Negative photosensitive coloring composition, cured film, method for producing cured film, partition-equipped substrate, and image display device

Abstract

To provide a negative type photosensitive coloring composition which enables formation of a cured film having high resolution, high reflectance and is excellent in heat resistance even when the cured film is thick.SOLUTION: A negative type photosensitive coloring composition contains (A) a siloxane resin, (B) a photopolymerization initiator, (C) a photopolymerization compound, (D) a white pigment and (E) an organic solvent, in which the (A) siloxane resin includes at least a repeating unit represented by formula (1) and / or a repeating unit represented by formula (2), and contains 20-70 mol% of the total of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) in the total repeating units of the (A) siloxane resin. In the formula (1), R1 represents an alkyl group having 3 to 12 carbon atoms; and R2 represents a monovalent organic group having 1 to 20 carbon atoms.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to a negative photosensitive coloring composition, a cured film, a method for producing the cured film, a partition-attached substrate, and an image display device. [Background technology]

[0002] Liquid crystal display devices, a type of image display device, generally display colors using a white light source such as an LED and color filters that selectively transmit red, green, and blue light. Conventional methods for manufacturing color filters involve applying a composition in which pigment powder is dispersed in a transparent resin such as a (meth)acrylic polymer onto a transparent substrate such as glass, drying the composition, and then utilizing the photosensitivity to pattern the composition to create red, green, and blue pixels on the transparent substrate. However, color displays using such color filters have poor light utilization efficiency and have issues with color reproducibility.

[0003] Therefore, as a color display device with high light utilization efficiency, for example, a color display device including a wavelength conversion unit made of a wavelength conversion phosphor, a polarization separation means, and a polarization conversion means has been proposed (see, for example, Patent Document 1). Also proposed is a liquid crystal display device including a blue light source, a liquid crystal element, a color filter having a phosphor that is excited by blue light to emit red fluorescence and a phosphor that is excited by blue light to emit green fluorescence, and a light-scattering film that scatters blue light (see, for example, Patent Document 2).

[0004] In color filters containing the aforementioned phosphors, the phosphor layers needed to be thick to adequately absorb light from a blue light source. Furthermore, the barrier ribs separating the phosphor layers also needed to be thick. Furthermore, since they are directly irradiated with light from the phosphors, they also needed to have high light resistance. Materials that have high light resistance and the ability to be processed into high-definition thick films have been proposed, including a material containing a condensate of a hydrolyzable silane, a radiation-sensitive compound, and an alcohol-based solvent (see, for example, Patent Document 3), and a material containing a white pigment, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator (see, for example, Patent Documents 4 and 5). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-131683 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-244383 [Patent Document 3] Japanese Patent Application Laid-Open No. 2012-37866 [Patent Document 4] International Publication No. 2014 / 126013 [Patent Document 5] International Publication No. 2015 / 12228 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the composition described in Patent Document 3 has a problem in that cracks tend to occur when heated when the film is thick, resulting in insufficient heat resistance. Also, the composition described in Patent Document 4 has a problem in that aromatic functional groups of the resin tend to separate when irradiated with light, resulting in insufficient light resistance.

[0007] Therefore, an object of the present invention is to provide a negative photosensitive coloring composition that can form a cured film that has high resolution and excellent heat resistance and light resistance, even if it is a thick film. [Means for solving the problem]

[0008] In order to solve the above problems, the present inventors have focused on the structure of siloxane resins in negative photosensitive coloring compositions and conducted extensive research. As a result, they have found that the above problems can be solved by including a siloxane resin having a structural unit derived from an organosilane compound having a long-chain alkyl group. That is, the present invention mainly has the following configuration.

[0009] A negative-tone photosensitive coloring composition containing (A) a siloxane resin, (B) a photopolymerization initiator, (C) a photopolymerizable compound, (D) a white pigment, and (E) an organic solvent, wherein the (A) siloxane resin contains at least a repeating unit represented by formula (1) and / or a repeating unit represented by formula (2), and the repeating units represented by formula (1) and the repeating units represented by formula (2) account for 20 to 70 mol% in total of all repeating units of the (A) siloxane resin.

[0010] [ka]

[0011] In formula (1) and formula (2), R 1 represents an alkyl group having 3 to 12 carbon atoms, and R 2 represents a monovalent organic group having 1 to 20 carbon atoms. * represents a bonding site. [Effects of the Invention]

[0012] According to the negative photosensitive coloring composition of the present invention, it is possible to form a thick cured film with high resolution and excellent heat resistance and light resistance. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a cross-sectional view showing one embodiment of a partition-attached substrate of the present invention having patterned partition walls. [Figure 2]FIG. 1 is a cross-sectional view showing one embodiment of a substrate with partition walls of the present invention having patterned partition walls and pixels containing a color-conversion light-emitting material. [Figure 3] FIG. 1 is a cross-sectional view showing the configuration of a display device used for evaluating color mixing. DETAILED DESCRIPTION OF THE INVENTION

[0014] The negative-tone photosensitive coloring composition of the present invention contains (A) a siloxane resin, (B) a photopolymerization initiator, (C) a photopolymerizable compound, (D) a white pigment, and (E) an organic solvent. By including the (A) siloxane resin having the specific structure described above, the composition exhibits excellent heat resistance and light resistance, and can suppress color change and cracking of the cured film. It also enables the formation of high-resolution patterns. By including the (B) photopolymerization initiator and the (C) photopolymerizable compound, radicals generated from the (B) photopolymerization initiator upon light irradiation promote polymerization of the (C) photopolymerizable compound, rendering the exposed portion of the negative-tone photosensitive coloring composition insoluble in an alkaline aqueous solution, thereby enabling the formation of negative patterns. Furthermore, by including the (D) white pigment, the reflectance of the resulting cured film can be improved. Furthermore, by including the (E) organic solvent, the viscosity of the negative-tone photosensitive coloring composition can be easily adjusted to a level suitable for coating, improving the uniformity of the coating film.

[0015] (A) Siloxane resin The negative photosensitive coloring composition of the present invention contains (A) a siloxane resin.

[0016] The siloxane resin (A) is a hydrolysis-dehydration condensation product of organosilane, and in the present invention contains at least a repeating unit represented by formula (1) and / or a repeating unit represented by formula (2).

[0017] [ka]

[0018] In formula (1) and formula (2), R 1represents an alkyl group having 3 to 12 carbon atoms, and R 2 represents a monovalent organic group having 1 to 20 carbon atoms. * represents a bonding site. The repeating unit represented by formula (1) and / or the repeating unit represented by formula (2) may be formed by the reaction of R 1 The siloxane resin is characterized by containing a long-chain alkyl group having 3 to 12 carbon atoms. By containing these repeating units, excessive thermal polymerization (condensation) of the siloxane resin due to heating can be suppressed, improving heat resistance. As a result, cracks and color changes during heat treatment can be suppressed.

[0019] The (A) siloxane resin is characterized by containing 20 to 70 mol% in total of the repeating units of formula (1) and the repeating units of formula (2) among all the repeating units of the (A) siloxane resin. If the total content of the repeating units of formula (1) and formula (2) is less than 20 mol%, the suppression of thermal polymerization (condensation) becomes insufficient, and the improvement of crack resistance becomes insufficient. The total content of the repeating units of formula (1) and formula (2) is preferably 30 mol% or more.

[0020] On the other hand, if the total content of the repeating units represented by formula (1) and formula (2) exceeds 70 mol%, the hydrophobicity of (B) the siloxane resin reduces compatibility with other components in the composition, resulting in reduced resolution. The total content of the repeating units represented by formula (1) and formula (2) is preferably 60 mol% or less.

[0021] The content ratio of the organosilane unit having the repeating unit represented by formula (1) and the repeating unit represented by formula (2) is 29 This can be determined by Si-NMR measurement, i.e., by calculating the ratio of the integral value of Si derived from organosilane units having repeating units represented by formula (1) and repeating units represented by formula (2) to the integral value of all Si derived from the organosilane.

[0022] In addition, R in the formula (2) 2 is preferably an alkyl group having 1 to 20 carbon atoms. R 2 By making is an alkyl group having 1 to 20 carbon atoms, a siloxane resin with excellent light resistance can be obtained. * represents a bonding site.

[0023] In the present invention, the siloxane resin (A) preferably contains a repeating unit represented by formula (3) and / or a repeating unit represented by formula (4).

[0024] [ka]

[0025] In formula (3) and formula (4), R 3 represents a linear alkylene group having 1 to 6 carbon atoms, and R 4 represents a hydrogen atom or a methyl group, and R 5 represents an alkyl group having 1 to 20 carbon atoms. * represents a bonding site. By containing a repeating unit represented by formula (3) and / or a repeating unit represented by formula (4), the contrast in the degree of cure between exposed and unexposed areas is easily achieved, thereby further improving resolution and further suppressing development residues.

[0026] The total content of the repeating units represented by formula (3) and the repeating units represented by formula (4) is preferably 5 to 25 mol % of the total repeating units in the siloxane resin (A). By containing 5 mol % or more of these repeating units, a contrast in the degree of cure between exposed and unexposed areas can be achieved, improving resolution. On the other hand, by containing 25 mol % or less of these repeating units, excessive cure in exposed areas can be suppressed, further improving resolution.

[0027] The content ratio of the organosilane unit including the repeating unit represented by formula (3) and the repeating unit represented by formula (4) is 29It can be determined by performing Si-NMR measurement and calculating the ratio of the integral value of Si derived from organosilane units having repeating units represented by formula (3) and repeating units represented by formula (4) to the integral value of all Si derived from the organosilane.

[0028] The siloxane resin (A) preferably contains a repeating unit represented by formula (5) and / or a repeating unit represented by formula (6).

[0029] [ka]

[0030] In formula (5) and formula (6), R 6 R represents a monovalent organic group having 1 to 20 carbon atoms and having a carboxyl group and / or a carboxylic anhydride group. 7 represents an alkyl group having 1 to 20 carbon atoms. * represents a bonding site. By containing a repeating unit represented by formula (5) and / or a repeating unit represented by formula (6), excellent developer solubility can be achieved, and resolution can be improved.

[0031] The repeating units represented by formula (5) and the repeating units represented by formula (6) preferably account for 5 to 20 mol % of the total repeating units in the siloxane resin (A). By containing 5 mol % or more of these repeating units, development residues can be further suppressed. On the other hand, by containing 20 mol % or less of these repeating units, resolution can be further improved.

[0032] The content ratio of the organosilane unit including the repeating unit represented by formula (5) and the repeating unit represented by formula (6) is 29 It can be determined by performing Si-NMR measurement and calculating the ratio of the integral value of Si derived from organosilane units having repeating units represented by formula (5) and repeating units represented by formula (6) to the integral value of all Si derived from the organosilane.

[0033] The siloxane resin (A) preferably contains a repeating unit represented by formula (7) and / or a repeating unit represented by formula (8).

[0034] [ka]

[0035] In formula (7) and formula (8), R 8 R is an alkyl group having 1 to 20 carbon atoms selected from the group consisting of linear, branched, and cyclic alkyl groups, and some of the hydrogen atoms of the alkyl group may be substituted with a group selected from the group consisting of an epoxy group, a ureido group, a hydroxyl group, an isocyanurate group, and a fluorine group. 9 represents an alkyl group having 1 to 20 carbon atoms. * represents a bonding site. By containing a repeating unit represented by formula (7) and / or a repeating unit represented by formula (8), it is possible to have excellent adhesion to the base substrate, suppress pattern peeling during development, and improve chemical resistance.

[0036] The content ratio of the organosilane unit including the repeating unit represented by formula (7) and the repeating unit represented by formula (8) is 29 It can be determined by performing Si-NMR measurement and calculating the ratio of the integral value of Si derived from organosilane units having repeating units represented by formula (7) and repeating units represented by formula (8) to the integral value of all Si derived from the organosilane.

[0037] The siloxane resin (A) may also contain other repeating units, preferably repeating units having a non-aromatic functional group, which can improve light resistance.

[0038] The repeating units represented by formulas (1) to (8) are derived from organosilane compounds represented by formulas (9) to (16), respectively. That is, the repeating unit represented by the formula (1) and / or the repeating unit represented by the formula (2) is derived from the organosilane compound represented by the formula (9) and / or the organosilane compound represented by the formula (10). The repeating unit represented by formula (3) and / or the repeating unit represented by formula (4) are derived from an organosilane compound represented by formula (11) and / or an organosilane compound represented by formula (12). The repeating unit represented by formula (5) and / or the repeating unit represented by formula (6) are derived from an organosilane compound represented by formula (13) and / or an organosilane compound represented by formula (14). The repeating unit represented by formula (7) and / or the repeating unit represented by formula (8) are derived from an organosilane compound represented by formula (15) and / or an organosilane compound represented by formula (16). The polysiloxane resin (A) having the repeating units represented by formulas (1) to (8) can be obtained by hydrolysis and polycondensation of the corresponding organosilane compounds represented by formulas (9) to (16). Other organosilane compounds may also be used.

[0039] [ka]

[0040] In the above formula (9) and formula (10), R 1 and R 2 are R in Equation (1) and Equation (2), respectively. 1 and R 2 R represents the same group as a may be the same or different and represent a monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.

