Composition

Abstract

The present invention relates to a composition containing an alkali-soluble polymer and a colorant.

Description

[Technical Field]

[0001] The present invention relates to a composition comprising an alkali-soluble polymer and a colorant.The present invention further relates to a method for producing a cured layer, a layer, a light-conversion device, an optical device, uses of the device, uses of the light-conversion device, and a method for producing an optical device. [Background technology]

[0002] JP 2022-33154 A and JP 2021-113977 A (Toray) describe polysiloxane-based resin compositions containing polysiloxane, a white pigment, and an organometallic compound (Examples).

[0003] JP 2021-161401 A (Toray) discloses a polysiloxane-based resin composition containing a photoradical generator, a polysiloxane, and a polymer of the (meth)acrylic polymer or cardo-type polymer described in claim 1. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-113977 [Patent Document 2] Japanese Patent Publication No. 2022-33154 [Patent Document 3] Patent Publication No. 2021-161401 Summary of the Invention

[0005] However, the present inventors have newly discovered that one or more of the following important problems still exist for which improvement is desired: enabling development with a low-concentration alkaline developer, preferably development in a shorter development time, and / or achieving both the reactivity and storage stability of the composition, realizing high sensitivity of the composition and reducing exposure energy and exposure time, improving the structure (bank structure) of the patterned cured film, particularly improving the bottom side structure of the patterned cured film, achieving improved reflection and / or high optical density (OD) of the cured film, particularly improving reflection and / or high OD of the cured film having white and black pigments (gray bank).

[0006] The inventors aimed to solve one or more of the problems set forth above. The inventors have surprisingly found that one or more of the above mentioned technical problems can be solved by the features defined in the claims.

[0007] That is, novel compositions have been discovered, preferably photocurable compositions, and preferably the compositions are completely free of polysiloxanes; at least i) an alkali-soluble polymer containing an ethylenic double bond; ii) a colorant.

[0008] In another aspect, the present invention also provides a method for producing a pharmaceutical composition comprising at least the following steps: (Xi) providing the composition of the present invention on a layer or substrate to form a coating layer; (Xii) baking the coating layer to obtain a hardened layer.

[0009] In another aspect, the present invention relates to a layer obtained or obtainable from the method of the present invention.

[0010] In another aspect, the present invention further relates to a color conversion device (100) obtainable or obtained from the method of the present invention.

[0011] In another aspect, the present invention also provides a method for producing a pharmaceutical composition comprising: i) a polymer (A) derived from or derivable from an alkali-soluble polymer containing an ethylenic double bond; and ii) Concerning the layer containing the colorant.

[0012] In another aspect, the present invention further relates to a photoconversion device comprising at least a layer of the present invention.

[0013] In another aspect, the present invention also relates to an optical device comprising at least the layer of the present invention or the light-conversion device of the present invention.

[0014] In another aspect, the present invention further relates to the use of the composition of the present invention or the layer of the present invention in a process for manufacturing a photoconversion device.

[0015] In another aspect, the present invention further relates to the use of the photo-conversion device of the present invention in a manufacturing process for an optical device.

[0016] In another aspect, the present invention further comprises at least A method of manufacturing an optical device includes providing the optical device with the photo-conversion device of the present invention.

[0017] Further advantages of the present invention will become apparent from the following detailed description. DETAILED DESCRIPTION OF THE INVENTION

[0018] In this specification, symbols, units, abbreviations and terms have the following meanings unless otherwise specified.

[0019] In this specification, unless otherwise specified, the singular includes the plural, and "one" or "it" means "at least one." In this specification, unless otherwise specified, a certain conceptual element may be expressed in plural, and when the amount thereof (e.g., mass %, mole %) is stated, it means the total of the plural kinds. "And / or" includes all combinations of elements, and also includes the single use of an element.

[0020] In this specification, when a numerical range is indicated using "to" or "to-," both endpoints are included and the units are the same. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less.

[0021] As used herein, hydrocarbon refers to a group containing carbon and hydrogen, and optionally oxygen or nitrogen. Hydrocarbyl groups refer to monovalent or polyvalent hydrocarbons. As used herein, aliphatic hydrocarbons refer to linear, branched, or cyclic aliphatic hydrocarbons, and aliphatic hydrocarbon groups refer to monovalent or polyvalent aliphatic hydrocarbons. Aromatic hydrocarbons refer to hydrocarbons containing aromatic rings, which may optionally contain an aliphatic hydrocarbon group as a substituent and may also be fused with an alicyclic ring. Aromatic hydrocarbon groups refer to monovalent or polyvalent aromatic hydrocarbons. Furthermore, aromatic rings refer to hydrocarbons containing a conjugated unsaturated ring structure, and alicyclic rings refer to hydrocarbons that have a ring structure but do not contain a conjugated unsaturated ring structure.

[0022] As used herein, alkyl refers to a group obtained by removing any one hydrogen from a straight-chain or branched-chain saturated hydrocarbon, and includes straight-chain alkyl and branched-chain alkyl, and cycloalkyl refers to a group obtained by removing one hydrogen from a saturated hydrocarbon containing a ring structure, and optionally contains a straight-chain or branched-chain alkyl as a side chain within the ring structure.

[0023] As used herein, aryl refers to a group obtained by removing any one hydrogen from an aromatic hydrocarbon, alkylene refers to a group obtained by removing any two hydrogens from a linear or branched saturated hydrocarbon, and arylene refers to a hydrocarbon group obtained by removing any two hydrogens from an aromatic hydrocarbon.

[0024] As used herein, "C x-y "," "C x -C y " and "C x " refers to the number of carbon atoms in a molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl having 1 to 6 carbons (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl). Furthermore, as used herein, fluoroalkyl refers to an alkyl in which one or more hydrogen atoms are substituted with fluorine atoms, and fluoroaryl refers to an aryl in which one or more hydrogen atoms are substituted with fluorine atoms.

[0025] In the present specification, when a polymer has multiple types of repeating units, these repeating units are copolymerized. The copolymerization may be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or any mixture thereof.

[0026] In this specification, "%" represents mass % and "ratio" represents mass ratio.

[0027] According to the present invention, the composition is preferably a photocurable composition, and preferably the composition does not contain any polysiloxanes, at least i) an alkali-soluble polymer containing an ethylenic double bond; ii) a colorant, and

[0028] -Alkali-soluble polymer The composition according to the present invention comprises an alkali-soluble polymer containing an ethylenic double bond.

[0029] Preferably, the alkaline polymer has a solid acid value of 30 to 160 mg KOH / g, more preferably 50 to 150 mg KOH / g, and even more preferably 60 to 80 mg KOH / g, from the viewpoints of enabling development with a low concentration alkaline developer, preferably development in a shorter development time, and achieving both reactivity and storage stability. For example, 2-propenoic acid having 2-hydroxyethyl 2-methyl-2-propenoate, 2-isocyanatoethyl 2-propenoate, and methyl 2-methyl-2-propenoate, 2-methyl-polymer (C6H10O3.C6H7NO3.C5H8O2.C4H6O2)x (CAS Registry Number 1615232-03-05), can be preferably used to form the polymer.

[0030] In a preferred embodiment of the present invention, from the viewpoints of desirable viscosity, reactivity, developability, and ease of handling, the weight average molecular weight of the alkali-soluble polymer is in the range of 1,000 to 100,000, more preferably 1,200 to 30,000, and even more preferably 3,000 to 8,000. In this specification, the weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography.

[0031] Such alkali-soluble polymers are available as the ACA series manufactured by DAICOLL Allnex Co., such as (ACA)Z200M, (ACA)Z250, (ACA)Z251, (ACA)Z254F, (ACA)Z300, and (ACA)Z320, as described in, for example, JP 2016-69400 A (Natoko).

[0032] Preferably, the alkali-soluble polymer is a polymer containing an acryloyl group. Thus, preferably, the alkali-soluble polymer is a (meth)acrylate polymer, more preferably, it is a methacrylate polymer, an acrylate polymer or a combination thereof, and even more preferably, the polymeric material is an acrylate polymer.

[0033] The alkali-soluble polymer used in the present invention may have a carboxy group, which can improve the solubility of the alkali-soluble polymer in a low-concentration developer.

