitive compositions prepared in Examples 2 to 32 and Comparative Examples 1 to 3 were evaluated as follows.

[0387] <Evaluation of solubility>

[0388] 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 based on the following evaluation criteria.

[0389] Evaluation benchmark

[0390] AA: The radiation sensitive composition is transparent and no turbidity is observed.

[0391] BB: White turbidity was observed in the radiation-sensitive composition.

[0392] <Evaluation of precipitation during dilution>

[0393] The prepared radiation sensitive composition was diluted 3, 10, and 50 times by mass using PGMEA and stirred thoroughly at room temperature (25° C.) The diluted solution was visually observed and the presence or absence of precipitation of components constituting the radiation sensitive composition due to dilution was evaluated according to the following evaluation criteria.

[0394] AA: The diluted solutions were transparent and no turbidity was observed at any dilution ratio.

[0395] BB: White turbidity was observed in any dilution.

[0396] <Patternability>

[0397] Each of the prepared radiation-sensitive compositions was applied onto an alkali-free glass substrate using a spinner, and then pre-baked on a hot plate at 85° C. for 3 minutes to form a coating film having a film thickness of 9.0 μm.

[0398] The obtained coating film was then exposed to light using a projection exposure apparatus (high-pressure mercury lamp; illumination at 365 nm: about 500 mW / cm2) through a photomask having a circular residual pattern with a diameter of 20 μm. 2 ) at 200mJ / cm 2 ~900mJ / cm 2 In the range of 100mJ / cm 2 The radiation is irradiated by changing the exposure amount in units of .

[0399] Then, a 2.38 mass % tetramethylammonium hydroxide aqueous solution at 23° C. was used as a developer, and development was performed by a flooding method at 25° C. for 60 seconds, followed by 60 seconds of pure water washing, and then the substrate was dried, thereby forming a pattern including a plurality of micro-bodies formed of the radiation-sensitive composition on the substrate (an enlarged photograph of the pattern at this time is shown in FIG. 1 ). Figure 1 After development, the substrate was observed using an optical microscope, and the substrate with the least residue and pattern peeling among the substrates obtained by irradiating the radiation with varying exposure amounts was evaluated for patterning properties according to the following evaluation criteria. In addition, when the polymer (A) does not have an alkali-soluble group (does not dissolve in an alkaline developer), the patterning properties were not evaluated.

[0400] Then, the substrate was post-baked in an oven at 85° C. for 40 minutes to form a pattern having a plurality of lens shapes formed of the radiation-sensitive composition on the substrate (an enlarged photograph of the pattern at this time is shown in FIG. 1 ). Figure 1 (b)).

[0401] Evaluation benchmark

[0402] AA: No residue other than the pattern is observed on the substrate, and pattern peeling is hardly observed.

[0403] BB: Residues other than the pattern or pattern peeling are slightly observed on the substrate.

[0404] CC: Residues other than the pattern were observed in most of the substrate, or the pattern was peeled off and almost no pattern remained on the substrate.

[0405] <Lens formation>

[0406] Each of the prepared radiation-sensitive compositions was applied onto an alkali-free glass substrate using a spinner, and then pre-baked on a hot plate at 85° C. for 3 minutes to form a coating film having a film thickness of 9.0 μm.

[0407] The obtained coating film was then exposed to light using a projection exposure apparatus (high-pressure mercury lamp; illumination at 365 nm: about 500 mW / cm2) through a photomask having a line pattern with a line width of 30 μm (space of 30 μm). 2 ) at 200mJ / cm 2 、300mJ / cm 2 、500mJ / cm 2 、700mJ / cm 2 、1,000mJ / cm 2 or 1,500mJ / cm 2 Radiation irradiation was performed at each exposure amount.

[0408] Then, for each of the substrates irradiated with radiation at each exposure amount, development was performed by a flooding method at 25° C. for 60 seconds using a 2.38 mass % tetramethylammonium hydroxide aqueous solution at 23° C. as a developer, followed by 60 seconds of pure water washing and drying the substrate, thereby forming a plurality of line patterns formed of the radiation-sensitive composition on the substrate.

[0409] Then, each substrate having a line pattern formed thereon was post-baked in an oven at 85°C for 40 minutes. Then, the cross-section (cross-section in a direction substantially perpendicular to the length direction of the line pattern) of each substrate pattern was observed using an optical microscope, and the lens forming property was evaluated according to the following evaluation criteria. In addition, in the case where the polymer (A) does not have an alkali-soluble group (does not dissolve in an alkaline developer), the evaluation of the lens forming property was not performed.