[0041] In the above formula (11) and formula (12), R 3 , R 4 and R 5 are R in Equation (3) and Equation (4), respectively. 3 , R4 and R 5 R represents the same group as a is R in the above formula (9) and formula (10). a represents the same group as

[0042] In the above formula (13) and formula (14), R 6 and R 7 are R in Equation (5) and Equation (6), respectively. 6 and R 7 R represents the same group as a is R in the above formula (9) and formula (10). a represents the same group as

[0043] In the above formula (15) and formula (16), R 8 and R 9 are R in Equation (7) and Equation (8), respectively. 8 and R 9 R represents the same group as a is R in the above formula (9) and formula (10). a represents the same group as

[0044] Examples of organosilane compounds represented by formula (9) include propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, dodecyltrimethoxysilane, propyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, propyltripropoxysilane, butyltrippropoxysilane, pentyltrippropoxysilane, octyltrippropoxysilane, decyltrippropoxysilane, and dodecyltrippropoxysilane. Two or more of these may be used.

[0045] Examples of organosilane compounds represented by formula (10) include methylpropyldimethoxysilane, ethylpropyldimethoxysilane, methylbutyldimethoxysilane, ethylbutyldimethoxysilane, methylpentyldimethoxysilane, methylhexyldimethoxysilane, methylheptyldimethoxysilane, methyloctyldimethoxysilane, methylnonyldimethoxysilane, methyldecyldimethoxysilane, methylpropyldiethoxysilane, methylbutyldiethoxysilane, methylpentyldiethoxysilane, methyloctyldiethoxysilane, methyldodecyldiethoxysilane, methylpropyldipropoxysilane, methylbutyldipropoxysilane, methylpentyldipropoxysilane, methyldecyldipropoxysilane, methyldodecyldipropoxysilane, etc. Two or more of these may be used.

[0046] Examples of the organosilane compound represented by formula (11) include γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, and γ-methacryloylpropyltriethoxysilane. Two or more of these may be used.

[0047] Examples of the organosilane compound represented by formula (12) include γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, and γ-methacryloylpropylmethyldiethoxysilane. Two or more of these may be used.

[0048] Examples of organosilane compounds having a structure represented by formula (13) include 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilylbutyric acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-triethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, and 3-triethoxysilylpropylphthalic anhydride. Two or more of these may be used.

[0049] Examples of organosilane compounds having a structure represented by formula (14) include 3-dimethylmethoxysilylpropionic acid, 3-dimethylethoxysilylpropionic acid, 4-dimethylmethoxysilylbutyric acid, 4-dimethylethoxysilylbutyric acid, 5-dimethylmethoxysilylvaleric acid, 5-dimethylethoxysilylvaleric acid, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3-dimethylethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-dimethylethoxysilylpropylcyclohexyldicarboxylic anhydride, etc. Two or more of these may be used.

[0050] Examples of organosilane compounds having a structure represented by formula (15) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-glycidoxypropyl Examples thereof include trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)propyltriethoxysilane, 3-ethyl-3-{[3-(trimethoxysilyl)propoxy]methyl}oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, trifluoropropyltrimethoxysilane, and trifluoropropyltriethoxysilane. Two or more of these may be used.

[0051] Examples of organosilane compounds having a structure represented by formula (16) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, 3-ureidopropylmethyldimethoxysilane, 3-ureidopropylethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)propylsilane, Examples of organosilane compounds include propylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)propylmethyldiethoxysilane, 3-ethyl-3-{[3-(dimethoxysilylmethyl)propoxy]methyl}oxetane, 3-ethyl-3-{[3-(diethoxysilylethyl)propoxy]methyl}oxetane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, and trifluoropropylethyldiethoxysilane. Two or more of these may be used.

[0052] Other organosilane compounds include, for example, organosilane compounds such as tetramethoxysilane, tetraethoxysilane, silicate 51 (tetraethoxysilane oligomer), etc. Two or more of these may be used.

[0053] From the viewpoint of coating properties, the weight average molecular weight (Mw) of the (A) siloxane resin is preferably 1,000 or more, more preferably 2,000 or more. On the other hand, from the viewpoint of developability, the Mw of the (A) siloxane resin is preferably 50,000 or less, more preferably 20,000 or less. Here, the Mw of the (A) siloxane resin in the present invention refers to the polystyrene equivalent value measured by gel permeation chromatography (GPC).

[0054] In the negative photosensitive coloring composition, the content of (A) siloxane resin can be arbitrarily set depending on the desired film thickness and application, but is generally 10 to 50 wt% of the solid content of the negative photosensitive coloring composition. Also, the content of (A) siloxane resin is preferably 10 wt% or more, more preferably 20 wt% or more, of the solid content of the negative photosensitive coloring composition. On the other hand, the content of (A) siloxane resin is preferably 50 wt% or less of the solid content of the negative photosensitive coloring composition.

[0055] The (A) siloxane resin can be obtained by hydrolyzing the aforementioned organosilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction in the presence or absence of a solvent.

[0056] Various conditions for hydrolysis can be set in accordance with properties suitable for the intended use, taking into consideration the reaction scale, size and shape of the reaction vessel, etc. Examples of various conditions include acid concentration, reaction temperature, reaction time, etc.

[0057] For the hydrolysis reaction, an acid catalyst such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids or their anhydrides, ion exchange resins, etc. Among these, an acidic aqueous solution containing formic acid, acetic acid, and / or phosphoric acid is preferred.

[0058] When an acid catalyst is used in the hydrolysis reaction, the amount of acid catalyst added is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, per 100 parts by weight of all organosilane compounds used in the hydrolysis reaction, from the viewpoint of promoting hydrolysis more rapidly. On the other hand, from the viewpoint of appropriately controlling the progress of the hydrolysis reaction, the amount of acid catalyst added is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, per 100 parts by weight of all organosilane compounds. Here, the amount of all organosilane compounds refers to the amount including all of the organosilane compounds, their hydrolysates, and their condensates, and the same applies hereinafter.

[0059] The hydrolysis reaction can be carried out in an organic solvent. The organic solvent can be appropriately selected taking into consideration the stability, wettability, volatility, etc. of the negative photosensitive coloring composition. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. ethers such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone, and the like; amides such as dimethylformamide and dimethylacetamide; acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may be used.

[0060] Among these, from the viewpoint of crack resistance of the cured film, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, γ-butyrolactone, etc. are preferably used.

[0061] When an organic solvent is produced by the hydrolysis reaction, it is also possible to carry out the hydrolysis without a solvent. After the hydrolysis reaction is completed, it is also preferable to add an organic solvent to adjust the concentration to an appropriate level for a negative photosensitive coloring composition. After the hydrolysis, it is also possible to distill and remove all or part of the produced alcohol, etc. by heating and / or under reduced pressure, and then add a suitable organic solvent.

[0062] When an organic solvent is used in the hydrolysis reaction, the amount of organic solvent added is preferably 50 parts by weight or more, more preferably 80 parts by weight or more, per 100 parts by weight of the total organosilane compounds, from the viewpoint of suppressing gel formation. On the other hand, the amount of organic solvent added is preferably 500 parts by weight or less, more preferably 200 parts by weight or less, per 100 parts by weight of the total organosilane compounds, from the viewpoint of promoting hydrolysis more rapidly.

[0063] The water used in the hydrolysis reaction is preferably ion-exchanged water. The amount of water can be set arbitrarily, but is preferably 1.0 to 4.0 moles per mole of the total organosilane compounds.

[0064] Examples of methods for the dehydration condensation reaction include heating the silanol compound solution obtained by the hydrolysis reaction of the organosilane compound as is. The heating temperature is preferably 50°C or higher and the boiling point of the solvent or lower, and the heating time is preferably 1 to 100 hours. To increase the degree of polymerization of the siloxane resin, reheating or the addition of a base catalyst may be performed. Depending on the purpose, after hydrolysis, an appropriate amount of the produced alcohol may be distilled and removed by heating and / or under reduced pressure, followed by the addition of a suitable solvent.

[0065] From the viewpoint of storage stability of the negative photosensitive coloring composition, it is preferable that the siloxane resin solution after hydrolysis and dehydration condensation does not contain the catalyst, and the catalyst can be removed as necessary. As a catalyst removal method, from the viewpoint of ease of operation and removability, water washing, treatment with an ion exchange resin, etc. are preferred. Water washing is a method in which the siloxane resin solution is diluted with an appropriate hydrophobic solvent, and then the organic layer obtained by washing with water several times is concentrated using an evaporator or the like. Treatment with an ion exchange resin is a method in which the siloxane resin solution is brought into contact with an appropriate ion exchange resin.

[0066] (B) Photopolymerization initiator The negative photosensitive coloring composition of the present invention contains (B) a photopolymerization initiator.

[0067] (B) The photopolymerization initiator may be any one that decomposes and / or reacts with light (including ultraviolet light and electron beams) to generate radicals, and examples thereof include α-aminoalkylphenone compounds such as 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; 2,4,6-trimethylbenzoyl Acylphosphine oxide compounds such as phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide; 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], 1-phenyl-1,2-butadione-2-(O-methoxycarbonyl)oxime, 1,3- Oxime ester compounds such as diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); benzil ketal compounds such as benzil dimethyl ketal; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)keto α-hydroxyketone compounds such as benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and other benzophenone compounds;Examples include acetophenone compounds such as 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, and 4-azidobenzalacetophenone; aromatic ketoester compounds such as methyl 2-phenyl-2-oxyacetate; and benzoate compounds such as ethyl 4-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, and methyl 2-benzoylbenzoate. Two or more of these may be contained.

[0068] In order to suppress coloration caused by the (B) photopolymerization initiator, the negative photosensitive coloring composition preferably uses an acylphosphine oxide-based photopolymerization initiator such as 2,4,6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, or bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide.

[0069] The content of the (B) photopolymerization initiator in the negative photosensitive coloring composition is preferably 0.01% by weight or more, more preferably 1% by weight or more, based on the solid content, from the viewpoint of effectively promoting radical curing. On the other hand, from the viewpoint of suppressing elution of the remaining (B) photopolymerization initiator and further suppressing coloration, the content of the (B) photopolymerization initiator is preferably 20% by weight or less, more preferably 10% by weight or less, based on the solid content.

[0070] (C) Photopolymerizable compound The negative photosensitive coloring composition of the present invention contains a photopolymerizable compound (C).

[0071] The (C) photopolymerizable compound refers to a compound having two or more ethylenically unsaturated double bonds in the molecule. In consideration of the ease of radical polymerization, the (C) photopolymerizable compound preferably has a (meth)acrylic group. Furthermore, the (C) photopolymerizable compound preferably has a double bond equivalent of 400 g / mol or less in order to further improve sensitivity in pattern processing. On the other hand, the (C) photopolymerizable compound preferably has a double bond equivalent of 80 g / mol or more in order to further improve resolution in pattern processing.

[0072] Examples of the photopolymerizable compound (C) include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethyloltricyclodecane diacrylate, pentaerythritol triacrylate, and the like. acrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentaerythritol undecaacrylate, pentaerythritol dodecaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentaerythritol undecamethacrylate, pentaerythritol dodecamethacrylate, and dimethylol-tricyclodecane diacrylate. Two or more of these may be contained.

[0073] Furthermore, it is preferable to contain, as other photopolymerizable compounds, a photopolymerizable compound having a structure represented by formula (17) and / or a photopolymerizable compound having a structure represented by formula (18).

[0074] [ka]

[0075] In formula (17), R 10 each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a phenyl group; and n represents an integer of 1 to 40. In formula (18), R 11 represents a hydrogen atom or a methyl group, and * represents a bonding site. By having such a structure, development is possible with alkaline developers of a wide range of concentrations even when processing thick films of 10 μm or more, and excellent crack resistance can be achieved.

[0076] A method for synthesizing the photopolymerizable compound (C) having the structure represented by formula (17) includes, for example, a method of reacting a compound having multiple active hydrogens or its halide with various alkylene oxides to obtain a polyol compound, and then reacting the resulting compound with (meth)acrylic acid. A method for synthesizing the photopolymerizable compound (C) having the structure represented by formula (18) includes, for example, a method of reacting a compound having multiple glycidyl ether groups, or a compound having a glycidyl ether group and a radical polymerizable group, with (meth)acrylic acid.