[0034] According to the present invention, the term "alkali-soluble polymer" means a polymer that is soluble in a 2.38% aqueous solution of TMAH at 23.0±0.1°C.

[0035] -(meth)acrylate polymer As used herein, the term "(meth)acrylate" is a generic term for acrylate and methacrylate.

[0036] According to the present invention, it is preferred to use one or more (meth)acrylate polymers when low concentration developers are used and / or when low curing temperatures are applied.

[0037] The alkali-soluble polymer used in the present invention can be selected from commonly used methacrylate polymers, acrylate polymers or combinations thereof, and is more preferably an acrylic polymer such as polyacrylic acid, polymethacrylic acid, polyalkyl acrylate, polyalkyl methacrylate, etc. The acrylic polymer used in the present invention preferably contains a repeating unit containing an acryloyl group, and preferably further contains a repeating unit containing a carboxy group.

[0038] The repeating unit containing a carboxy group is not particularly limited as long as it contains a carboxy group in the side chain, but is preferably a repeating unit derived from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof.

[0039] Furthermore, the above-mentioned polymer preferably contains a repeating unit containing a hydroxy group derived from a hydroxy group-containing unsaturated monomer.

[0040] Furthermore, a (patterned) cured film can be formed by applying the composition of the present invention to a substrate, exposing it to light, and developing it. At this stage, it is necessary for there to be a difference in solubility between the exposed and unexposed regions, and the coating film in the unexposed regions should have a certain level of solubility in a developer. For example, if the dissolution rate (hereinafter also referred to as alkaline dissolution rate or ADR, details of which will be described later) of the prebaked coating film in a 2.38% aqueous solution of tetramethylammonium hydroxide (hereinafter also referred to as TMAH) is 50 Å / sec or higher, it is believed that a pattern can be formed by exposure and development. However, since the required solubility varies depending on the film thickness and development conditions of the cured film to be formed, it is necessary to appropriately select an alkali-soluble polymer depending on the development conditions. Although this will vary depending on the type and amount of photosensitizer or silanol catalyst contained in the composition, for example, when the film thickness is 0.1 to 100 μm (1,000 to 1,000,000 Å), the dissolution rate in a 2.38% TMAH aqueous solution is preferably 50 to 20,000 Å / sec, and more preferably 100 to 10,000 Å / sec.

[0041] -Thiolic acid-containing polyfunctional compounds According to the present invention, in a preferred embodiment, the composition further comprises a thiol-containing polyfunctional compound. Preferably, the thiol-containing polyfunctional compound contains a pentaerythritol structure. In a more preferred embodiment, the thiol-containing polyfunctional compound has the following chemical formula: x ), [ka] During the ceremony, R 1a , R 1b , R 1c , and R 1dare each independently selected from a hydrogen atom, an alkyl chain having 1 to 10 carbon atoms, a cyclo group having 3 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; at least one H atom is replaced by an SH group; one or more non-adjacent CH groups may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH; one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2; R 1a , R 1b , R 1c , and R 1d is not a hydrogen atom, and preferably R 1a , R 1b , R 1c , and R 1d At least two of the R 1a , R 1b , R 1c But it is not a hydrogen atom.

[0042] As the thiol-containing polyfunctional compound, a commonly available one can be used. Examples of such a thiol-containing polyfunctional compound include bifunctional thiols such as 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(2-(sulfanylbutanoyloxy)ethyl), tris-[(3-mercaptopropionyloxy)-ethyl-]-isocyanurate, trimethylolpropane tris(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylol-ethanetris(3-mercaptobutyrate), and trimethylol-ethanetris(3-mercaptobutyrate). Examples of suitable thiol-containing polyfunctional compounds include trimethylolpropane tris(3-mercaptobutyrate) (Karenz MT-TPMB™) and pentaerythritol tetrakis(3-mercaptobutyrate) (Karenz MT-PE-1™), as well as other trifunctional and tetrafunctional thiols such as 2-hydroxymethyl-2-methyl-1,3-propanediol tris-(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), and pentaerythritol tetrakis(3-sulfanylbutanoate). Among these, from the viewpoint of achieving high sensitivity with reduced exposure energy and shorter exposure times, preferred thiol-containing polyfunctional compounds are those containing a pentaerythritol structure, such as trimethylolpropane tris(3-mercaptobutyrate) (Karenz MT-TPMB™) and pentaerythritol tetrakis(3-mercaptobutyrate) (Karenz MT-PE-1™).

[0043] -Polymerization initiator The composition according to the present invention may contain a polymerization initiator. Examples of the polymerization initiator include a polymerization initiator that generates an acid, a base, or a radical when exposed to radiation, and a polymerization initiator that generates an acid, a base, or a radical when exposed to heat.

[0044] Therefore, in a preferred embodiment of the present invention, the composition further comprises a polymerization initiator, more preferably selected from a photoradical initiator, a photoacid generator, or a combination of a photoradical initiator and a photoacid generator.

[0045] From the viewpoint of optimizing the bank structure, a photoacid generator is preferred. Because the composition contains a colorant, when the composition is coated on the surface of a substrate and then irradiated with light to create a bank pattern, the amount / intensity of light irradiated to the underside of the coated composition is smaller than that of the upper side of the coated composition. This means that the underside of the coated composition is not sufficiently photocured, resulting in a distorted bank structure. It is believed that adding a photoacid generator can minimize or solve this problem because the photogenerated acid spreads throughout the composition.

[0046] Examples of the photoacid generator include diazomethane compounds, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts, and sulfonamide compounds. The structure of these photoacid generators is represented by the formula (A): R + X - (A) In formula (A), R + is an organic ion modified with hydrogen or carbon atoms or other heteroatoms, where the organic ion is selected from the group consisting of alkyl, aryl, alkenyl, acyl, and alkoxy groups. For example, R + is a diphenyliodonium ion or a triphenylsulfonium ion.

[0047] Furthermore, X - is preferably a counterion represented by any of the following formulas: SbY6 - , AsY6 - , R a p PY 6-p - , R a q BY 4-q - , R a q Gay 4-q -, R a SO3 - , (R a SO2)3C - , (R a SO2)2N - , R a COO - , and SCN - and During the ceremony, Y is a halogen atom, R a is an alkyl group of 1 to 20 carbon atoms or an aryl group of 6 to 20 carbon atoms, each of which is substituted with a substituent selected from the group consisting of fluorine, nitro, and cyano; R b is hydrogen or an alkyl group of 1 to 8 carbon atoms; p is a number from 0 to 6, q is a number from 0 to 4.

[0048] A specific example of a counter ion is BF4 - , (C6F5)4B - , ((CF3)2C6H3)4B - , PF6 - , (CF3CF2)3PF3 - , SbF6 - , (C6F5)4Ga - , ((CF3)2C6H3)4Ga - , SCN - , (CF3SO2)3C - , (CF3SO2)2N - , formate ion, acetate ion, trifluoromethanesulfonate ion, nonafluorobutanesulfonate ion, methanesulfonate ion, butanesulfonate ion, benzenesulfonate ion, p-toluenesulfonate ion, and sulfonate ion.

[0049] Among the photoacid generators usable in the present invention, those that generate sulfonic acid or boric acid are particularly preferred, such as tricumyl iodonium tetrakis(pentafluorophenyl)borate (PHOTOINITIATOR 2074™, manufactured by Rhodorsil), diphenyl iodonium tetra(perfluorophenyl)borate, and compounds having a sulfonium ion and a pentafluoroborate ion as the cation and anion moieties, respectively. Further examples of the photoacid generator include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium tetra(perfluorophenyl)borate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium trifluoromethanesulfonate, 1-(4,7-dibutoxy-1-naphthalenyl)tetrahydrothiophenium trifluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, and diphenyliodonium hexafluoroarsenate. In addition, a photoacid generator represented by the following formula can also be used: [ka] During the ceremony, each A is independently a substituent selected from the group consisting of an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylcarbonyl group of 1 to 20 carbon atoms, an arylcarbonyl group of 6 to 20 carbon atoms, a hydroxy group, and an amino group; each p is independently an integer from 0 to 5; B - is a fluorinated alkylsulfonate group, a fluorinated arylsulfonate group, a fluorinated alkylborate group, an alkylsulfonate group or an arylsulfonate group.