[0410] When the evaluation result is "AA", it is considered that the line pattern (particularly the upper portion of the line pattern on the opposite side of the substrate) whose pattern cross section is rectangular due to post-baking is reflowed, whereby the pattern cross section becomes semicircular. In the above evaluation, when the evaluation result is "AA" even though a line pattern is formed, it is highly likely that a lens (microlens) is formed by forming a dot pattern.

[0411] Evaluation benchmark

[0412] AA: Among the patterns on the obtained substrates (substrates after post-baking obtained by irradiating with radiation at each exposure amount), the cross section of the pattern after post-baking on at least one substrate is semicircular.

[0413] BB: The pattern cross section after post-baking in all the obtained substrates (substrates after post-baking obtained by irradiating with radiation at each exposure amount) was a rectangle.

[0414] <Evaluation of refractive index>

[0415] Each radiation-sensitive composition was applied onto an alkali-free glass substrate using a spinner and pre-baked on a hot plate at 100°C for 3 minutes to form a coating film with a thickness of 9.0 μm. The obtained coating film was then illuminated using a high-pressure mercury lamp (illuminance at 365 nm: about 500 mW / cm 2 ) at 500mJ / cm 2 The substrate was irradiated with an exposure amount of radiation. Then, a 2.38 mass % tetramethylammonium hydroxide aqueous solution at 23°C was used as a developer, and the developer was developed for 60 seconds at 25°C by a liquid coating method, followed by 60 seconds of pure water washing, and then the substrate was dried. Then, the substrate was post-baked in an oven at 85°C for 40 minutes to form a cured film. The refractive index of the obtained cured film under light of a wavelength of 550nm was measured using a rotary compensator type spectroscopic ellipsometer SE-2000 (manufactured by Semilab Semiconductor Physics Laboratory Co. Ltd.), and evaluated according to the following evaluation criteria.

[0416] Evaluation benchmark

[0417] AA: Refractive index ≥ 1.64

[0418] BB: 1.64>Refractive index ≧1.60

[0419] [Table 2] Table 2

[0420]

Claims

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

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); In the 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, 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 are independently single bonds, CR 14 R 15 , C=O, O, S, SO, SO2 or NR 16 , where R 14 and R 15 are independently a hydrogen atom or a monovalent organic group, R 14 and R 15 Can bond with each other to form a ring, 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); * indicates a bonding bond, In the 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, Y 1 and Y 2 Each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms and may have a branched structure; * indicates a bonding bond.

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

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

5. The radiation-sensitive composition according to claim 1, wherein The partial structure represented by the formula (1) is the partial structure represented by the following formula (2); In formula (2), Ar, X 1 and X 2 The same symbols as in formula (1) have the same meanings, X 3 is S, O or NR', wherein 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, * indicates a bonding bond.

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

7. The radiation-sensitive composition according to claim 1, wherein The polymer having the partial structure represented by the formula (1) is soluble in propylene glycol monomethyl ether acetate 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 heat flow method. 9 . A cured product obtained by curing the radiation sensitive composition according to claim 1 . 10 . The cured product according to claim 9 , which has a refractive index of 1.60 or more under light of a wavelength of 550 nm. The cured product according to claim 9 , which is used for optical components.

12. A display device comprising the hardened material according to claim 9.

13. An imaging device comprising the hardened material according to claim 9.

14. A method for manufacturing a hardened object, comprising: A step of applying the radiation-sensitive composition according to any one of claims 1 to 8 onto a substrate; a step of irradiating the radiation-sensitive composition coated on the substrate with radiation; and A step of developing the radiation-sensitive composition after irradiation with radiation. 15 . The method for producing a cured product according to claim 14 , further comprising the step of heating the developed radiation-sensitive composition.

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

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

18. A polymer having a partial structure represented by the following formula (1); In formula (1), Ar is a divalent organic group containing either or both of an aromatic ring and a heterocyclic ring, X 1 and X 2 are independently S or NR, X 1 and X 2 One of them is S, wherein R is a hydrogen atom or a monovalent organic group, * indicates a bonding bond. The polymer according to claim 18 , which has a refractive index of 1.63 or more at a wavelength of 550 nm. 20 . The polymer according to claim 18 , which is soluble in propylene glycol monomethyl ether acetate at 25° C. in an amount of 10% by mass or more.

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