[0077] Examples of the photopolymerizable compound having a structure represented by formula (17) and the photopolymerizable compound having a structure represented by formula (18) include ethylene glycol diglycidyl ether (meth)acrylate, propylene glycol diglycidyl ether (meth)acrylate, diethylene glycol diglycidyl ether (meth)acrylate, dipropylene glycol diglycidyl ether (meth)acrylate, triethylene glycol diglycidyl ether (meth)acrylate, tripropylene glycol diglycidyl ether (meth)acrylate, tetraethylene glycol diglycidyl ether (meth)acrylate, tetrapropylene ... Ethylene glycol diglycidyl ether (meth)acrylate, tetrapropylene glycol diglycidyl ether (meth)acrylate, polyethylene glycol 200-diglycidyl ether (meth)acrylate, polyethylene glycol 300-diglycidyl ether (meth)acrylate, polyethylene glycol 400-diglycidyl ether (meth)acrylate, bisphenol A diglycidyl ether (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol Lithium di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol 200-di(meth)acrylate, polyethylene glycol 300-di(meth)acrylate, polyethylene glycol 400-di(meth)acrylate, polyethylene glycol 500-di(meth)acrylate, polyethylene glycol 600-di(meth)acrylate, polyethylene glycol 700-di(meth)acrylate, polyethylene glycol 800-di(meth)acrylate, polyethylene glycol 900-di(meth)acrylate acrylate, polyethylene glycol 1000-di(meth)acrylate, trimethylolpropane-EO modified tri(meth)acrylate (average EO number = 3, EO = ethylene oxide), trimethylolpropane-EO modified tri(meth)acrylate (average EO number = 6), trimethylolpropane-EO modified tri(meth)acrylate (average EO number = 9), trimethylolpropane-PO modified tri(meth)acrylate (average PO number = 3, PO = propylene oxide), trimethylolpropane-PO modified tri(meth)acrylate (average PO number = 6),Trimethylolpropane-PO modified tri(meth)acrylate (average PO number = 9), glycerin-EO modified tri(meth)acrylate (average EO number = 3), glycerin-EO modified tri(meth)acrylate (average EO number = 6), glycerin-EO modified tri(meth)acrylate (average EO number = 9), glycerin-PO modified tri(meth)acrylate (average PO number = 3), glycerin-PO modified tri(meth)acrylate (average PO number = 6), glycerin-PO modified tri(meth)acrylate (average PO number = 9), bisphenol A-EO modified tri(meth)acrylate (average EO number = 4), bisphenol A-EO modified tri(meth)acrylate (average EO number = 10), bisphenol A-EO modified tri(meth)acrylate (average EO number = 30), bisphenol A-PO modified tri(meth)acrylate Examples of the ester include phthalic anhydride propylene oxide (meth)acrylate (average PO number = 4), bisphenol A-PO-modified tri(meth)acrylate (average PO number = 10), bisphenol A-PO-modified tri(meth)acrylate (average PO number = 30), isocyanuric acid-EO-modified tri(meth)acrylate (average EO number = 3), isocyanuric acid-EO-modified di(meth)acrylate (average EO number = 3), isocyanuric acid-PO-modified tri(meth)acrylate (average PO number = 3), isocyanuric acid-PO-modified di(meth)acrylate (average PO number = 3), 1,2-ethanedithiol-EO-modified di(meth)acrylate (average EO number = 4), 1,2-propanedithiol-EO-modified di(meth)acrylate (average EO number = 4), phthalic anhydride propylene oxide (meth)acrylic acid ester, and trimellitic acid diethylene glycol (meth)acrylic acid ester. Two or more of these may be contained.

[0078] The content of the (C) photopolymerizable compound in the negative photosensitive coloring composition is preferably 1% by weight or more in the solid content of the negative photosensitive coloring composition from the viewpoint of effectively promoting radical curing. On the other hand, from the viewpoint of suppressing excessive radical reaction and further improving resolution, the content of the (C) photopolymerizable compound is preferably 40% by weight or less in the solid content.

[0079] (D) White pigment The negative photosensitive coloring composition of the present invention contains (D) a white pigment.

[0080] Examples of (D) white pigments include titanium dioxide, magnesium oxide, barium sulfate, zirconium oxide, zinc oxide, and white lead. Two or more of these may be contained. Among these, it is preferable to contain at least one of titanium dioxide, zirconium oxide, zinc oxide, barium sulfate, and composite compounds thereof, and titanium dioxide, which has high reflectance and is easy to use industrially, is more preferable.

[0081] The crystal structure of titanium dioxide is classified into anatase type, rutile type, and brookite type. Among these, rutile type titanium oxide is preferred because of its low photocatalytic activity.

[0082] The (D) white pigment may be surface-treated. Surface treatment with Al, Si and / or Zr is preferred, as this improves the dispersibility of the (D) white pigment in the negative photosensitive coloring composition and can further improve the light resistance and heat resistance of the cured film.

[0083] The average primary particle size of the (D) white pigment is preferably 170 to 310 nm from the viewpoint of further improving reflectance, where the average primary particle size of the (D) white pigment refers to the median diameter calculated from the particle size distribution measured by laser diffraction.

[0084] (D) Examples of titanium dioxide pigments that are preferably used as white pigments include R960 (manufactured by DuPont Co., Ltd.) (rutile type, SiO2 / Al2O3 treated, average primary particle size 210 nm), CR-97 (manufactured by Ishihara Sangyo Kaisha, Ltd.) (rutile type, Al2O3 / ZrO2 treated, average primary particle size 250 nm), JR-301 (manufactured by Teika Corporation) (rutile type, Al2O3 treated, average primary particle size 300 nm), JR-405 (manufactured by Teika Corporation) (rutile type, Al2O3 treated, average primary particle size 210 nm), JR-600A (manufactured by Teika Corporation) (rutile type, Al2O3 treated, average primary particle size 250 nm), and JR-603 (manufactured by Teika Corporation) (rutile type, Al2O3 / ZrO2 treated, average primary particle size 280 nm). Two or more of these may be used.

[0085] The content of the (D) white pigment is preferably 10% by weight or more, more preferably 20% by weight or more, of the solid content of the negative photosensitive coloring composition from the viewpoint of further improving the reflectance, while the content of the (D) white pigment is preferably 80% by weight or less, more preferably 60% by weight or less, of the solid content from the viewpoint of suppressing development residues and forming a pattern with higher resolution.

[0086] The negative photosensitive coloring composition may contain a pigment dispersant together with the white pigment (D), which can improve the dispersibility of the white pigment (D) in the negative photosensitive coloring composition. The pigment dispersant can be appropriately selected depending on the type and surface condition of the white pigment used. The pigment dispersant preferably contains an acidic group and / or a basic group. Examples of commercially available pigment dispersants include "Disperbyk" (registered trademark) 106, "Disperbyk" 108, "Disperbyk" 110, "Disperbyk" 180, "Disperbyk" 190, "Disperbyk" 2001, "Disperbyk" 2155, "Disperbyk" 140, and "Disperbyk" 145 (all trade names, manufactured by BYK-Chemie Co., Ltd.). Two or more of these may be contained.

[0087] (E) Organic solvent The negative photosensitive coloring composition of the present invention contains (E) an organic solvent.

[0088] As the organic solvent, it is preferable to combine an organic solvent having a boiling point of 150°C or higher and 250°C or lower at atmospheric pressure with an organic solvent having a boiling point of less than 150°C. By including an organic solvent having a boiling point of 150°C or higher and 250°C or lower, the organic solvent volatilizes appropriately during application, allowing the coating film to dry more rapidly, thereby suppressing coating unevenness and improving film thickness uniformity. Furthermore, by including an organic solvent having a boiling point of less than 150°C at atmospheric pressure, it is possible to suppress the organic solvent from remaining in the cured film of the present invention, as described below. From the perspective of suppressing the organic solvent from remaining in the cured film and further improving chemical resistance and adhesion over a long period of time, it is preferable to include an organic solvent having a boiling point of less than 150°C at atmospheric pressure in an amount of 50% by weight or more of the total organic solvents.

[0089] Examples of organic solvents having a boiling point of less than 150°C under atmospheric pressure include ethanol, isopropyl alcohol, 1-propyl alcohol, 1-butanol, 2-butanol, isopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, methoxymethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, acetol, acetylacetone, methyl isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl lactate, toluene, cyclopentanone, cyclohexane, normal heptane, benzene, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, and 5-hydroxy-2-pentanone. Two or more of these may be used.

[0090] Examples of organic solvents having a boiling point of 150°C or higher and 250°C or lower under atmospheric pressure include ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, diisobutyl ketone, diacetone alcohol, ethyl lactate, butyl lactate, dimethylformamide, dimethylacetamide, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, cycloheptanone, diethylene glycol monobutyl ether, and ethylene glycol dibutyl ether. Two or more of these may be used.

[0091] The content of the organic solvent can be arbitrarily set depending on the coating method, etc. For example, when forming a film by spin coating, the content of the organic solvent in the negative photosensitive coloring composition is generally 50% by weight or more and 95% by weight or less.

[0092] The negative photosensitive coloring composition of the present invention preferably further contains a black pigment (F), which can improve the light-blocking properties of the cured film.

[0093] (F) Examples of black pigments include black organic pigments, mixed-color organic pigments, and black inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone-based pigments. These may be coated with a resin. Examples of mixed-color organic pigments include pseudo-black pigments obtained by mixing two or more pigments, such as red, blue, green, purple, yellow, magenta, and / or cyan. Among these, a mixed pigment of a red pigment and a blue pigment is preferred from the viewpoint of achieving both a moderately high OD value and pattern processability. The weight ratio of the red pigment to the blue pigment is preferably 20 / 80 to 80 / 20, and more preferably 30 / 70 to 70 / 30. Specific examples of representative pigments, expressed by Color Index (CI) numbers, include the following: Examples of red pigments include Pigment Red (hereinafter abbreviated as PR) 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, PR220, PR223, PR224, PR226, PR227, PR228, PR240, and PR254. Two or more of these may be contained. Examples of blue pigments include Pigment Blue (hereinafter abbreviated as PB) 15, PB15:3, PB15:4, PB15:6, PB22, PB60, and PB64. Two or more of these may be contained. Examples of black inorganic pigments include graphite, fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, gold, platinum, and palladium, metal oxides, metal composite oxides, metal sulfides, metal nitrides, metal oxynitrides, and metal carbides. Two or more of these may be contained. Among the above black pigments, titanium nitride, zirconium nitride, carbon black, and a mixed pigment of red and blue pigments are more preferred because they have high light-blocking properties. The content of the black pigment is preferably 0.2 wt % or more, more preferably 0.5 wt % or more, from the viewpoint of adjusting reflectance and OD to suppress color mixing of light in adjacent pixels. On the other hand, from the viewpoint of adjusting reflectance and OD, the content of the black pigment is preferably 5 wt % or less, more preferably 3 wt % or less.

[0094] The negative photosensitive coloring composition of the present invention preferably further contains (G) an organometallic compound, which decomposes and aggregates to form a black pigment in the exposure step and / or heating step during pattern formation of the cured film, thereby improving the light-blocking properties.

[0095] (G) The organometallic compound preferably contains at least one metal selected from the group consisting of silver, gold, platinum, and palladium, due to its high light-shielding properties. Examples of metal compounds selected from the group consisting of silver, gold, platinum, and palladium include silver-containing organometallic compounds such as silver neodecanoate, silver octoate, and silver salicylate; gold-containing organometallic compounds such as chloro(triphenylphosphine)gold and tetrachloroauric acid tetrahydrate; platinum-containing organometallic compounds such as bis(acetylacetonato)platinum, dichlorobis(triphenylphosphine)platinum, and dichlorobis(benzonitrile)platinum; and palladium-containing organometallic compounds such as bis(acetylacetonato)palladium, dichlorobis(triphenylphosphine)palladium, dichlorobis(benzonitrile)palladium, tetrakis(triphenylphosphine)palladium, and dibenzylideneacetonepalladium. Two or more of these may be contained. Among these, from the viewpoint of further improving the light-shielding property, bis(acetylacetonato)palladium, dichlorobis(triphenylphosphine)palladium, dichlorobis(benzonitrile)palladium, and tetrakis(triphenylphosphine)palladium are more preferred.

[0096] The content of the (G) organometallic compound in the solid content of the negative photosensitive coloring composition is preferably 0.2 to 5% by weight. By making the content of the organometallic compound 0.2% by weight or more, the OD value can be further improved. The content of the organometallic compound is more preferably 1.5% by weight or more. On the other hand, by making the content of the organometallic compound 5% by weight or less, the reflectance can be further improved.

[0097] The negative photosensitive coloring composition of the present invention further preferably contains (H) a coordination compound having a phosphorus atom (hereinafter, may be referred to as "coordination compound"). The coordination compound coordinates with the organometallic compound in the negative photosensitive coloring composition, improves the solubility of the organometallic compound in the solvent, promotes the decomposition of the organometallic compound, and can further improve the light-shielding property.

[0098] Examples of the coordinating compound include triphenylphosphine, tri-t-butylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-t-butylphosphine tetrafluoroborate, tri(2-furyl)phosphine, tris(1-adamantyl)phosphine, tris(diethylamino)phosphine, tris(4-methoxyphenyl)phosphine, and tris(O-tolyl)phosphine. Two or more of these may be contained. The content of the coordinating compound in the negative photosensitive coloring composition of the present invention is preferably 0.5 to 3.0 molar equivalents relative to the organometallic compound.

[0099] The negative photosensitive coloring composition of the present invention preferably further contains (I) a liquid-repellent compound. By containing the liquid-repellent compound, it is possible to impart liquid-repellent properties to the cured film, and for example, when a partition wall substrate having a pattern of the cured film described below is produced and pixels containing a color-converting luminescent material are formed, it is possible to easily coat each pixel with a different color-converting luminescent material having a different composition.