[0050] It is also possible to use a photoacid generator in which the cations and anions of the above formulas are exchanged with each other, or in which various other cations and anions are combined.For example, any one of the sulfonium ions represented by the above formulas can be combined with a tetra(perfluorophenyl)borate ion, and any one of the iodonium ions represented by the above formulas can be combined with a tetra(perfluorophenyl)borate ion.These can also be used as photoacid generators.

[0051] In the present invention, the reaction starts immediately after irradiation with radiation, and the reheating process carried out after irradiation with radiation and before the development process can be omitted. Therefore, from the viewpoints of shortening the process and reducing costs, a photoradical generator is more preferred.

[0052] The photoradical generator can improve the resolution by strengthening the pattern shape or increasing the development contrast. The photoradical generator used in the present invention is a photoradical generator that generates radicals upon irradiation with radiation. In this specification, examples of radiation include visible light, ultraviolet light, infrared light, X-rays, electron beams, α rays, and γ rays.

[0053] The optimal amount of photoradical generator added depends on the type and amount of active substance generated by decomposition of the photoradical generator, the required photosensitivity, and the required dissolution contrast between exposed and unexposed regions. It is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass, based on the total mass of the alkali-soluble polymer. If the amount added is less than 0.001% by mass, the dissolution contrast between exposed and unexposed regions may be too low, resulting in ineffective addition. On the other hand, if the amount added exceeds 50% by mass, cracks may occur in the formed coating film, or coloration due to decomposition of the photoradical generator may become significant, resulting in a decrease in the colorless transparency of the coating film. Furthermore, if the amount added is too high, thermal decomposition of the photoradical generator may cause deterioration in the electrical insulation of the cured product or release gas, which may cause problems in subsequent processes. Furthermore, it may also reduce the resistance of the coating film to photoresist stripping solutions containing monoethanolamine or other compounds as a major component.

[0054] Examples of photoradical generators include azo-based, peroxide-based, acylphosphine oxide-based, alkylphenone-based, oxime ester-based, and titanocene-based initiators. Among these, alkylphenone-based, acylphosphine oxide-based, and oxime ester-based initiators are preferred, and examples thereof include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholino-2-methylpropionyl) ... 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)-phenyl]-1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), bis(2,4-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium(IV), and the like.

[0055] - a compound containing at least two (meth)acryloyloxy groups In a preferred embodiment of the present invention, the composition further comprises a compound containing at least two (meth)acryloyloxy groups. Preferably, the at least two (meth)acryloyloxy groups are two or more acryloyloxy groups, methacryloyloxy groups, or a combination thereof, and the total amount of the compound containing at least two (meth)acryloyloxy groups based on the total amount of the alkali-soluble polymer is preferably 5% by weight to 1,000% by weight, more preferably 10% by weight to 500% by weight, and even more preferably 15% by weight to 300% by weight, from the viewpoint of compatibility with the resin. Preferably, the compound is a monomer having a molecular weight of 2,000 or less, more preferably in the range of 2,000 to 50, and even more preferably 1,000 to 100. Preferably, from the viewpoint of reactivity, the compound is relatively smaller than the alkali-soluble polymer.

[0056] In this specification, the term "(meth)acryloyloxy group" is a general term for an acryloyloxy group and a methacryloyloxy group. This compound is capable of forming a crosslinked structure by reacting with an alkali-soluble polymer. In this specification, a compound containing two or more reactive acryloyloxy groups or methacryloyloxy groups is required to form a crosslinked structure, and in order to form a higher-order crosslinked structure, it is preferable that the compound contain three or more acryloyloxy groups or methacryloyloxy groups.

[0057] Furthermore, the (meth)acryloyloxy group-containing compounds can be used alone or in combination of two or more kinds.

[0058] Preferably, the compound containing at least two (meth)acryloyloxy groups is a polyacrylate monomer having at least three (meth)acryloyloxy groups, and more preferably, it is a polyacrylate monomer selected from one or more members of the group consisting of a polyacrylate monomer having three (meth)acryloyloxy groups, a polyacrylate monomer having four (meth)acryloyloxy groups, a polyacrylate monomer having five (meth)acryloyloxy groups, and a polyacrylate monomer having six (meth)acryloyloxy groups. and even more preferably, it is a polyacrylate monomer having five (meth)acryloyloxy groups, a polyacrylate monomer having six (meth)acryloyloxy groups, or a mixture thereof, and preferably, the polyacrylate monomer having three (meth)acryloyloxy groups is selected from one or more members of the group consisting of trimethylolpropane triacrylate, trimethylolpropane ethoxy triacrylate, trimethylolpropane propoxy triacrylate, glycerin propoxy triacrylate, pentaerythritol triacrylate; Preferably, the polyacrylate monomer having four (meth)acryloyloxy groups is selected from one or more members of the group consisting of pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, pentaerythritolehoxy tetraacrylates; Preferably, the polyacrylate monomer having five (meth)acryloyloxy groups is dipentaerythritol hexaacrylate, preferably, the polyacrylate monomer having six (meth)acryloyloxy groups is dipentaerythritol pentaacrylate, and most preferably, the compound is dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, or a mixture thereof.

[0059] -Surfactants Furthermore, the composition according to the present invention may optionally contain a surfactant, preferably a nonionic surfactant, such as a hydrocarbon-based nonionic surfactant, a fluorine-based nonionic surfactant, for example, Fluorad (trade name, 3M Japan Limited), Megafac (trade name, DIC Corporation), or Surflon (trade name, AGC Inc.), or an organosilicon-based nonionic surfactant, for example, KP341 (trade name, Shin-Etsu Chemical Co., Ltd.). Co., Ltd.) or a combination thereof, and more preferably, the hydrocarbon-based nonionic surfactant is selected from the group consisting of polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diesters; polyoxyethylene fatty acid monoesters; polyoxyethylene polyoxypropylene block polymers; acetylene alcohols; acetylene glycols such as 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-2,4-dimethyl-3,6-dimethyl-4 ... The surfactant is preferably selected from one or more members of the group consisting of tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, and 2,5-dimethyl-2,5-hexanediol; polyethoxylates of acetylene alcohols; and acetylene glycol derivatives, such as polyethoxylates of acetylene glycol. Preferably, the fluorine-based nonionic surfactant is selected from one or more fluorine-containing surfactants. Preferably, the hydrocarbon-based nonionic surfactant is selected from organosiloxane surfactants. Preferably, the surfactant is a fluorine-based nonionic surfactant. In particular, the Megafac RS series (trade name, DIC Corporation) is ideal for the present invention from the viewpoint of improving the hydrophobicity and / or oil-repellency of the bank surface (particularly, realizing oil-repellency of the top surface of the bank after bank creation).

[0060] Preferably, the total amount of surfactants is in the range of 0.001 to 5 wt %, more preferably 0.01 to 4 wt %, even more preferably 0.05 to 3 wt %, and even more preferably 0.1 to 1 wt %, based on the total amount of total solids in the composition.

[0061] The surfactant is added for the purposes of improving coating properties, improving developability, realizing improved hydrophobicity of the bank surface, and / or realizing improved oil repellency of the bank surface.

[0062] -Coloring agent According to the present invention, the composition contains a colorant, and preferably the total amount of the colorant is 3 to 80% by weight, preferably 5 to 50% by weight, based on the total amount of solids in the composition.

[0063] Preferably, the colorant is a first colorant selected from organic colorants and / or inorganic colorants, more preferably a black colorant selected from organic black pigments and / or inorganic black pigments or a white colorant selected from organic white pigments and / or inorganic white pigments, even more preferably a black colorant selected from organic black pigments and / or inorganic black pigments, still more preferably an inorganic black pigment, and particularly preferably the inorganic black pigment is zirconium nitride or tinatnina oxide, which may be coated with a polymer and / or inorganic layer.

[0064] The colorant (preferably a black colorant) used in the present invention may be either an inorganic pigment or an organic pigment, or a combination of two or more pigments, as long as it satisfies the required absorbance.

[0065] When an organic black colorant is used in the bank, it is preferable to combine two or more organic pigments to obtain a black pigment. For example, a black pigment can be obtained by mixing red, green, and blue organic pigments.

[0066] The colorant used in the present invention can be used in combination with a dispersant, such as an organic compound-based dispersant such as the polymer dispersant described in JP-A-2004-292672.

[0067] In a preferred embodiment of the present invention, the composition further comprises another colorant that is different from the first colorant. Preferably, the other colorant is a second colorant selected from organic colorants and / or inorganic colorants, more preferably a black colorant selected from organic black pigments and / or inorganic black pigments or a white colorant selected from organic white pigments and / or inorganic white pigments, even more preferably a white colorant selected from organic white pigments and / or inorganic white pigments, and even more preferably an inorganic white pigment.

[0068] Therefore, in a further preferred embodiment of the present invention, the composition comprises a first colorant and a second colorant, wherein the first colorant is a black pigment and the second colorant is a white pigment, thereby achieving a gray colored composition and a gray colored pattern bank.

[0069] -solvent In a preferred embodiment of the present invention, the composition further comprises a solvent.

[0070] The type of solvent is not particularly limited, and any commonly available solvent can be used as long as it can uniformly dissolve or disperse the above-mentioned alkali-soluble polymer, polymerization initiator, and compound containing at least two (meth)acryloyloxy groups.

[0071] Preferably, the solvent is an ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; a diethylene glycol dialkyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; an ethylene glycol alkyl ether acetate such as methyl cellosolve acetate and ethyl cellosolve acetate; a propylene glycol monoalkyl ether such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; a propylene glycol alkyl ether acetate such as PGMEA, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone. More preferably, the solvent is a combination of a propylene glycol alkyl ether acetate or ester and a cyclic ester such as γ-butyrolactone. Preferably, the total amount of the solvent based on the total amount of the composition is in the range of 1% by weight to 99% by weight, preferably 5% by weight to 90% by weight, even more preferably 10% by weight to 80% by weight, and even more preferably 20% by weight to 70% by weight.

[0072] -Other additives The composition according to the present invention may optionally contain other additives, such as a developer dissolution promoter, a scum remover, an adhesion promoter, a polymerization inhibitor, a defoamer, a surfactant, a photosensitizer, a crosslinking agent, and a curing agent.

[0073] Therefore, according to the present invention, preferably the composition further comprises at least one additive selected from one or more members of the group consisting of developer dissolution promoters, scum removers, adhesion promoters, polymerization inhibitors, antifoaming agents, surfactants, photosensitization accelerators, crosslinking agents, and / or hardeners.

[0074] The developer dissolution promoter or scum remover functions to adjust the solubility of the formed coating film in the developer and prevent scum from remaining on the substrate after development. Crown ethers can be used as such additives. The crown ether with the simplest structure has the general formula (-CH2-CH2-O-) n In the present invention, preferred is one in which n is 4 to 7. When x is the total number of atoms constituting the ring and y is the number of oxygen atoms contained therein, the crown ether is sometimes called an x-crown-y-ether. In the present invention, preferred is one selected from the group consisting of crown ethers in which x=12, 15, 18, or 21 and y=x / 3, as well as their benzo-condensation products and cyclohexyl-condensation products. More preferred examples of crown ethers include 21-crown-7 ether, 18-crown-6 ether, 15-crown-5 ether, 12-crown-4 ether, dibenzo-21-crown-7 ether, dibenzo-18-crown-6 ether, dibenzo-15-crown-5 ether, dibenzo-12-crown-4 ether, dicyclohexyl-21-crown-7 ether, dicyclohexyl-18-crown-6 ether, dicyclohexyl-15-crown-5 ether, and dicyclohexyl-12-crown-4 ether. In the present invention, among these, 18-crown-6 ether and 15-crown-5 ether are most preferred. The content of the crown ether is preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the alkali-soluble polymer.

[0075] The adhesion promoter has the effect of preventing peeling of the pattern due to stress applied after baking when a cured film is formed using the composition of the present invention. Examples of the adhesion promoter include imidazoles and silane coupling agents. Among imidazoles, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, and 2-aminoimidazole are preferred, with 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, and imidazole being particularly preferred.

[0076] As the silane coupling agent, known ones are suitably used, and examples thereof include epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, etc. Specifically, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-ureidopropyl triethoxysilane, 3-chloropropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, etc. are preferred. These can be used alone or in combination of two or more, and the amount added is preferably 0.05 to 15 mass% based on the total mass of the alkali-soluble polymer.

[0077] Furthermore, as the silane coupling agent, a silane compound or a siloxane compound having an acid group can be used. Examples of the acid group include a carboxy group, an acid anhydride group, and a phenolic hydroxy group. When a monobasic acid group such as a carboxy group or a phenolic hydroxy group is contained, it is preferable that one silicon-containing compound has multiple acid groups.

[0078] Specific examples of such silane coupling agents include those represented by the following formula (C): X n Si(OR C3 ) 4-n (C) A compound represented by or a polymer obtained by using it as a repeating unit. In this case, X or R C3 A combination of multiple repeating units with different repeating units can be used.

[0079] In the formula, R C3 Examples of R include hydrocarbon groups, such as alkyl groups such as methyl, ethyl, n-propyl, isopropyl, and n-butyl. C3 Each R C3 may be the same or different.

[0080] Examples of X include those having an acid group such as a phosphonium group, a borate group, a carboxy group, a phenol group, a peroxide group, a nitro group, a cyano group, a sulfo group, or an alcohol group, and those in which the acid group is protected by an acetyl group, an aryl group, an amyl group, a benzyl group, a methoxymethyl group, a mesyl group, a tolyl group, a trimethoxysilyl group, a triethoxysilyl group, a triisopropylsilyl group, or a trityl group, and an acid anhydride group.

[0081] Among them, R such as silicone containing acid anhydride groups C3 Preferred is a compound having a methyl group as X and a carboxylic acid anhydride group as X. More specifically, a compound represented by the following formula (X-12-967C (trade name, Shin-Etsu Chemical Co., Ltd.)) and a polymer containing a corresponding structure at the end or side chain of a silicon-containing polymer such as silicone are preferred. [ka]

[0082] Furthermore, compounds in which an acid group such as thiol, phosphonium, borate, carboxy, phenol, peroxide, nitro, cyano, or sulfo group is provided at the end of a dimethyl silicone are also preferred. Examples of such compounds include the compounds represented by the following formula (X-22-2290AS and X-22-1821 (both trade names, Shin-Etsu Chemical Co., Ltd.)). [ka]

[0083] When the silane coupling agent has a silicone structure, if the molecular weight is too large, compatibility with the polysiloxane contained in the composition will be poor, solubility in the developer will not be improved, reactive groups will remain in the film, and adverse effects such as an inability to maintain chemical resistance sufficient to withstand subsequent processes may occur. For this reason, the mass average molecular weight of the silane coupling agent is preferably 5000 or less, more preferably 4000 or less. The content of the silane coupling agent is preferably 0.01 to 15 mass% based on the total mass of the alkali-soluble polymer.

[0084] Examples of polymerization inhibitors that can be added include ultraviolet absorbers, nitrones, nitroxide radicals, hydroquinones, catechols, phenothiazines, phenoxazines, hindered amines, and derivatives thereof. Among these, methylhydroquinone, catechol, 4-t-butylcatechol, 3-methoxycatechol, phenothiazines, chlorpromazines, phenoxazines, and hindered amines such as TINUVIN 144, 292, and 5100 (BASF), and ultraviolet absorbers such as TINUVIN 326, 328, 384-2, 400, and 477 (BASF) are preferred. These can be used alone or in combination of two or more, and their content is preferably 0.01 to 20% by mass based on the total mass of the alkali-soluble polymer.

[0085] As the defoaming agent, the alcohol (C 1-18), higher fatty acids such as oleic acid and stearic acid, higher fatty acid esters such as glycerin monolaurate, polyethers such as polyethylene glycol (PEG) (Mn: 200 to 10,000) and polypropylene glycol (PPG) (Mn: 200 to 10,000), silicone compounds such as dimethylsilicone oil, alkyl-modified silicone oil and fluorosilicone oil, and organosiloxane surfactants. These can be used alone or in combination, and the content thereof is preferably 0.1 to 3 mass% based on the total mass of the alkali-soluble polymer.