[0100] The liquid-repellent compound preferably has a fluorine atom, and examples thereof include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di(1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2 Examples include compounds having fluoroalkyl or fluoroalkylene groups at the end, main chain and / or side chain, such as 8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N-[3-(perfluorooctanesulfonamido)propyl]-N,N'-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis(N-perfluorooctylsulfonyl-N-ethylaminoethyl)phosphate, and monoperfluoroalkylethyl phosphate ester. Commercially available fluorine-containing compounds include "Megafac" (registered trademark) F142D, F172, F173, F183, F444, and F477 (all manufactured by Dainippon Ink and Chemicals, Inc.), F-Top EF301, EF303, and EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Fluorad FC-430 and FC-431 (manufactured by Sumitomo 3M Limited), and "A Examples include "SAHIGUARD" (registered trademark) AG710, "SURFLON" (registered trademark) S-382, SC-101, SC-102, SC-103, SC-104, SC-105, and SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15, FTX-218, and DFX-18 (manufactured by Neos Corporation). Two or more of these may be used. Among these, those having a photopolymerizable group are more preferred because they are highly reactive and can form a strong bond with the resin.Examples of liquid-repellent compounds having a fluorine atom and a photopolymerizable group include "Megafac" RS-76-E, RS-56, RS-72-K, RS-75, RS-76-E, RS-76-NS, and RS-90 (all trade names, manufactured by DIC Corporation).

[0101] From the viewpoint of improving the liquid repellency of the cured film and improving inkjet coating properties, the content of the liquid repellent compound is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, while from the viewpoint of improving compatibility with resins and white pigments, the content of the liquid repellent compound is preferably 10% by weight or less, more preferably 5% by weight or less.

[0102] Furthermore, the negative photosensitive coloring composition of the present invention may further contain a crosslinking agent, an adhesion improver, an ultraviolet absorber, a polymerization inhibitor, a surfactant, and the like, if necessary.

[0103] By including a crosslinking agent in the negative-tone photosensitive coloring composition, crosslinking of the siloxane resin is promoted during thermal curing, increasing the degree of crosslinking in the cured film. This prevents a decrease in pattern resolution due to melting of the fine pattern during thermal curing. Examples of curing agents include nitrogen-containing organic compounds, silicone resin curing agents, isocyanate compounds and their polymers, methylolated melamine derivatives, methylolated urea derivatives, various metal alcoholates, various metal chelate compounds, thermal acid generators, and photoacid generators. Two or more of these may be included. Among these, methylolated melamine derivatives, methylolated urea derivatives, and photoacid generators are preferably used from the viewpoints of curing agent stability and coating film processability.

[0104] By containing an adhesion improver in the negative photosensitive coloring composition, the adhesion to the substrate is improved, and a highly reliable cured film can be obtained. As the adhesion improver, an alicyclic epoxy compound or a silane coupling agent is preferred because it has high heat resistance and can suppress color change after heating.

[0105] Examples of alicyclic epoxy compounds include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone, 3,4-epoxycyclohexylmethyl methacrylate, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, hydrogenated bisphenol A bis(propylene glycol glycidyl ether) ether, hydrogenated bisphenol A bis(ethylene glycol glycidyl ether) ether, 1,4-cyclohexanedicarboxylate diglycidyl, and 1,4-cyclohexanedimethanol diglycidyl ether. Two or more of these may be contained.

[0106] The silane coupling agent is preferably a compound represented by formula (19).

[0107] [ka]

[0108] In the above formula (19), each R 12 each independently represents an alkyl group having 1 to 6 carbon atoms. p represents 0 or 1. From the viewpoint of further improving adhesion to the substrate, p is preferably 0. R 13 represents a trivalent organic group having 3 to 30 carbon atoms, and preferably a trivalent hydrocarbon group having 3 to 10 carbon atoms. 14 each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

[0109] Examples of the silane coupling agent represented by the above formula (19) include 3-(tert-butylcarbamoyl)-6-(trimethoxysilyl)hexanoic acid, 2-(2-(tert-butylamino)-2-oxoethyl)-5-(trimethoxysilyl)pentanoic acid, 3-(isopropylcarbamoyl)-6-(trimethoxysilyl)hexanoic acid, 2-(2-(isopropylamino)-2-oxoethyl)-5-(trimethoxysilyl)pentanoic acid, Acid, 3-(isobutylcarbamoyl)-6-(trimethoxysilyl)hexanoic acid, 3-(tert-pentylcarbamoyl)-6-(trimethoxysilyl)hexanoic acid, 2-(2-(tert-pentylamino)-2-oxoethyl)-5-(trimethoxysilyl)pentanoic acid, 6-(dimethoxymethylsilyl)-3-(tert-butylcarbamoyl)hexanoic acid, 5-(dimethoxy(methyl)silyl-2-(2-(tert-butylamino) Examples of the adhesion promoter include 2-(2-(tert-butylamino)-2-oxoethyl)pentanoic acid, 3-(tert-butylcarbamoyl)-6-(trimethoxysilyl)pentanoic acid, 2-(2-(tert-butylamino)-2-oxoethyl)-5-(trimethoxysilyl)butanoic acid, 2-(tert-butylcarbamoyl)-4-(2-(trimethoxysilyl)ethyl)cyclohexanecarboxylic acid, and 2-(tert-butylcarbamoyl)-5-(2-(trimethoxysilyl)ethyl)cyclohexanecarboxylic acid. Two or more of these may be contained. The content of the adhesion promoter in the negative photosensitive coloring composition of the present invention is preferably 0.1% by weight or more, more preferably 1% by weight or more, based on the solid content, from the viewpoint of further improving adhesion to the substrate. On the other hand, the content of the adhesion promoter is preferably 20% by weight or less, more preferably 10% by weight or less, based on the solid content of the negative photosensitive coloring composition, from the viewpoint of further suppressing color change due to heating.

[0110] By including an ultraviolet absorber in the negative photosensitive coloring composition, the light resistance of the cured film can be improved, and the resolution can be further improved.As the ultraviolet absorber, from the viewpoint of further suppressing color change due to heating, benzotriazole compounds such as 2-(2H-benzotriazole-2-yl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-tert-pentylphenol, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazole-2-yl)-6-dodecyl-4-methylphenol, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole are preferably used; benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone; triazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol.These may contain two or more kinds.

[0111] By including a polymerization inhibitor in the negative-tone photosensitive coloring composition, resolution can be improved. Examples of polymerization inhibitors include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol. Commercially available polymerization inhibitors include "IRGANOX" (registered trademark) 1010, "IRGANOX" 1035, "IRGANOX" 1076, "IRGANOX" 1098, "IRGANOX" 1135, "IRGANOX" 1330, "IRGANOX" 1726, "IRGANOX" 1425, "IRGANOX" 1520, "IRGANOX" 245, "IRGANOX" 259, "IRGANOX" 3114, "IRGANOX" 565, and "IRGANOX" 295 (all trade names, manufactured by BASF Japan Ltd.). Two or more of these may be contained.

[0112] The negative photosensitive coloring composition contains a surfactant, which can improve flow properties during application. Examples of surfactants include fluorine-based surfactants such as "Megafac" (registered trademark) F142D, "Megafac" F172, "Megafac" F173, "Megafac" F183, "Megafac" F445, "Megafac" F470, "Megafac" F475, and "Megafac" F477 (all trade names, manufactured by DIC Corporation); silicone-based surfactants such as "BYK" (registered trademark)-333, "BYK"-301, "BYK"-331, "BYK"-345, and "BYK"-307 (all trade names, manufactured by BYK-Chemie Japan Co., Ltd.); polyalkylene oxide-based surfactants; and poly(meth)acrylate-based surfactants. Two or more of these may be contained.

[0113] The solid content concentration of the negative photosensitive coloring composition of the present invention can be arbitrarily set depending on the application method, etc. For example, when forming a film by spin coating as described below, the solid content concentration is generally set to 5% by weight or more and 50% by weight or less. The solid content here refers to all components contained in the negative photosensitive coloring composition, excluding volatile components such as solvents. The amount of solid content can be determined by heating the negative photosensitive coloring composition at 250 ° C for 30 minutes, evaporating the volatile components, and measuring the residue.

[0114] Next, the method for producing the negative photosensitive coloring composition of the present invention will be described below. The negative photosensitive coloring composition of the present invention can be obtained by mixing the above-mentioned components (A) to (E) and, if necessary, other components. More specifically, for example, it is preferable to stir and dissolve (A) siloxane resin, (B) photopolymerization initiator, (C) photopolymerizable compound, (D) white pigment, (E) organic solvent, and, if necessary, other components, and then filter.

[0115] Next, the cured film of the present invention will be described. The cured film of the present invention is a cured film of the negative photosensitive coloring composition of the present invention described above. In addition, the cured film of the present invention preferably has a thickness of 10 μm or more in order to exhibit good reflectivity.

[0116] The method for producing the cured film of the present invention will now be described. The method for producing a cured film of the present invention includes (I) a step of applying the negative photosensitive coloring composition of the present invention onto a substrate to form a coating film, (II) a step of exposing and developing the coating film, and (III) a step of heating the coating film after the development. Each step will be described below.

[0117] (I) A step of applying the negative photosensitive coloring composition of the present invention onto a substrate to form a coating film. Examples of the substrate include glass substrates such as soda lime glass and alkali-free glass.

[0118] Examples of the coating method include spin coating, slit coating, screen printing, inkjet coating, and bar coater coating.

[0119] It is preferable to dry (pre-bake) the substrate coated with the negative photosensitive coloring composition. Examples of drying methods include vacuum drying and heat drying. Examples of heating devices include a hot plate and an oven. The heating temperature is preferably 60 to 150°C, and the heating time is preferably 30 seconds to 3 minutes. The film thickness after pre-baking is preferably 5 to 20 μm.

[0120] (II) a step of exposing and developing the coating film The exposure may be performed through a desired mask or without a mask. Examples of the exposure device include a stepper, a mirror projection mask aligner (MPA), and a parallel light mask aligner (hereinafter referred to as "PLA"). The exposure intensity is 10 to 4000 J / m 2(Equivalent to an exposure dose at a wavelength of 365 nm) Examples of exposure light sources include ultraviolet rays such as i-line, g-line, and h-line, KrF lasers (wavelength 248 nm), and ArF lasers (wavelength 193 nm).

[0121] Examples of the developing method include showering, dipping, and puddling. The immersion time in the developer is preferably 5 seconds to 10 minutes. Examples of the developer include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, and borates; amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine; and aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and choline. After development, the film is preferably rinsed with water, and may then be dry baked at 50 to 140°C.

[0122] (III) A step of heating the coating film after the development Examples of the heating device include a hot plate, an oven, etc. The heating temperature is preferably 120 to 250° C., and the heating time is preferably 15 minutes to 2 hours.

[0123] Next, a description will be given of a partition-attached substrate having partition walls on a base substrate of the present invention, where the partition walls are patterned with a cured film. The partition-attached substrate has partition walls (K) patterned on the base substrate (hereinafter, sometimes referred to as "partition walls (K)"). The base substrate functions as a support for the partition-attached substrate, and the partition walls, when they have pixels containing the color-converting luminescent material (L) described below, function to prevent light from mixing between adjacent pixels.

[0124] 1 shows a cross-sectional view of one embodiment of the substrate with partition walls of the present invention, which has partition walls formed in a pattern. 2 is formed on a base substrate 1 .

[0125] <Base substrate> Examples of the base substrate include a glass plate, a resin plate, and a resin film. The glass plate is preferably made of alkali-free glass. The resin plate and the resin film are preferably made of polyester, (meth)acrylic polymer, transparent polyimide, polyethersulfone, and the like. The thickness of the glass plate and the resin plate is preferably 1 mm or less, and more preferably 0.8 mm or less. The thickness of the resin film is preferably 100 μm or less.

[0126] <Bulkhead (K)> The partition walls (K) preferably have a reflectance of 20% to 95% and an OD value of 0.5 to 3.0 per 10 μm thickness at a wavelength of 550 nm. Here, the thickness of the partition walls (K) refers to the length of the partition walls (K) in a direction approximately perpendicular to the base substrate (height direction). In the case of the substrate with partition walls shown in FIG. 1, the thickness of the partition walls 2 is represented by the symbol H. The length of the partition walls (K) in a direction approximately horizontal to the base substrate is referred to as the width of the partition walls (K). In the case of the substrate with partition walls shown in FIG. 1, the width of the partition walls 2 is represented by the symbol L. In the present invention, reflection on the side surfaces of the partition walls is considered to contribute to improving brightness. On the other hand, the reflectance and OD value per thickness are considered to be the same regardless of the thickness direction or width direction, so in the present invention, attention is focused on the reflectance and OD value per thickness. As will be described later, the thickness of the partition walls (K) is preferably 0.5 to 50 μm, and the width is preferably 5 to 40 μm. Therefore, in the present invention, 10 μm was selected as a representative value for the thickness of the partition walls (K), and attention was paid to the reflectance and OD value per 10 μm thickness.