[0086] -Photosensitizer A photosensitizer accelerator can be optionally added to the bank composition according to the present invention. Examples of photosensitizer accelerators that are preferably used in the composition according to the present invention include coumarin, ketocoumarin and derivatives thereof, thiopyrylium salts, and acetophenones, specifically, p-bis(o-methylstyryl)benzene, 7-dimethylamino-4-methylquinolone-2,7-amino-4-methylcoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 2-(p-dimethylaminostyryl)-pyridylmethyl-iodide, 7-diethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 2,3,5,6-1H,4H-tetrahydro-8-methyl-quinolizino-<9,9a,1-gh>coumarin, 7-diethylamino-4-trifluoromethylcoumarin, 7-dimethylamino-4-trifluoromethylcoumarin, 7-amino-4-trifluoromethylcoumarin, 2,3,5,6-1H,4H- Examples of sensitizing dyes include tetrahydroquinolizino-<9,9a,1-gh>coumarin, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin, 2,3,5,6-1H,4H-tetrahydro-9-carbethoxyquinolizino-<9,9a,1-gh>coumarin, 3-(2'-N-methylbenzimidazolyl)-7-N,N-diethylaminocoumarin, N-methyl-4-trifluoromethylpiperidino-<3,2-g>coumarin, 2-(p-dimethylaminostyryl)-benzothiazolylethyl iodide, 3-(2'-benzimidazolyl)-7-N,N-diethylaminocoumarin, 3-(2'-benzothiazolyl)-7-N,N-diethylaminocoumarin, and pyrylium salts and thiopyrylium salts represented by the following chemical formulas. The addition of a sensitizing dye enables patterning using an inexpensive light source such as a high-pressure mercury lamp (360 to 430 nm). The content of the sensitizing dye is preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the alkali-soluble polymer. [ka] [Table 1]

[0087] Furthermore, anthracene skeleton-containing compounds can also be used as the photosensitization promoter. Specific examples include compounds represented by the following formula: [ka] In the formula, R 31 each independently represents a substituent selected from the group consisting of an alkyl group, an aralkyl group, an allyl group, a hydroxyalkyl group, an alkoxyalkyl group, a glycidyl group, and a halogenated alkyl group; R 32 each independently represents a substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxy group, an amino group, and a carboalkoxy group; Each k is independently selected from 0 and an integer of 1 to 4.

[0088] When such a photosensitization accelerator having an anthracene skeleton is used, the content thereof is preferably 0.01 to 5% by mass based on the total mass of the alkali-soluble polymer.

[0089] In another aspect, the present invention further comprises at least the following steps: (Xi) providing the composition of the present invention on a layer or substrate to form a coating layer; (Xii) baking the coating layer to obtain a hardened layer. Preferably, the method further comprises, after step (Xi) and before step (Xii), one or more of the following steps: (Xiii) a step of pre-baking (heat treating) the coating layer in order to dry the coating layer and reduce the amount of residual solvent in the coating layer, the pre-baking process being preferably carried out at a temperature of generally 50 to 150°C, preferably 90 to 120°C, for 10 to 300 seconds, preferably 30 to 120 seconds, in the case of using a hot plate, or for 1 to 30 minutes in the case of using a clean oven; (Xiv) irradiating the coating layer with light (applying light irradiation), preferably with light having a peak maximum wavelength in the range of 360 to 430 nm, preferably using a patterned mask when performing the light irradiation; (Xv) applying a post-exposure bake process, and / or (Xvi) applying a development process to form a patterned hardened layer;

[0090] - a method for producing a hardened layer (preferably a bank production process) Step (Xi): Application process First, the above-described composition is applied to a substrate. The formation of a coating film of the composition of the present invention can be carried out by any method conventionally known as a method for applying a photosensitive composition. Specifically, the method can be freely selected from dip coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, slit coating, and the like. Furthermore, suitable substrates such as silicon substrates, glass substrates, and resin films can be used as the substrate to which the composition is applied. Various semiconductor devices can be formed on these substrates as needed. When the substrate is a film, gravure coating can also be used. If desired, a drying process can be further provided after the film is applied. Furthermore, if necessary, the application process can be repeated once or twice or more times to achieve the desired thickness of the coating film formed.

[0091] Step (Xiii): Pre-bake process After applying the composition to form a coating film of the composition, the coating film is preferably prebaked (heat-treated) to dry it and reduce the amount of solvent remaining in the coating film. The prebaking process is preferably carried out at a temperature of generally 50 to 150°C, preferably 90 to 120°C, for 10 to 300 seconds, preferably 30 to 120 seconds, using a hot plate, or for 1 to 30 minutes using a clean oven.

[0092] Step (Xiv): Exposure process After the coating film is formed, the surface of the coating film is then irradiated with light. Any light source conventionally used in pattern formation methods can be used for the light irradiation. Examples of such light sources include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, xenon lamps, laser diodes, and LEDs. Ultraviolet rays such as g-rays, h-rays, and i-rays are usually used as the irradiated light. Except for ultrafine processing of semiconductors and the like, light of 360 to 430 nm (high-pressure mercury lamps) is generally used for patterning of several μm to several tens of μm. The energy of the irradiated light varies depending on the light source and the thickness of the coating film, but is usually 5 to 2000 mJ / cm. 2 , preferably 10 to 1000 mJ / cm 2 The irradiation light energy is 5 mJ / cm 2 On the other hand, if the irradiation light energy is less than 2000 mJ / cm, sufficient resolution may not be obtained. 2 If it exceeds this value, the amount of exposure becomes excessive, which may result in the occurrence of halation.

[0093] A general photomask can be used to irradiate light in a pattern shape. Such a photomask can be freely selected from known photomasks. The environment during irradiation is not particularly limited, and can usually be an atmospheric atmosphere (in air) or a nitrogen atmosphere. Furthermore, when a film is formed on the entire surface of a substrate, the entire surface of the substrate can be irradiated with light. In the present invention, the patterned film also includes a case where a film is formed on the entire surface of a substrate.

[0094] Step (Xv): Post-exposure bake process After exposure, post-exposure baking can be performed as needed to promote the reaction between polymers in the film caused by the polymerization initiator. This heat treatment differs from the heating process (6) described below in that it does not completely harden the coating film, but rather is performed to leave only the desired pattern on the substrate after development and make the remaining areas removable by development. Therefore, this is not essential in the present invention.

[0095] When performing post-exposure baking, a hot plate, oven, furnace, or the like can be used. Since it is undesirable for acids, bases, or radicals generated in the exposed region by light irradiation to diffuse to the unexposed region, the heating temperature should not be too high. From this perspective, the post-exposure heating temperature range is preferably 40 to 150°C, more preferably 60 to 120°C. Stepwise heating can be applied as necessary to control the curing rate of the composition. Furthermore, the heating atmosphere is not particularly limited and can be selected from an inert gas such as nitrogen, under vacuum, under reduced pressure, or in oxygen gas, etc., in order to control the curing rate of the composition. Furthermore, the heating time is preferably at least a certain length to maintain a high degree of uniformity in the temperature history within the wafer surface, and is preferably not too long to suppress the diffusion of the generated acids, bases, and radicals. From this perspective, the heating time is preferably 20 to 500 seconds, more preferably 40 to 300 seconds.

[0096] Step (Xvi): Development process After exposure, optionally followed by post-exposure baking, the coating film is developed. Any developer conventionally used for developing photosensitive compositions can be used as the developer. Preferred examples of developers include alkaline developers, which are aqueous solutions of alkaline compounds such as tetraalkylammonium hydroxide, choline, alkali metal hydroxides, alkali metal metasilicate (hydrates), alkali metal phosphate (hydrates), aqueous sodium carbonate, ammonia, alkylamines, alkanolamines, and heterocyclic amines. Particularly preferred alkaline developers are aqueous tetramethylammonium hydroxide, potassium hydroxide, sodium hydroxide, or sodium carbonate. If necessary, these alkaline developers may further contain a water-soluble organic solvent such as methanol or ethanol, or a surfactant. In the present invention, development can be performed using a developer with a lower concentration than the 2.38% by mass TMAH developer typically used as a developer. Examples of such developers include a 0.05 to 1.5 mass % TMAH aqueous solution, a 0.1 to 2.5 mass % sodium carbonate aqueous solution, and a 0.01 to 1.5 mass % potassium hydroxide aqueous solution. The development time is usually 10 to 300 seconds, preferably 30 to 180 seconds. The development method can also be freely selected from conventionally known methods. Specific examples include immersion in the developer (dip), puddle, shower, slit, cap coat, and spray methods. After developing with the developer to obtain a pattern, it is preferable to rinse with water.

[0097] Step (Xii): Heating process After development, the resulting pattern film is cured by heating. The heating device used in the heating process can be the same as that used in the post-exposure heating described above. The heating temperature in this heating process is not particularly limited as long as it is a temperature at which the coating film can be cured, and can be freely determined.

[0098] The composition according to the present invention can be cured at a relatively low temperature. Specifically, it is preferably cured by heating at 350°C or less. To maintain a high residual film rate after curing, the curing temperature is more preferably 300°C or less, and particularly preferably 250°C or less.

[0099] On the other hand, in order to promote the curing reaction and obtain a sufficiently cured film, the curing temperature is preferably 70°C or higher, more preferably 100°C or higher. According to the present invention, a low curing temperature, such as about 100°C, is more preferable. Furthermore, the heating time is not particularly limited, but is usually 10 minutes to 24 hours, preferably 30 minutes to 3 hours. In addition, this heating time is the time after the temperature of the pattern film reaches the desired heating temperature. It usually takes several minutes to several hours for the pattern film to reach the desired temperature from the temperature before heating.

[0100] In another aspect, the present invention further relates to a layer obtained or obtainable from the method of the present invention.

[0101] In another aspect, the present invention further comprises at least i) a polymer (A) derived or derivable from an alkali-soluble polymer containing an ethylenic double bond, Preferably, the solid acid value of the alkaline polymer is in the range of 30 to 160 mg KOH / g, more preferably 50 to 150 mg KOH / g, and even more preferably 60 to 80 mg KOH / g; Preferably, the weight average molecular weight of the alkali-soluble polymer is in the range of 1,000 to 100,000, more preferably 1,200 to 30,000, and even more preferably 3,000 to 8,000; Preferably, the alkali-soluble polymer is selected from (meth)acrylate polymers, more preferably a methacrylate polymer, an acrylate polymer or a combination thereof, and even more preferably the polymeric material is an acrylate polymer; and ii) a colorant; and Preferably, the layer is a patterned layer. Preferably, the colorant is a first colorant selected from organic colorants and / or inorganic colorants, more preferably a black colorant selected from organic black pigments and / or inorganic black pigments or a white colorant selected from organic white pigments and / or inorganic white pigments, even more preferably a black colorant selected from organic black pigments and / or inorganic black pigments, still more preferably an inorganic black pigment, and particularly preferably the inorganic black pigment is zirconium nitride or tinatnina oxide, which may be coated with a polymer and / or inorganic layer.

[0102] In a preferred embodiment of the present invention, the optical density (OD) value of the layer at a layer thickness of 10 μm at a light wavelength of 460 nm is in the range of 1.0 to 3.0, the OD value of the layer at a layer thickness of 10 μm at a light wavelength of 540 nm is in the range of 1.0 to 3.0, and / or the OD value of the layer at a layer thickness of 10 μm at a light wavelength of 630 nm is in the range of 1.0 to 3.0.

[0103] In a preferred embodiment of the present invention, the reflectance of a layer with a layer thickness of 10 μm is in the range of 30 to 90% at a light wavelength of 460 nm, in the range of 30 to 90% at a light wavelength of 540 nm, and / or in the range of 30 to 90% at a light wavelength of 630 nm.

[0104] In another aspect, the present invention further relates to a light-converting device comprising at least the layer of the present invention. Preferably, the light-converting device further comprises a substrate. Preferably, the light-converting device is a color-filtered, pixelated color-converting device.

[0105] In another aspect, the present invention further relates to an optical device comprising at least the layer of the present invention or the photo-conversion device of the present invention. Preferably, the optical device is a display device, more preferably the display device is selected from the group consisting of OLED, LCD, LED and μLED.

[0106] In another aspect, the present invention further relates to the use of the composition of the present invention or the layer of the present invention in a process for manufacturing a photoconversion device.

[0107] In another aspect, the present invention further relates to the use of the photo-conversion device of the present invention in a manufacturing process for an optical device.

[0108] In another aspect, the present invention further comprises at least A method of manufacturing an optical device includes providing the optical device with the photo-conversion device of the present invention.

[0109] Preferred Embodiments 1. A composition, preferably a photocurable composition, preferably the composition does not contain any polysiloxane; at least i) an alkali-soluble polymer containing an ethylenic double bond, Preferably, the solid acid value of the alkaline polymer is in the range of 30 to 160 mg KOH / g, more preferably 50 to 150 mg KOH / g, and even more preferably 60 to 80 mg KOH / g; Preferably, the weight average molecular weight of the alkali-soluble polymer is in the range of 1,000 to 100,000, more preferably 1,200 to 30,000, and even more preferably 3,000 to 8,000; Preferably, the alkali-soluble polymer is a (meth)acrylate polymer, more preferably a methacrylate polymer, an acrylate polymer or a combination thereof, and even more preferably, the polymeric material is an acrylate polymer; and ii) a colorant, and a composition comprising, consisting essentially of, or consisting of. Preferably, the colorant is a first colorant selected from organic colorants and / or inorganic colorants, more preferably a black colorant selected from organic black pigments and / or inorganic black pigments or a white colorant selected from organic white pigments and / or inorganic white pigments, even more preferably a black colorant selected from organic black pigments and / or inorganic black pigments, still more preferably an inorganic black pigment, and particularly preferably the inorganic black pigment is zirconium nitride or tinatnina oxide, which may be coated with a polymer and / or inorganic layer.

[0110] 2. The composition of embodiment 1, further comprising a thiol-containing polyfunctional compound. Preferably, the thiol-containing polyfunctional compound contains a pentaerythritol structure. More preferably, the thiol-containing polyfunctional compound has the following chemical formula (I): x ), [ka] During the ceremony, R 1a , R 1b , R 1c , and R 1d are each independently selected from a hydrogen atom, an alkyl chain having 1 to 10 carbon atoms, a cyclo group having 3 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; at least one H atom is replaced by an SH group; one or more non-adjacent CH groups may be replaced by an oxygen atom, C=O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH; one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2; R 1a , R 1b , R 1c , and R 1d At least one of R is not a hydrogen atom, and preferably R 1a , R 1b , R1c , and R 1d At least two of R are not hydrogen atoms, and more preferably, at least R 1a , R 1b , R 1c But it is not a hydrogen atom.

[0111] 3. The composition of embodiment 1 or 2, further comprising a polymerization initiator. Preferably, the polymerization initiator is selected from a photoradical initiator, a photoacid generator, or a combination of a photoradical initiator and a photoacid generator.

[0112] 4. The composition of any one of the preceding embodiments, further comprising a compound containing at least two (meth)acryloyloxy groups. Preferably, the at least two (meth)acryloyloxy groups are two or more acryloyloxy groups, methacryloyloxy groups, or a combination thereof, and preferably, the total amount of the compound containing at least two (meth)acryloyloxy groups based on the total amount of the alkali-soluble polymer is in the range of 5% by weight to 1,000% by weight, more preferably 10% by weight to 500% by weight, and even more preferably 15% by weight to 300% by weight, and preferably, the compound is a monomer having a molecular weight of 2,000 or less, more preferably in the range of 2,000 to 50, and even more preferably 1,000 to 100, and preferably contains at least three (meth)acryloyloxy groups. and more preferably it is a polyacrylate monomer selected from one or more members of the group consisting of a polyacrylate monomer having three (meth)acryloyloxy groups, a polyacrylate monomer having four (meth)acryloyloxy groups, a polyacrylate monomer having five (meth)acryloyloxy groups, a polyacrylate monomer having six (meth)acryloyloxy groups, and even more preferably it is a polyacrylate monomer having five (meth)acryloyloxy groups, a polyacrylate monomer having six (meth)acryloyloxy groups, or a mixture thereof; Preferably, the polyacrylate monomer having three (meth)acryloyloxy groups is selected from one or more members of the group consisting of trimethylolpropane triacrylate, trimethylolpropane ethoxy triacrylate, trimethylolpropane propoxy triacrylate, glycerin propoxy triacrylate, pentaerythritol triacrylate; Preferably, the polyacrylate monomer having four (meth)acryloyloxy groups is selected from one or more members of the group consisting of pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, pentaerythritolehoxy tetraacrylates; Preferably, the polyacrylate monomer having five (meth)acryloyloxy groups is dipentaerythritol hexaacrylate, and preferably, the polyacrylate monomer having six (meth)acryloyloxy groups is dipentaerythritol pentaacrylate; Most preferably, the compound is dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, or a mixture thereof.