[0127] The reflectance per 10 μm of thickness is preferably 20% or more from the viewpoint of improving the brightness of the display device. On the other hand, from the viewpoint of improving the accuracy of pattern formation, the reflectance is preferably 95% or less, more preferably 90% or less. The reflectance per 10 μm of thickness at a wavelength of 550 nm of the partition walls (K) can be measured in SCI mode from the top surface of the partition walls (K) having a height direction thickness of 10 μm using a spectrophotometer (e.g., CM-2600d manufactured by Konica Minolta, Inc.). However, if an area sufficient for measurement cannot be secured or a measurement sample having a thickness of 10 μm cannot be obtained, and the composition of the partition walls (K) is known, a 10 μm-thick solid film having the same composition as the partition walls (K) may be prepared, and the reflectance of the solid film may be measured in the same manner instead of the partition walls (K). For example, a solid film may be prepared using the same material as that used to form the partition walls (K), with a thickness of 10 μm, under the same processing conditions as those used to form the partition walls (K), except that no patterning is performed. The reflectance of the resulting solid film may be measured from the top surface in the same manner. The OD value per 10 μm of thickness is preferably 1.0 or more, more preferably 1.5 or more, from the viewpoint of suppressing color mixing between adjacent pixels. On the other hand, from the viewpoint of utilizing reflections on the side surfaces of the partition walls to improve the brightness of the display device, the OD value per 10 μm of thickness is preferably 2.5 or less. The OD value per 10 μm of thickness can be calculated by measuring the intensities of incident light and transmitted light from the top surface of a 10 μm-thick partition wall (K) using an optical densitometer (e.g., a 361T (visual) manufactured by X-rite) and using Equation (20). However, if a sufficient area for measurement cannot be secured or a measurement sample with a thickness of 10 μm cannot be obtained, and the composition of the partition walls (K) is known, a solid film with a thickness of 10 μm and the same composition as the partition walls (K) can be prepared, as in the case of measuring the reflectance, and the OD value of the solid film can be measured in the same manner as for the partition walls (K).

[0128] OD value = log10(I0 / I) (20) I0: Incident light intensity I: transmitted light intensity.

[0129] In addition, as a means for setting the reflectance and OD value within the above range, for example, the above-mentioned negative photosensitive coloring composition of the present invention can be used and patterned by the above-mentioned preferred manufacturing method.

[0130] Furthermore, the partition walls (K) preferably have a taper angle of 45° to 110°. The taper angle refers to the angle between the side edge and the bottom edge of the partition wall cross section. In the case of the substrate with partition walls shown in FIG. 1, the taper angle of the partition walls (K) is represented by the symbol θ. By setting the taper angle to 45° or more, the difference in width between the top and bottom of the partition walls (K) becomes small, and the width of the partition walls (K) can be easily formed within the above-mentioned preferred range. The taper angle is more preferably 70° or more. On the other hand, by setting the taper angle to 110° or less, ink breakage can be suppressed when forming pixels containing the color-converting luminescent material (L) described below by inkjet coating, and inkjet coating properties can be improved. The taper angle is more preferably 95° or less. The taper angle of the partition wall (K) can be determined by observing an arbitrary cross section of the partition wall (K) using an optical microscope (FE-SEM (e.g., S-4800 manufactured by Hitachi, Ltd.)) at an accelerating voltage of 3.0 kV and a magnification of 2,500 times, and measuring the angle between the side edge and the bottom edge of the cross section of the partition wall (K).

[0131] In addition, as a means for setting the reflectance and taper angle of the partition wall (K) within the above range, for example, it can be obtained by using the above-mentioned negative type photosensitive coloring composition of the present invention and patterning it by the above-mentioned preferable production method.

[0132] The partition-equipped substrate of the present invention preferably further comprises pixels (hereinafter sometimes referred to as "pixels (L)") containing a color-converting luminescent material (L) arranged and separated by the partitions (K). The pixels (L) have the function of converting at least a part of the wavelength range of incident light and emitting output light in a wavelength range different from that of the incident light, thereby achieving color display.

[0133] Fig. 2 shows a cross-sectional view of one embodiment of a substrate with partition walls of the present invention, which has patterned partition walls and pixels containing a color-converting luminescent material. Patterned partition walls 2 are provided on a base substrate 1, and pixels 3 are arranged in areas separated by the partition walls 2.

[0134] The color conversion material preferably contains an inorganic phosphor and / or an organic phosphor. For example, in the case of a display device that combines a backlight that emits blue light, liquid crystal formed on a TFT, and pixels (L) as color filters, the region corresponding to the red pixel preferably contains a red phosphor that is excited by blue excitation light and emits red fluorescence, the region corresponding to the green pixel preferably contains a green phosphor that is excited by blue excitation light and emits green fluorescence, and the region corresponding to the blue pixel preferably does not contain a phosphor. On the other hand, the partition-equipped substrate of the present invention can also be used in a display device that uses blue micro LEDs corresponding to each pixel, separated by white partition walls on the substrate, as a backlight. Turning each pixel on / off is possible by turning the blue micro LED on / off, and no liquid crystal is required. Therefore, it is preferable to have two types of partition walls: one that separates each pixel on the substrate and one that separates the blue micro LEDs in the backlight.

[0135] Examples of inorganic phosphors include those that are excited by excitation light with a wavelength of 400 to 500 nm and have an emission spectrum peak in the region of 500 to 700 nm, inorganic semiconductor fine particles known as quantum dots, etc. The former inorganic phosphors may have a shape such as a sphere or a column.

[0136] Inorganic phosphors emit various colors, such as green and red, depending on the peak wavelength of their emission spectrum. Examples of such inorganic phosphors include YAG-based phosphors, TAG-based phosphors, SiAlON-based phosphors, Mn4+-activated fluoride complex phosphors, and inorganic semiconductors known as quantum dots. Two or more of these may be used. Among these, quantum dots are preferred. Because quantum dots have a smaller average particle diameter than other phosphors, they can smooth the surface of the (L) pixel and suppress light scattering on the surface, thereby further improving light extraction efficiency and brightness.

[0137] Examples of quantum dots include semiconductors of Group II-IV, Group III-V, Group IV-VI, and Group IV. Examples of inorganic semiconductors include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, SiN, GeN, and AlO. Two or more of these may be used.

[0138] The quantum dots may contain a p-type dopant or an n-type dopant. The quantum dots may have a core-shell structure. In the core-shell structure, any suitable functional layer (single layer or multiple layers) may be formed around the shell depending on the purpose, and the shell surface may be surface-treated and / or chemically modified.

[0139] Examples of the shape of quantum dots include spherical, columnar, flaky, plate-like, and amorphous shapes. The average particle size of quantum dots can be selected arbitrarily depending on the desired emission wavelength, and is preferably 1 to 30 nm. If the average particle size of quantum dots is 1 to 10 nm, the peaks in the emission spectrum can be sharpened for each of blue, green, and red. For example, when the average particle size of quantum dots is approximately 2 nm, blue light is emitted, when it is approximately 3 nm, green light is emitted, and when it is approximately 6 nm, red light is emitted. The average particle size of quantum dots is preferably 2 nm or more and 8 nm or less. The average particle size of quantum dots can be measured by dynamic light scattering. Examples of devices for measuring the average particle size include the dynamic light scattering photometer DLS-8000 (manufactured by Otsuka Electronics Co., Ltd.).

[0140] Examples of organic fluorescent materials include pyrromethene derivatives having a basic skeleton represented by the following structural formula (21), which are fluorescent materials that emit red fluorescence when excited by blue excitation light, and pyrromethene derivatives having a basic skeleton represented by the following structural formula (22), which are fluorescent materials that emit green fluorescence when excited by blue excitation light. Other examples include perylene-based derivatives, porphyrin-based derivatives, oxazine-based derivatives, and pyrazine-based derivatives, which emit red or green fluorescence depending on the selection of substituents. Two or more of these may be contained. Among these, pyrromethene derivatives are preferred due to their high quantum yield. Pyrromethene derivatives can be obtained, for example, by the method described in JP 2011-241160 A.

[0141] [ka]

[0142] Organic fluorescent materials are preferable because they are soluble in solvents and therefore pixels (L) of a desired thickness can be easily formed. The thickness of the pixel (L) is preferably 0.5 μm or more, more preferably 1 μm or more, from the viewpoint of improving color characteristics, while the thickness of the pixel (L) is preferably 30 μm or less, more preferably 20 μm or less, from the viewpoint of thinning the display device and curved surface processability.

[0143] The size of each pixel (L) is generally about 20 to 200 μm. The pixels (L) are preferably arranged so as to be separated by partition walls (K). By providing partition walls between pixels, it is possible to further suppress the diffusion and color mixing of emitted light.

[0144] The pixels (L) can be formed, for example, by filling a color-converting luminescent material coating liquid containing a color-converting luminescent material into spaces separated by partition walls (K). The color-converting luminescent material coating liquid may further contain a resin and a solvent.

[0145] As a method for filling the color-changing luminescent material coating liquid, an ink-jet coating method or the like is preferred from the viewpoint of easily coating different types of color-changing luminescent materials in each pixel.

[0146] The obtained coating film may be dried under reduced pressure and / or dried by heating. When drying under reduced pressure, the temperature for drying under reduced pressure is preferably 80°C or lower to prevent the drying solvent from re-condensing on the inner wall of the vacuum chamber. The pressure for drying under reduced pressure is preferably equal to or lower than the vapor pressure of the solvent contained in the coating film, and is preferably 1 to 1000 Pa. The time for drying under reduced pressure is preferably 10 to 600 seconds. When drying by heating, examples of the heating drying device include an oven and a hot plate. The temperature for heating and drying is preferably 60 to 200°C. The time for heating and drying is preferably 1 to 60 minutes. [Example]

[0147] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Among the compounds used in the synthesis examples, preparation examples, and examples, those for which abbreviations are used are shown below. PGMEA: Propylene glycol monomethyl ether acetate DAA: Diacetone alcohol BHT: dibutylhydroxytoluene.

[0148] The solids concentration of the siloxane resin solution in Synthesis Examples 1 to 8 was determined by the following method. 1.5 g of the siloxane resin solution or acrylic resin solution was weighed into an aluminum cup and heated on a hot plate at 250°C for 30 minutes to evaporate the liquid. The weight of the solids remaining in the aluminum cup after heating was weighed, and the solids concentration of the siloxane resin solution or acrylic resin solution was determined from the ratio to the weight before heating.

[0149] The weight-average molecular weight of the acrylic resin in the siloxane resin in Synthesis Examples 1 to 8 was determined by the following method: Using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation) and tetrahydrofuran as a fluidized bed, GPC analysis was performed in accordance with JIS K7252-3 (established on March 20, 2008) to measure the weight-average molecular weight in terms of polystyrene.

[0150] The content ratio of each repeating unit in the siloxane resin in Synthesis Examples 1 to 8 was determined by the following method. The siloxane resin solution was poured into an NMR sample tube made of "Teflon" (registered trademark) with a diameter of 10 mm. 29 Si-NMR measurements were performed, and the content ratio of each repeating unit was calculated from the ratio of the integral value of Si derived from a specific organosilane to the integral value of all Si derived from organosilanes. 29 The Si-NMR measurement conditions are as follows: Equipment: Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.) Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6693MHz ( 29 Si nucleus) Spectral width: 20000Hz Pulse width: 12 μs (45° pulse) Pulse repetition time: 30.0 seconds Solvent: acetone-d6 Reference material: tetramethylsilane Measurement temperature: 23℃ Sample rotation speed: 0.0 Hz.

[0151] Synthesis Example 1 Siloxane resin (A-1) solution A 1000 ml three-neck flask was charged with 65.72 g (0.400 mol) of propyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 40.67 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 27.24 g (0.200 mol) of methyltrimethoxysilane, 0.0407 g of BHT, and 117.63 g of PGMEA. An aqueous phosphoric acid solution prepared by dissolving 0.897 g of phosphoric acid (0.5 wt % relative to the charged monomers) in 54.00 g of water was added over 30 minutes with stirring at room temperature.

[0152] The flask was then immersed in a 70°C oil bath and stirred for 90 minutes, after which the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the mixture was heated and stirred for 1 hour and 30 minutes (internal temperature 100-110°C), yielding a siloxane resin solution. During the temperature increase and heating and stirring, a gas mixture of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 L / min. A total of 115.83 g of by-products, methanol and water, was distilled during the reaction. PGMEA was added to the resulting siloxane resin solution to adjust the solids concentration to 40% by weight, yielding a siloxane resin (A-1) solution. The weight-average molecular weight of the resulting siloxane resin (A-1) was 5,000 (polystyrene equivalent).

[0153] Also, 29From the results of Si-NMR measurement, the molar ratios of repeating units derived from propyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-methacryloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in siloxane resin (A-1) were 40 mol%, 17.5 mol%, 17.5 mol%, 5 mol%, and 20 mol%, respectively.

[0154] Synthesis Example 2 Siloxane resin (A-2) solution A 1000 ml three-neck flask was charged with 32.86 g (0.200 mol) of propyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 40.67 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 54.48 g (0.400 mol) of methyltrimethoxysilane, 0.407 g of BHT, and 112.01 g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 0.869 g of phosphoric acid (0.5 wt % relative to the charged monomers) in 54.00 g of water was added over 30 minutes with stirring at room temperature.

[0155] Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 114.83 g of by-products, methanol and water, was distilled off. PGMEA was added to the obtained siloxane resin solution so that the solids concentration was 40 wt %, to obtain a siloxane resin (A-2) solution. The weight-average molecular weight of the obtained siloxane resin (A-2) was 6,200 (polystyrene equivalent).

[0156] Also, 29From the results of Si-NMR measurement, the molar ratios of repeating units derived from propyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-methacryloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in siloxane resin (A-2) were 20 mol%, 17.5 mol%, 17.5 mol%, 5 mol%, and 40 mol%, respectively.

[0157] Synthesis Example 3 Siloxane resin (A-3) solution A 1000 ml three-neck flask was charged with 98.58 g (0.600 mol) of propyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 40.67 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 0.0407 g of BHT, and 123.25 g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 0.926 g of phosphoric acid (0.5 wt % based on the charged monomers) in 54.00 g of water was added over 30 minutes with stirring at room temperature.

[0158] Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 114.33 g of by-products, methanol and water, was distilled off. PGMEA was added to the obtained siloxane resin solution so that the solids concentration was 40 wt %, to obtain a siloxane resin (A-3) solution. The weight-average molecular weight of the obtained siloxane resin (A-3) was 4,500 (polystyrene equivalent).

[0159] Also, 29 From the Si-NMR measurement results, the molar ratios of repeating units derived from propyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid anhydride, 3-methacryloxypropylmethyldimethoxysilane, and 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane in the siloxane resin (A-3) were 60 mol%, 17.5 mol%, 17.5 mol%, and 5 mol%, respectively.

[0160] Synthesis Example 4 Siloxane resin (A-4) solution A 1000 ml three-neck flask was charged with 82.56 g (0.400 mol) of hexyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 40.67 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 27.24 g (0.200 mol) of methyltrimethoxysilane, 0.0407 g of BHT, and 134.47 g of PGMEA. An aqueous phosphoric acid solution prepared by dissolving 0.982 g of phosphoric acid (0.5 wt % relative to the charged monomers) in 54.00 g of water was added over 30 minutes with stirring at room temperature.

[0161] Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 115.63 g of by-products, methanol and water, was distilled off. PGMEA was added to the obtained siloxane resin solution so that the solids concentration was 40 wt %, to obtain a siloxane resin (A-4) solution. The weight-average molecular weight of the obtained siloxane resin (A-4) was 4,800 (polystyrene equivalent).

[0162] Also, 29 From the results of Si-NMR measurement, the molar ratios of repeating units derived from hexyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-methacryloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in siloxane resin (A-4) were 40 mol%, 17.5 mol%, 17.5 mol%, 5 mol%, and 20 mol%, respectively.

[0163] Synthesis Example 5 Siloxane resin (A-5) solution A 1000 ml three-neck flask was charged with 105.00 g (0.400 mol) of decyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 40.67 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 27.24 g (0.200 mol) of methyltrimethoxysilane, 0.0407 g of BHT, and 156.91 g of PGMEA. An aqueous phosphoric acid solution prepared by dissolving 1.094 g of phosphoric acid (0.5 wt % relative to the charged monomers) in 54.00 g of water was added over 30 minutes with stirring at room temperature.

[0164] Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 114.60 g of by-products, methanol and water, was distilled off. PGMEA was added to the obtained siloxane resin solution so that the solids concentration was 40 wt %, to obtain a siloxane resin (A-5) solution. The weight-average molecular weight of the obtained siloxane resin (A-5) was 4,600 (polystyrene equivalent).

[0165] Also, 29 From the results of Si-NMR measurement, the molar ratios of repeating units derived from decyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-methacryloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in siloxane resin (A-5) were 40 mol%, 17.5 mol%, 17.5 mol%, 5 mol%, and 20 mol%, respectively.

[0166] Synthesis Example 6 Siloxane resin (A-6) solution A 1000 ml three-neck flask was charged with 65.72 g (0.400 mol) of propyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 12.32 g (0.05 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 51.08 g (0.375 mol) of methyltrimethoxysilane, and 89.64 g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 0.813 g of phosphoric acid (0.5 wt % based on the charged monomers) in 57.15 g of water was added over 30 minutes with stirring at room temperature.

[0167] The flask was then immersed in a 70°C oil bath and stirred for 90 minutes, after which the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the mixture was heated and stirred for 1 hour and 30 minutes (internal temperature 100-110°C), yielding a siloxane resin solution. During the temperature increase and heating and stirring, a gas mixture of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 L / min. A total of 130.18 g of by-products, methanol and water, was distilled during the reaction. PGMEA was added to the resulting siloxane resin solution to adjust the solids concentration to 40% by weight, yielding a siloxane resin (A-6) solution. The weight-average molecular weight of the resulting siloxane resin (A-6) was 5,500 (polystyrene equivalent).

[0168] Also, 29 From the Si-NMR measurement results, the molar ratios of repeating units derived from propyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in the siloxane resin (A-6) were 40 mol%, 17.5 mol%, 5 mol%, and 37.5 mol%, respectively.

[0169] Synthesis Example 7 Siloxane resin (A-7) solution A 1000 ml three-necked flask was charged with 16.43 g (0.100 mol) of propyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 40.67 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32 g (0.05 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 68.10 g (0.500 mol) of methyltrimethoxysilane, 0.0407 g of BHT, and 109.20 g of PGMEA. A phosphoric acid aqueous solution prepared by dissolving 0.855 g of phosphoric acid (0.5 wt.% based on the charged monomer) in 54.00 g of water was added over 30 minutes while stirring at room temperature. A siloxane resin solution was then obtained in the same manner as in Synthesis Example 1. A total of 115.90 g of by-products, methanol and water, was distilled during the reaction. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration became 40% by weight, and a siloxane resin (A-7) solution was obtained. The weight average molecular weight of the obtained siloxane resin (A-7) was 5,500 (polystyrene equivalent). 29 From the results of Si-NMR measurement, the molar ratios of repeating units derived from propyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid anhydride, 3-methacryloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and methyltrimethoxysilane in siloxane resin (A-7) were 10 mol%, 17.5 mol%, 17.5 mol%, 5 mol%, and 50 mol%, respectively.

[0170] Synthesis Example 8 Siloxane resin (A-8) solution A 1000 ml three-neck flask was charged with 131.44 g (0.800 mol) of propyltrimethoxysilane, 26.21 g (0.100 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 23.24 g (0.100 mol) of 3-methacryloxypropylmethyldimethoxysilane, 0.0232 g of BHT, and 115.97 g of PGMEA. A phosphoric acid solution prepared by dissolving 0.904 g of phosphoric acid (0.5 wt.% based on the charged monomers) in 54.00 g of water was added over 30 minutes while stirring at room temperature. A siloxane resin solution was then obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 118.90 g of by-products, methanol and water, was distilled off. Additional PGMEA was added to the resulting siloxane resin solution to adjust the solids concentration to 40 wt. Siloxane resin (A-8) solution was obtained. The weight average molecular weight of the obtained siloxane resin (A-8) was 4,100 (polystyrene equivalent). 29 From the Si-NMR measurement results, the molar ratios of repeating units derived from propyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid anhydride, and 3-methacryloxypropylmethyldimethoxysilane in the siloxane resin (A-8) were 80 mol%, 10 mol%, and 10 mol%, respectively.

[0171] Synthesis Example 9 Siloxane resin (A-9) solution A 1000ml three-neck flask was charged with 45.87g (0.175mol) of 3-trimethoxysilylpropyl succinic anhydride, 40.67g (0.175mol) of 3-methacryloxypropylmethyldimethoxysilane, 12.32g (0.05mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 27.24g (0.200mol) of methyltrimethoxysilane, 97.75g (0.400mol) of diphenyldimethoxysilane, 0.0407g of BHT, and 158.86g of PGMEA. A phosphoric acid aqueous solution prepared by dissolving 1.058g of phosphoric acid (0.5% by weight based on the charged monomer) in 46.80g of water was added over 30 minutes while stirring at room temperature. A siloxane resin solution was then obtained in the same manner as in Synthesis Example 1. A total of 99.43g of by-products, methanol and water, was distilled during the reaction. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration was 40% by weight, thereby obtaining a siloxane resin (A-9) solution. The weight average molecular weight of the obtained siloxane resin (A-9) was 3,800 (polystyrene equivalent). 29 From the results of Si-NMR measurement, the molar ratios of repeating units derived from 3-trimethoxysilylpropylsuccinic acid anhydride, 3-methacryloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and diphenyldimethoxysilane in siloxane resin (A-9) were 17.5 mol%, 17.5 mol%, 5 mol%, 20 mol%, and 40 mol%, respectively. The raw material compositions of the siloxane resins in Synthesis Examples 1 to 9 are shown in Table 1.

[0172] [Table 1]

[0173] Synthesis Example 10 Silane coupling agent (J1) solution To 200 g of PGMEA, 41.97 g (0.16 mol) of 3-trimethoxysilylpropylsuccinic anhydride and 11.70 g (0.16 mol) of t-butylamine were added and stirred at room temperature for a while, followed by stirring at 40°C for 2 hours. The temperature was then raised to 80°C and heated and stirred for 6 hours. PGMEA was added to the resulting solution so that the solids concentration was 20 wt%, yielding a silane coupling agent (J1), which was a mixed solution of 3-(tert-butylcarbamoyl)-6-(trimethoxysilyl)hexanoic acid and 2-(2-(tert-butylamino)-2-oxoethyl)-5-(trimethoxysilyl)pentanoic acid.

[0174] Synthesis Example 11 Green organic phosphor 3,5-Dibromobenzaldehyde (3.0 g), 4-t-butylphenylboronic acid (5.3 g), tetrakis(triphenylphosphine)palladium(0) (0.4 g), and potassium carbonate (2.0 g) were placed in a flask and purged with nitrogen. Degassed toluene (30 mL) and degassed water (10 mL) were added and refluxed for 4 hours. The reaction solution was cooled to room temperature, and the organic layer was separated and washed with saturated brine.

[0175] The organic layer was dried over magnesium sulfate, filtered, and the solvent was removed by distillation. The resulting reaction product was purified by silica gel column chromatography to obtain 3.5 g of 3,5-bis(4-t-butylphenyl)benzaldehyde as a white solid. Next, 1.5 g of 3,5-bis(4-t-butylphenyl)benzaldehyde and 0.7 g of 2,4-dimethylpyrrole were placed in a flask, and 200 mL of dehydrated dichloromethane and 1 drop of trifluoroacetic acid were added. The mixture was stirred for 4 hours under a nitrogen atmosphere. 0.85 g of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in dehydrated dichloromethane was added, followed by stirring for an additional hour.

[0176] After the reaction was completed, boron trifluoride diethyl ether complex (7.0 mL) and diisopropylethylamine (7.0 mL) were added and stirred for 4 hours, after which water (100 mL) was added and stirred, and the organic layer was separated. This organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. The resulting reaction product was purified by silica gel column chromatography to obtain 0.4 g of a green powder (yield 17%). 1 The results of H-NMR analysis are as follows, and it was confirmed that the green powder obtained above was [G-1] represented by the following structural formula. 1 H-NMR (CDCl3(d=ppm)): 7.95(s,1H), 7.63-7.48(m,10H), 6.00(s,2H), 2.58(s,6H), 1.50(s,6H), 1.37(s,18H).

[0177] [ka]

[0178] Synthesis Example 12 Red organic phosphor A mixed solution of 300 mg of 4-(4-t-butylphenyl)-2-(4-methoxyphenyl)pyrrole, 201 mg of 2-methoxybenzoyl chloride, and 10 mL of toluene was heated at 120°C for 6 hours under a nitrogen stream. After cooling to room temperature, the mixture was evaporated. After washing with 20 mL of ethanol and drying under vacuum, 260 mg of 2-(2-methoxybenzoyl)-3-(4-t-butylphenyl)-5-(4-methoxyphenyl)pyrrole was obtained. Next, a mixed solution of 260 mg of 2-(2-methoxybenzoyl)-3-(4-t-butylphenyl)-5-(4-methoxyphenyl)pyrrole, 180 mg of 4-(4-t-butylphenyl)-2-(4-methoxyphenyl)pyrrole, 206 mg of methanesulfonic anhydride, and 10 mL of degassed toluene was heated at 125°C for 7 hours under a nitrogen stream.

[0179] After cooling to room temperature, 20 ml of water was added and the mixture was extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, evaporated, and vacuum-dried to obtain the pyrromethene derivative as a residue. Next, 305 mg of diisopropylethylamine and 670 mg of boron trifluoride diethyl ether complex were added to a mixed solution of the obtained pyrromethene derivative and 10 ml of toluene under a nitrogen stream and stirred at room temperature for 3 hours. 20 ml of water was added and the mixture was extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, dried over magnesium sulfate, and evaporated. After purification by silica gel column chromatography and vacuum-drying, 0.27 g of a reddish-purple powder was obtained (yield 70%).

[0180] The resulting reddish purple powder 1 The results of H-NMR analysis are as follows, and it was confirmed that the reddish-purple powder obtained above was [R-1] represented by the following structural formula. 1 H-NMR (CDCl3(d=ppm)): 1.19(s,18H),3.42(s,3H),3.85(s,6H),5.72(d,1H),6.20(t,1H),6.42-6.97(m,16H),7.89(d,4H).