[0113] 5. The composition of any one of the preceding embodiments, further comprising a surfactant. Preferably, the total amount of surfactant is in the range of 0.001 to 5 wt %, more preferably 0.01 to 4 wt %, even more preferably 0.05 to 3 wt %, and even more preferably 0.1 to 1 wt %, based on the total solids content of the composition.

[0114] 6. The composition of any one of the preceding embodiments, further comprising a solvent. Preferably, the solvent is selected from ethylene glycol monoalkyl ethers (preferably selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether); diethylene glycol dialkyl ethers (preferably selected from diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether); ethylene glycol alkyl ether acetates (preferably selected from methyl cellosolve acetate and ethyl cellosolve acetate); propylene glycol monoalkyl ethers (preferably selected from propylene glycol monomethyl ether and propylene glycol monoethyl ether); propylene glycol alkyl ether acetates (preferably selected from PGMEA, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate). aromatic hydrocarbons (preferably selected from benzene, toluene, and xylene); ketones (preferably selected from methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone); alcohols (preferably selected from ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin); esters (preferably selected from ethyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate); and cyclic esters (preferably γ-butyrolactone), more preferably the solvent is a combination of a propylene glycol alkyl ether acetate or ester and a cyclic ester, which is preferably γ-butyrolactone, and preferably the total amount of the solvent based on the total amount of the composition is in the range of 1 wt % to 99 wt %, preferably 5 wt % to 90 wt %, even more preferably 10 wt % to 80 wt %, and even more preferably 20 wt % to 70 wt %.

[0115] 7. The composition of any one of the preceding embodiments, further comprising another colorant different from the colorant of embodiment 1. Preferably, the other colorant is a second colorant selected from organic colorants and / or inorganic colorants, more preferably a black colorant selected from organic black pigments and / or inorganic black pigments or a white colorant selected from organic white pigments and / or inorganic white pigments, even more preferably a white colorant selected from organic white pigments and / or inorganic white pigments, and even more preferably an inorganic white pigment.

[0116] 8. The composition of any one of the preceding embodiments, further comprising at least one additive selected from one or more members of the group consisting of developer dissolution promoters, descumming agents, adhesion promoters, polymerization inhibitors, antifoaming agents, surfactants, photosensitizer accelerators, crosslinking agents, and hardeners.

[0117] 9. A method for producing a hardened layer, comprising at least the following steps: (Xi) providing the composition according to any one of embodiments 1 to 8 on a layer or on a substrate to form a coating layer; (Xii) baking the coating layer to obtain a hardened layer. Preferably, the method comprises, after step (Xi) and before step (Xii), the following step: (Xiii) a step of pre-baking (heat treating) the coating layer to dry the coating layer and reduce the amount of residual solvent in the coating layer (preferably, the pre-baking process is generally carried out at a temperature of 50 to 150°C, preferably 90 to 120°C, for 10 to 300 seconds, preferably 30 to 120 seconds, in the case of using a hot plate, or for 1 to 30 minutes in the case of using a clean oven); (Xiv) irradiating the coating layer with light (applying light irradiation), preferably with light having a peak maximum wavelength in the range of 360 to 430 nm, preferably using a patterning mask when performing the light irradiation; (Xv) applying a post-exposure bake process, and / or (Xvi) applying a development process to form a patterned hardened layer.

[0118] 10. A layer obtained or obtainable from the method according to embodiment 9.

[0119] 11. At least i) a polymer (A) derived or derivable from an alkali-soluble polymer containing an ethylenic double bond, Preferably, the solid acid value of the alkaline polymer is in the range of 30 to 160 mg KOH / g, more preferably 50 to 150 mg KOH / g, and even more preferably 60 to 80 mg KOH / g; Preferably, the weight average molecular weight of the alkali-soluble polymer is in the range of 1,000 to 100,000, more preferably 1,200 to 30,000, and even more preferably 3,000 to 8,000; Preferably, the alkali-soluble polymer is selected from (meth)acrylate polymers, more preferably a methacrylate polymer, an acrylate polymer or a combination thereof, and even more preferably the polymeric material is an acrylate polymer; and ii) a colorant. Preferably, the layer is a patterned layer. Preferably, the colorant is a first colorant selected from organic colorants and / or inorganic colorants, more preferably a black colorant selected from organic black pigments and / or inorganic black pigments or a white colorant selected from organic white pigments and / or inorganic white pigments, even more preferably a black colorant selected from organic black pigments and / or inorganic black pigments, still more preferably an inorganic black pigment, and particularly preferably the inorganic black pigment is zirconium nitride or tinatnina oxide, which may be coated with a polymer and / or inorganic layer.

[0120] 12. The layer according to embodiment 10 or 11, wherein the optical density (OD) value of the layer at a layer thickness of 10 μm is in the range of 1.0 to 3.0 at a light wavelength of 460 nm, in the range of 1.0 to 3.0 at a light wavelength of 540 nm, and / or in the range of 1.0 to 3.0 at a light wavelength of 630 nm.

[0121] 13. The layer according to any one of claims 10 to 12, wherein the reflectance of the layer at a layer thickness of 10 μm is in the range of 30 to 90% at a light wavelength of 460 nm, in the range of 30 to 90% at a light wavelength of 540 nm, and / or in the range of 30 to 90% at a light wavelength of 630 nm.

[0122] 14. A photo-conversion device comprising at least the layer according to any one of embodiments 10 to 13. Preferably, the photo-conversion device further comprises a substrate.

[0123] 15. An optical device comprising at least the layer according to any one of embodiments 10 to 13 or the photo-conversion device according to embodiment 14.

[0124] 16. Use of the composition according to any one of embodiments 1 to 8 or the layer according to any one of embodiments 10 to 13 in a process for producing a photoconversion device.

[0125] 17. Use of the photo-conversion device according to embodiment 14 in a manufacturing process for an optical device.

[0126] 18. A method for manufacturing an optical device, comprising: 15. A method comprising at least providing the photo-conversion device of embodiment 14 to an optical device.

[0127] Technical Effects of the Invention The present invention provides one or more of the following advantages: To enable development with a low concentration alkaline developer, preferably in a shorter development time, and / or to achieve both reactivity and storage stability of the composition; to realize high sensitivity of the composition and reduce exposure energy and exposure time; to improve the structure (bank structure) of the patterned cured film, particularly to improve the bottom side structure of the patterned cured film; to achieve improved reflection and / or high optical density (OD) of the cured film, particularly to achieve improved reflection and / or high OD of the cured film having white and black pigments (gray bank).

[0128] The following examples provide an explanation of the invention as well as detailed descriptions of their preparation, however, the invention need not be limited to the examples. [Example]

[0129] Working Example (WE) 1: Preparation of bank composition Bank composition 1 is prepared using the following ingredients: [Table 2]

[0130] Acrylic Polymer A: An acrylic random polymer made from a carbon acid monomer and a monomer containing at least one aromatic ring group (Shin-Nakajima). Acrylic Polymer B: 2-Propenoic acid, 2-methyl-polymer with 2-hydroxyethyl 2-methyl-2-propenoate, 2-isocyanatoethyl 2-propenoate, and methyl 2-methyl-2-propenoate (Natoco). Herein, the PGMEA solvent is added such that after adding the solvent, the composition contains 45 wt. % total solids and 55 wt. % solvent, based on the total weight of the composition.