[0181] [ka]

[0182] Preparation Example 1 Color-changing light-emitting material composition (CL-1) 20 parts by weight of a 0.4 wt % toluene solution of the green phosphor G-1 obtained in Synthesis Example 11, 45 parts by weight of DPHA, 5 parts by weight of "Irgacure" (registered trademark) 907 (manufactured by BASF Japan Ltd.), 166 parts by weight of a 30 wt % PGMEA solution of acrylic resin (SPCR-18 (trade name), manufactured by Showa Denko K.K.), and 117 parts by weight of toluene were mixed and stirred to form a uniform solution. The mixture was filtered through a 0.45 μm syringe filter to prepare a color-converting luminescent material composition (CL-1). Preparation Example 2 Color-changing light-emitting material composition (CL-2) A color-converting luminescent material composition (CL-2) was prepared in the same manner as in Preparation Example 1, except that 0.4 parts by weight of the red phosphor R-1 obtained in Synthesis Example 12 was used instead of the green phosphor G-1. The evaluations in each of the examples and comparative examples were carried out by the following methods.

[0183] <resolution> Using a spin coater (product name 1H-360S, manufactured by Mikasa Co., Ltd.), the negative photosensitive coloring composition obtained in each example and comparative example was spin coated onto a 10 cm square alkali-free glass substrate so that the film thickness after curing would be 10 μm, and then using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.), the film was prebaked at a temperature of 90 ° C. for 2 minutes to produce a prebaked film with a film thickness of 10 μm.

[0184] The prepared prebaked film was exposed to light using a parallel light mask aligner (product name PLA-501F, manufactured by Canon Inc.) at a dose of 200 mJ / cm through a mask having line and space patterns with widths of 100 μm, 80 μm, 60 μm, 50 μm, 40 μm, 30 μm, and 20 μm, using an ultra-high pressure mercury lamp as a light source. 2 The film was exposed to i-line radiation with a gap of 100 μm, and then shower-developed with a 0.045 wt % potassium hydroxide aqueous solution for 100 seconds using an automatic developing apparatus (Takizawa Sangyo Co., Ltd., "AD-2000 (trade name)"), followed by rinsing with water for 30 seconds.

[0185] The developed pattern was observed under magnification using a microscope adjusted to 100x magnification, and the narrowest line width of the pattern in which no residue was found in the unexposed area was taken as the resolution. However, if there was residue in the unexposed area near the 100 μm wide pattern, it was recorded as ">100 μm."

[0186] <Reflectance> Using a spin coater (trade name: 1H-360S, manufactured by Mikasa Co., Ltd.), the negative photosensitive coloring compositions obtained in each example and comparative example were spin-coated onto a 10 cm square non-alkali glass substrate so that the film thickness after curing was 10 μm, and pre-baked at a temperature of 90 °C for 2 minutes using a hot plate (SCW-636) to form a pre-baked film. The pre-baked film thus prepared was exposed, developed, and rinsed in the same manner as the evaluation method of <resolution> described above, except without using a mask. Further, using an oven (trade name: IHPS-222, manufactured by Espec Corporation), curing was performed at a temperature of 230 °C for 30 minutes in air to produce a cured film. For the non-alkali glass substrate having the cured film, the reflectance at a wavelength of 550 nm in the SCI mode was measured from the solid film side using a spectrophotometer (trade name: CM-2600d, manufactured by Konica Minolta Co., Ltd.). However, when cracks occurred in the solid film, accurate values could not be obtained due to cracks or the like, so the reflectance measurement was not performed.

[0187] <Light resistance> For the non-alkali glass substrate having the cured film on which the above-mentioned <reflectance> was measured, ultraviolet light with a wavelength of 365 nm and an illuminance of 0.6 mW / cm 2 was irradiated in air at a temperature of 40 °C for 300 hours, and then the reflectance was measured in the same manner as the evaluation method of the above-mentioned <reflectance> to obtain the reflectance after ultraviolet light irradiation. The absolute value of the numerical value obtained by subtracting the value of the reflectance after ultraviolet light irradiation from the value of the reflectance before ultraviolet light irradiation was evaluated as the change width, and the smaller the change width, the better the light resistance. The change width of the reflectance is preferably 1.0 or less, more preferably 0.8 or less, and even more preferably 0.5 or less.

[0188] <OD value> Using a spin coater (1H-360S; manufactured by Mikasa Co., Ltd.), the negative photosensitive coloring compositions obtained in each Example and Comparative Example were applied to a 10 cm square alkali-free glass substrate so that the film thickness after curing would be 10 μm, and a cured film was produced in the same manner as in the evaluation method for <Reflectance> described above. For the glass substrate with the obtained cured film, the intensities of incident light and transmitted light were measured using an optical densitometer (361T (visual); manufactured by X-rite Co., Ltd.), and the OD value was calculated using the equation (20) described below. OD value = log10(I0 / I) (20) I0: Incident light intensity I: transmitted light intensity.

[0189] <Crack resistance> Using a spin coater (1H-360S; manufactured by Mikasa Co., Ltd.), the negative-tone photosensitive coloring compositions obtained in each Example and Comparative Example were applied to 10 cm square alkali-free glass substrates so that the cured film thicknesses were 5 μm, 10 μm, 15 μm, and 20 μm, respectively. The substrates were then prebaked at 90°C for 2 minutes using a hot plate (SCW-636) to form prebaked films. The prebaked films were exposed, developed, and rinsed in the same manner as in the evaluation method for <Resolution> described above, except that no mask was used. Furthermore, the prebaked films were cured in air at 230°C for 30 minutes using an oven (trade name IHPS-222; manufactured by Espec Corporation) to form cured films.

[0190] The produced cured films were visually observed to evaluate the presence or absence of cracks. If even one crack was found, it was determined that there was no crack resistance at that film thickness. For example, if there were no cracks at a film thickness of 15 μm but cracks were present at a film thickness of 20 μm, the crack-resistant film thickness was determined to be "≦15 μm." Furthermore, if there were no cracks even at 20 μm, the crack-resistant film thickness was determined to be "≦20 μm," and if there were cracks even at 5 μm, the crack-resistant film thickness was determined to be "<5 μm," and these were used to determine the crack resistance.

[0191] <Taper angle> Using a spin coater (1H-360S; manufactured by Mikasa Co., Ltd.), the negative photosensitive coloring composition obtained in each example and comparative example was applied to a 10 cm square alkali-free glass substrate so that the film thickness after curing would be 10 μm, and then dried at a temperature of 90° C. for 2 minutes using a hot plate (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a dried film. The produced dried film was then irradiated with an ultra-high pressure mercury lamp as a light source through a photomask using a parallel light mask aligner (trade name PLA-501F, manufactured by Canon Inc.) at an exposure dose of 200 mJ / cm . 2 The film was exposed to i-line radiation. The film was then shower-developed for 100 seconds using a 0.045 wt % potassium hydroxide aqueous solution using an automatic developing apparatus (Takizawa Sangyo Co., Ltd., "AD-2000 (trade name)"), followed by rinsing with water for 30 seconds. The film was then heated in air at 230°C for 30 minutes using an oven (trade name IHPS-222, Espec Corp.), resulting in a substrate on the glass substrate with a grid-like pattern of 10 μm high, 20 μm wide barrier ribs with a short side of 100 μm and a long side of 300 μm pitch. An arbitrary cross section of the barrier rib-equipped substrate was observed using an optical microscope (FE-SEM (S-4800); Hitachi, Ltd.) at an accelerating voltage of 3.0 kV, and the taper angle was measured. The taper angle refers to the angle between the side and bottom edges of the barrier rib cross section. In the case of the substrate with partition walls shown in FIG. 1, the taper angle of the partition walls 2 is represented by the symbol θ.

[0192] <Inkjet coating properties> The negative photosensitive coloring compositions obtained in each Example and Comparative Example were processed in the same manner as in the evaluation method for <Taper Angle> described above to form substrates with partition walls patterned in a grid shape. PGMEA was used as ink to inkjet coat the pixel areas surrounded by the grid-shaped partition walls using an inkjet coater (InkjetLabo, manufactured by Cluster Technology Co., Ltd.). 160 pL of PGMEA was applied per grid pattern, and the presence or absence of breakage (a phenomenon in which the ink overcomes the partition walls and mixes into adjacent pixel areas) was observed, and the inkjet coatability was evaluated according to the following criteria. The less breakage there was, the higher the liquid repellency and the better the inkjet coatability. A: The ink did not overflow from within the pixels. B: In some areas, ink overflowed from within the pixels onto the top surface of the partition wall.

[0193] <Brightness> The negative photosensitive coloring compositions obtained in each of the Examples and Comparative Examples were processed in the same manner as in the evaluation method for <Taper Angle> described above to form substrates on which partition walls were patterned in a grid pattern. Then, a color-changing light-emitting material composition (CL-1) was applied using an inkjet method under a nitrogen atmosphere and dried at 100°C for 30 minutes to form pixels with a thickness of 5.0 μm, thereby obtaining a substrate with partition walls as shown in Figure 2. A surface light-emitting device equipped with a commercially available LED backlight (peak wavelength 465 nm) was used as a light source, and the obtained substrate with partition walls was placed so that the pixel section faced the light source. A current of 30 mA was passed through this surface light-emitting device to light the LED elements, and the luminance (unit: cd / m ) based on the CIE 1931 standard was measured using a spectroradiometer (CS-1000, manufactured by Konica Minolta). 2 The luminance was evaluated as a relative value, with the initial luminance of Comparative Example 2 being taken as the standard 100.

[0194] <Color mixture> In the substrates with partition walls obtained in each Example and Comparative Example before pixel formation, a color-converting luminescent material composition (CL-1) was applied by inkjet printing to a part of the pixel area surrounded by the lattice-shaped partition walls, and dried at 100°C for 30 minutes to form a pixel with a thickness of 5.0 μm. Thereafter, a color-converting luminescent material composition (CL-2) was applied by inkjet printing to an area of ​​the pixel area surrounded by the lattice-shaped partition walls adjacent to the area where the color-converting luminescent material composition (CL-1) was applied, and dried at 100°C for 30 minutes to form a pixel with a thickness of 5.0 μm.

[0195] On the other hand, a blue organic EL cell having the same width as the pixel portion surrounded by the lattice-shaped partition wall was fabricated, and the blue organic EL cell was placed opposite the aforementioned substrate with partition wall and bonded to it with a sealant to obtain the display device shown in Figure 3.

[0196] Of the blue organic EL cells 4 in Figure 3, only the blue organic EL cell attached directly below pixel 3 (CL-1) formed with color-converting luminescent material composition (CL-1) was turned on. With this in mind, the absorbance intensity A (630 nm) at a wavelength of 630 nm was measured for pixel 3 (CL-2) formed with color-converting luminescent material composition (CL-2) using a microspectrophotometer LVmicro-V (manufactured by Lambda Vision Co., Ltd.). The smaller the value of absorbance intensity A (630 nm), the less likely color mixing is to occur. Color mixing was evaluated according to the following criteria. A:A(630nm)<0.01 B: 0.01≦A(630nm)≦0.5 C:0.5 <A(630nm)。

[0197] Example 1 5.00 g of titanium dioxide pigment (R-960; manufactured by BASF Japan Ltd.) as (D) white pigment was mixed with 5.00 g of siloxane resin (A-1) solution as (A) siloxane resin, and the mixture was dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-1).

[0198] Next, 6.400 g of pigment dispersion (MW-1), 3.225 g of siloxane resin (A-1) solution, (B) 0.120 g of ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) ("Irgacure" (registered trademark) OXE-02 (trade name) manufactured by BASF Japan Ltd. (hereinafter referred to as "OXE-02")) as a photopolymerization initiator, 0.240 g of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("Irgacure"-819 (trade name) manufactured by BASF Japan Ltd.), (C) 3.20 g of a 50 wt % PGMEA diluted solution of pentaerythritol acrylate ("Light Acrylate" (registered trademark) PE-4A (trade name) manufactured by Kyoeisha Chemical Co., Ltd.) as a photopolymerizable compound, and siloxane resin (A-2) solution were mixed. 0.400 g of a 20 wt % PGMEA diluted solution of the dimethylaminobenzoate coupling agent (J1), 0.160 g of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("Celloxide" (registered trademark)-2021P (trade name), manufactured by Daicel Corporation), 0.024 g of ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] ("Irganox" (registered trademark)-1010 (trade name), manufactured by BASF Japan Ltd.), and 0.060 g of a 10 wt % PGMEA diluted solution (corresponding to a concentration of 300 ppm) of an acrylic surfactant (trade name "BYK" (registered trademark)-352, manufactured by BYK Japan K.K.) were dissolved in a mixed solvent of 1.200 g of DAA and 4.971 g of PGMEA, and the mixture was stirred. Then, it is filtered through a 5.0 μm filter to obtain a negative type photosensitive coloring composition (P-1). For the obtained negative type photosensitive coloring composition (P-1), it is evaluated for resolution, reflectance, lightfastness, OD value, crack resistance, lightfastness, inkjet characteristics, brightness, and color mixing.

[0199] Examples 2 to 6 Instead of the siloxane resin (A-1) solution, the siloxane resin (A-2) to (A-6) solutions were used, respectively, in the same manner as in Example 1, to obtain negative photosensitive coloring compositions (P-2) to (P-6). Using the obtained negative photosensitive coloring compositions (P-2) to (P-6), evaluations were carried out in the same manner as in Example 1.

[0200] Example 7 Instead of the siloxane resin (A-1) solution, a siloxane resin (A-2) solution was used, and (C) as a photopolymerizable compound, instead of pentaerythritol acrylate ("Light Acrylate" (registered trademark) PE-4A (trade name), manufactured by Kyoeisha Chemical Co., Ltd.), trimethylolpropane-PO (propylene oxide) modified triacrylate (average PO number = 3) ("Aronix" (registered trademark) M-310 (trade name), manufactured by Toagosei Co., Ltd.)) was used, except that the same procedure as in Example 1 was carried out to obtain a negative photosensitive coloring composition (P-7). Using the obtained negative photosensitive coloring composition (P-7), evaluation was carried out in the same manner as in Example 1.

[0201] Example 8 Instead of the siloxane resin (A-1) solution, a siloxane resin (A-2) solution was used, and (C) as a photopolymerizable compound, pentaerythritol acrylate ("Light Acrylate" (registered trademark) PE-4A (trade name), manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of tripropylene glycol diglycidyl ether acrylate (manufactured by Kyoeisha Chemical Co., Ltd.) ("Epoxy Ester" (registered trademark) 200PA (trade name), manufactured by Kyoeisha Chemical Co., Ltd.) was used. The same procedure as in Example 1 was carried out to obtain a negative photosensitive coloring composition (P-8). The obtained negative photosensitive coloring composition (P-8) was evaluated in the same manner as in Example 1.

[0202] Example 9 5.00 g of titanium nitride (manufactured by Wako Pure Chemical Industries, Ltd.; particle size: 50 nm, titanium content: 74.3 wt %, nitrogen content: 20.3 wt %, oxygen content: 2.94 wt %) as the (F) black pigment was mixed with 5.00 g of siloxane resin (A-1) solution as the (A) siloxane resin, and the mixture was dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-2).

[0203] The amount of siloxane resin (A-1) solution added was changed to 3.183 g, the PGMEA mixed solvent was changed to 4.989, and 0.24 g of pigment dispersion (MW-2) was added, except that the same procedure as in Example 1 was carried out to obtain a negative photosensitive coloring composition (P-9). Using the obtained negative photosensitive coloring composition (P-9), evaluation was carried out in the same manner as in Example 1.

[0204] Example 10 5.00 g of a mixed pigment of red pigment PR254 and blue pigment PB64 in a weight ratio of 60 / 40 as the (F) black pigment was mixed with 5.00 g of a siloxane resin (A-1) solution as the (A) siloxane resin, and the mixture was dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-3).

[0205] The amount of siloxane resin (A-1) solution added was changed to 3.183 g, the PGMEA mixed solvent was changed to 4.9890, and 0.24 g of pigment dispersion (MW-3) was added, except that the same procedure was followed as in Example 1 to obtain a negative photosensitive coloring composition (P-10). Using the obtained negative photosensitive coloring composition (P-10), evaluation was carried out in the same manner as in Example 1.

[0206] Example 11 (G) As an organometallic compound, 2.00 g of bis(acetylacetonato)palladium was dissolved in 8.00 g of DAA to obtain an organometallic compound solution (OM-1).

[0207] The amount of siloxane resin (A-1) solution added was changed to 2.865 g, the mixed solvent PGMEA was changed to 5.1870 g, DAA was changed to 0.624 g, and 0.720 g of organometallic compound solution (OM-1) was added, except that the same procedure as in Example 1 was carried out to obtain a negative photosensitive coloring composition (P-11). Using the obtained negative photosensitive coloring composition (P-11), evaluation was carried out in the same manner as in Example 1.

[0208] Example 12 (H) As a coordination compound having a phosphorus atom, 2.00 g of triphenylphosphine was dissolved in 8.00 g of DAA to obtain a solution of a coordination compound having a phosphorus atom (OH-1).

[0209] The amount of siloxane resin (A-1) solution added was changed to 2.585g, the mixed solvent PGMEA was changed to 5.355g, DAA was changed to 0.176g, and 0.72g of organometallic compound solution (OM-1), 0.56g of phosphorus atom-containing coordination compound solution (OH-1) was added, except that the same procedure as in Example 1 was carried out to obtain a negative photosensitive coloring composition (P-12). Using the obtained negative photosensitive coloring composition (P-12), evaluation was carried out in the same manner as in Example 1.

[0210] Example 13 (I) As a liquid-repellent compound, 0.300 g of a 20 wt% PGMEA diluted solution of a photopolymerizable fluorine-containing compound ("Megafac" (registered trademark) RS-75-A (trade name) manufactured by DIC Corporation (hereinafter referred to as "RS-75-A")) was added, the amount of siloxane resin (A-1) solution added was changed to 3.075 g, and the PGMEA mixed solvent was changed to 4.821 g. Except for this, the same procedure as in Example 1 was carried out to obtain a negative photosensitive coloring composition (P-13). Using the obtained negative photosensitive coloring composition (P-13), evaluation was carried out in the same manner as in Example 1.

[0211] Example 14 The amount of siloxane resin (A-1) solution added was changed to 3.033 g, the PGMEA mixed solvent was changed to 4.839 g, 0.24 g of pigment dispersion (MW-2) was added, and 0.300 g of 20 wt% PGMEA diluted solution of RS-75-A was added, except that the same procedure as in Example 1 was carried out to obtain a negative photosensitive coloring composition (P-14). Using the obtained negative photosensitive coloring composition (P-14), evaluation was carried out in the same manner as in Example 1.

[0212] Example 15 The amount of siloxane resin (A-1) solution added was changed to 3.033 g, the PGMEA mixed solvent was changed to 4.839 g, 0.24 g of pigment dispersion (MW-3) was added, and 0.300 g of 20 wt% PGMEA diluted solution of RS-75-A was added, except that the same procedure as in Example 1 was carried out to obtain a negative photosensitive coloring composition (P-15). Using the obtained negative photosensitive coloring composition (P-15), evaluation was carried out in the same manner as in Example 1.

[0213] Example 16 The amount of siloxane resin (A-1) solution added was changed to 2.715g, the mixed solvent PGMEA was changed to 5.037g, DAA was changed to 0.624g, and organometallic compound solution (OM-1) 0.720g, except that 20 wt% PGMEA diluted solution of RS-75-A 0.300g was added, the same procedure as in Example 1 was carried out to obtain a negative photosensitive coloring composition (P-16). Using the obtained negative photosensitive coloring composition (P-16), evaluation was carried out in the same manner as in Example 1.

[0214] Example 17 The amount of siloxane resin (A-1) solution added was changed to 2.435g, the mixed solvent PGMEA was changed to 5.205g, DAA was changed to 0.176g, and organometallic compound solution (OM-1) 0.720g, phosphorus atom-containing coordination compound solution (OH-1) 0.560g, except that 20 wt% PGMEA diluted solution of RS-75-A 0.300g was added, carried out in the same manner as in Example 1, to obtain a negative photosensitive coloring composition (P-17). Using the obtained negative photosensitive coloring composition (P-17), evaluation was carried out in the same manner as in Example 1.

[0215] Comparative Examples 1 to 3 Instead of the siloxane resin (A-1) solution, the siloxane resin (A-7) to (A-9) solutions were used, respectively, in the same manner as in Example 1, to obtain negative photosensitive coloring compositions (P-18) to (P-20). Using the obtained negative photosensitive coloring compositions (P-18) to (P-20), evaluations were carried out in the same manner as in Example 1.

[0216] Comparative Example 4 The amount of siloxane resin (A-1) solution added was changed to 14.425 g, the amount of PGMEA mixed solvent was changed to 0.171 g, and the pigment dispersion liquid (MW-1) was not added, except that the same procedure was carried out as in Example 1 to obtain a negative photosensitive coloring composition (P-21). Using the obtained negative photosensitive coloring composition (P-21), evaluation was carried out in the same manner as in Example 1.

[0217] The compositions of Examples 1 to 17 and Comparative Examples 1 to 4 are shown in Tables 2 and 3, and the evaluation results are shown in Table 4.

[0218] [Table 2]

[0219] [Table 3]

[0220] [Table 4] [Explanation of symbols]

[0221] 1: Base substrate 2: Bulkhead 3: Pixels 3 (CL-1): Pixel formed with color-converting light-emitting material composition (CL-1) 3 (CL-2): Pixels formed with color-changing light-emitting material composition (CL-2) 4: Blue organic EL cell H: Thickness of the partition wall L: Width of the partition θ: Taper angle

Claims

1. A negative photosensitive coloring composition containing (A) a siloxane resin, (B) a photopolymerization initiator, (C) a photopolymerizable compound, (D) a white pigment, and (E) an organic solvent, A negative-type photosensitive coloring composition in which the (A) siloxane resin contains at least a repeating unit represented by formula (1), and the repeating units represented by formula (1) account for 20 to 70 mol% in total of all repeating units of the (A) siloxane resin (excluding cases in which the (A) siloxane resin is a silsesquioxane having a sulfanylpropyl group and an n-butyl group). 【Chemical 1】 (In formula (1), R １ represents an alkyl group having 3 carbon atoms. * represents a bonding site.)

2. 2. The negative photosensitive coloring composition according to claim 1, wherein the siloxane resin (A) contains a repeating unit represented by formula (3) and / or a repeating unit represented by formula (4). 【Chemistry 2】 (In formula (3) and formula (4), R ３ represents a linear alkylene group having 1 to 6 carbon atoms, R ４ represents a hydrogen atom or a methyl group, R ５ represents an alkyl group having 1 to 20 carbon atoms. * represents a bonding site.)

3. 3. The negative photosensitive coloring composition according to claim 1, wherein the siloxane resin (A) contains a repeating unit represented by formula (5) and / or a repeating unit represented by formula (6). 【Chemistry 3】 (In formula (5) and formula (6), R ６ represents a monovalent organic group having 1 to 20 carbon atoms and having a carboxyl group and / or a carboxylic anhydride group. ７ represents an alkyl group having 1 to 20 carbon atoms. * represents a bonding site.)

4. The negative photosensitive coloring composition according to any one of claims 1 to 3, wherein the (A) siloxane resin contains a repeating unit represented by formula (7) and / or a repeating unit represented by formula (8). 【Chemistry 4】 (In formula (7) and formula (8), R ８ R is an alkyl group having 1 to 20 carbon atoms selected from the group consisting of linear, branched, and cyclic alkyl groups, and some of the hydrogen atoms of the alkyl group may be substituted with a group selected from the group consisting of an epoxy group, a ureido group, a hydroxyl group, an isocyanurate group, and a fluorine group. ９ represents an alkyl group having 1 to 20 carbon atoms. * represents a bonding site.)

5. The (C) photopolymerizable compound contains a compound having a structure represented by formula (17) and / or a compound having a structure represented by formula (18), the negative photosensitive colored resin composition according to any one of claims 1 to 4. 【Chemistry 5】 (In formula (17), R １０ each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a phenyl group, and n represents an integer of 1 to 40. In formula (18), R １１ represents a hydrogen atom or a methyl group, and * represents a bonding site.)

6. The (D) white pigment contains at least one of titanium dioxide, zirconium oxide, zinc oxide, barium sulfate, and composite compounds thereof, and the content of the (D) white pigment is 10% by weight or more and 80% by weight or less. The negative photosensitive coloring composition according to any one of claims 1 to 5.

7. The negative photosensitive coloring composition according to any one of claims 1 to 6, further comprising (F) a black pigment.

8. The negative photosensitive coloring composition according to any one of claims 1 to 7, wherein the (F) black pigment comprises at least one of titanium nitride, zirconium nitride, carbon black, and a mixed pigment of a red pigment and a blue pigment.

9. The negative photosensitive coloring composition according to any one of claims 1 to 8, further comprising (G) an organometallic compound.

10. The negative photosensitive coloring composition according to any one of claims 1 to 9, wherein the metal in the (G) organometallic compound comprises at least one metal selected from the group consisting of silver, gold, platinum and palladium.

11. The negative photosensitive coloring composition according to any one of claims 1 to 10, further comprising (H) a coordination compound having a phosphorus atom.

12. The negative photosensitive coloring composition according to any one of claims 1 to 11, further comprising (I) a liquid repellent compound.

13. A cured film of the negative photosensitive coloring composition according to any one of claims 1 to 12.

14. (I) a step of applying the negative photosensitive coloring composition according to any one of claims 1 to 12 onto a substrate to form a coating film; (II) exposing and developing the coating; and (III) A step of heating the coating film after the development A method for producing a cured film comprising the steps of:

15. A substrate with partition walls, comprising a base substrate and partition walls on which the cured film according to claim 13 is formed in a pattern.

16. An image display device comprising the partition-attached substrate according to claim 15.

Images