[0131] Examples 2 to 11: Preparation of bank compositions Bank Compositions 2-11 are prepared in the same manner as described in Example 1 above, except that the following materials listed in Table 2 are used in place of the materials used in Example 1. Here, PGMEA solvent (not listed in Table 2) is added such that, after adding the solvent, the compositions contain 45 wt. % total solids and 55 wt. % solvent, based on the total weight of the composition, as in Example 1. [Table 3] [Table 4]

[0132] Example 12: Preparation of cured film (cured composition) For sample OD and reflectance measurements, samples 1 to 11 are prepared by using compositions WE1 to WE11. First, the bank compositions obtained in WE1 to WE11 were each coated separately onto a glass substrate using a spin coater (MS-A100, MIKASA). Then, the coated glass substrates 1 to 11 were prebaked on a hot plate (HHP-411V, AS ONE) at 100°C for 90 seconds to obtain a prebaked composition with an average layer thickness of 15 μm coated on the substrate. Next, without using a pattern mask, a ghi-line exposure machine for photolithography (NES2W-ghi06, Nikon) was used to expose the film to 120 mJ / cm 2 After the sample is subjected to full exposure, a post-exposure bake process is applied to the sample using a hot plate (HHP-411V, AS ONE) at 120° C. for 90 seconds. The post-exposure baked Samples 1 to 11 are then developed for 180 seconds with 0.03 wt % KOHaq used as the developer. The obtained sample is baked in an oven (DP-200 Yamato) at 230°C for 30 minutes to promote curing. The baked samples were then cooled to room temperature. Finally, samples 1 to 11 were obtained.

[0133] Example 13: Measurement of optical density (OD) values The transmission spectra of Samples 1 to 11 obtained in Example 12 are measured using a spectrophotometer (CM-5 Konica Minolta), and the OD values of each sample at 460, 540, and 630 nm are calculated.

[0134] Example 14: Measurement of sample reflectance The reflectance spectrum of each sample obtained is measured using a spectrophotometer (CM-5 Konica Minolta), and the reflectance at 460, 540, and 630 nm of each sample is calculated separately. The results for WE13 and WE14 are shown in Table 3.

[0135] Example 15: Evaluation of developability 1. Preparation of evaluation samples 1 to 11 Evaluation samples 1 to 11 are produced using compositions WE1 to WE11. First, the bank compositions obtained from WE1 to WE11 were separately coated onto glass substrates using a spin coater (MS-A100, MIKASA). Then, the coated glass substrates 1 to 11 were prebaked on a hot plate (HHP-411V, AS ONE) at 100°C for 90 seconds to obtain prebaked compositions with an average layer thickness of 15 μm. Next, using a pattern mask, a ghi-line exposure machine for photolithography (NES2W-ghi06, Nikon) was used to expose the film at 120 mJ / cm 2 The sample was exposed to light at 1000 W at 120°C for 90 seconds, and a hole pattern of 150 × 150 μm was created after the development process. The sample was then subjected to a post-exposure bake process using a hot plate (HHP-411V, AS ONE) at 120°C for 90 seconds. The baked samples 1 to 11 are then developed for 150 seconds with 0.03 wt % KOHaq used as the developer to create a 150×150 μm hole pattern. The obtained sample is baked in an oven (DP-200 Yamato) at 230°C for 30 minutes to promote curing. The baked samples were then cooled to room temperature. Finally, samples 1 to 11 were obtained.

[0136] 2. Evaluation of the developability of the obtained samples Using an optical microscope (MX61A, OLYMPUS), the developability / patternability of the obtained evaluation samples 1A to 11A is evaluated. In particular, for the obtained samples 1 to 11, whether there is any development residue in the unexposed area of each sample is evaluated using the microscope. The results obtained are shown in Table 3. Here, the result "A" means "no development residue in the unexposed area" and "no pattern defects." Result "B": Development residue and / or pattern defects are observed in the unexposed areas. [Table 5] [Table 6]

Claims

1. a composition, preferably a photocurable composition, preferably said composition does not contain any polysiloxane; at least i) an alkali-soluble polymer containing an ethylenic double bond; ii) a colorant; and A composition comprising:

2. 2. The composition of claim 1, wherein the solid acid number of the alkaline polymer is in the range of 30 to 160 mg KOH / g, more preferably 50 to 150 mg KOH / g, and even more preferably 60 to 80 mg KOH / g.

3. 3. The composition of claim 1 or 2, further comprising a thiol-containing polyfunctional compound: Preferably, the thiol-containing polyfunctional compound contains a pentaerythritol structure, More preferably, the thiol-containing polyfunctional compound has the following chemical formula (I): ｘ ) and 【Chemical 1】 During the ceremony, R １ａ , R １ｂ , R １ｃ , and R １ｄ are each independently selected from a hydrogen atom, an alkyl chain having 1 to 10 carbon atoms, a cyclo group having 3 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, wherein at least one H atom is replaced by an SH group and one or more non-adjacent CH ２ The group is an oxygen atom, C═O, C═S, C═Se, C═NH, or SiH ２ , SO, SO ２ , OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ and R １ａ , R １ｂ , R １ｃ , and R １ｄ is not a hydrogen atom, and preferably R １ａ , R １ｂ , R １ｃ , and R １ｄ At least two of R are not hydrogen atoms, and more preferably at least R １ａ , R １ｂ , R １ｃ But it is not a hydrogen atom.

4. The composition according to any one of claims 1 to 3, further comprising a polymerization initiator.

5. The composition according to any one of claims 1 to 4, further comprising a compound containing at least two (meth)acryloyloxy groups.

6. The composition according to any one of claims 1 to 5, further comprising a surfactant.

7. The composition of any one of claims 1 to 6, further comprising a solvent.

8. The composition according to any one of claims 1 to 7, further comprising another colorant different from the colorant according to claim 1.

9. The composition of any one of claims 1 to 8, further comprising at least one additive selected from one or more members of the group consisting of developer dissolution promoters, scum removers, adhesion promoters, polymerization inhibitors, antifoaming agents, surfactants, photosensitizer accelerators, crosslinking agents, and hardeners.

10. A method for producing a cured layer, comprising at least the following steps: (Xi) providing a composition according to any one of claims 1 to 9 on a layer or on a substrate to form a coating layer; (Xii) baking the coating layer to obtain a hardened layer, Preferably, the method comprises, after step (Xi) and before step (Xii), the following step: (Xiii) a step of pre-baking (heat treating) the coating layer to dry the coating layer and reduce the amount of the solvent remaining in the coating layer; (Xiv) irradiating the coating layer with light (applying photoirradiation), preferably with light having a peak maximum wavelength in the range of 360 to 430 nm, preferably using a patterned mask when performing the photoirradiation; (Xv) applying a post-exposure bake process, and / or (Xvi) applying a development process to form a patterned hardened layer; The method further comprises one or more of:

11. at least i) a polymer (A) derived or derivable from an alkali-soluble polymer containing an ethylenic double bond, Preferably, the alkaline polymer has a solid acid value in the range of 30 to 160 mg KOH / g, more preferably 50 to 150 mg KOH / g, and even more preferably 60 to 80 mg KOH / g; ii) a colorant; and Including, layers.

12. 12. The layer according to claim 11, wherein the layer has an optical density (OD) value at a layer thickness of 10 μm in the range of 1.0 to 3.0 at a light wavelength of 460 nm, in the range of 1.0 to 3.0 at a light wavelength of 540 nm, and / or in the range of 1.0 to 3.0 at a light wavelength of 630 nm.

13. 13. The layer according to claim 11 or 12, wherein the reflectivity of the layer at a layer thickness of 10 μm is in the range of 30 to 90% at a light wavelength of 460 nm, in the range of 30 to 90% at a light wavelength of 540 nm, and / or in the range of 30 to 90% at a light wavelength of 630 nm.

14. A photoconversion device comprising at least a layer according to any one of claims 11 to 13, and preferably further comprising a substrate.

15. An optical device comprising at least a layer according to any one of claims 11 to 13 or a photo-conversion device according to claim 14.

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