TW201939164A - Negative photosensitive coloring composition, cured film, and touch panel using same - Google Patents

Abstract

Provided is a negative photosensitive coloring composition comprising: (A) a white pigment, (B) a siloxane resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an organic solvent, wherein the (B) siloxane resin comprises, at least, a repeating unit expressed by general formula (1) and/or a repeating unit expressed by general formula (2), and a repeating unit expressed by general formula (3), and the sum of the repeating unit expressed by general formula (1) and the repeating unit expressed by general formula (2) is 40-80 mol% with respect to all the repeating units in the (B) siloxane resin. In general formulae (1)-(3), R1 represents an alkyl group, an alkenyl group, an aryl group, or an arylalkyl group having 1-10 carbon atoms in which hydrogen is partially or entirely substituted with fluorine; R2 represents a single bond, -O-, -CH2-CO, -CO- or -O-CO-; R3 represents a monovalent organic group having 1-20 carbon atoms; and the R4s may be same or different, each representing a monovalent organic group having 1-20 carbon atoms. By using this negative photosensitive coloring composition, a cured film can be formed which exhibits high resolution and has high reflectivity and high heat-resistance even when the film is thick.

Description

Negative photosensitive coloring composition, cured film, and touch panel using the same

The present invention relates to a negative photosensitive coloring composition, a cured film, a method for manufacturing the same, and a touch panel using the same.

In recent years, mobile devices using projection type capacitive touch panels, such as smart phones and personal computers (PCs), are rapidly spreading. The projection type capacitive touch panel usually has a pattern of an indium tin oxide (ITO) film in a screen area, and further includes a metal wiring portion such as molybdenum in a peripheral portion thereof. Further, from a design point of view, in order to hide the metal wiring portion, a light-shielding pattern such as black or white is often provided inside the cover glass of the projection type capacitive touch panel. With the diversification of terminals equipped with touch panels, higher-definition light-shielding patterns are required. As a method for forming the light-shielding patterns, instead of the previous printing method, the lithography method that can realize higher-resolution processing has become mainstream. (For example, refer to Patent Document 1). In addition, as for the white light-shielding pattern, since the light-shielding property of a white pigment is generally low, thick film processing is required.

The touch panel methods are roughly divided into an out-cell type in which a touch panel layer is formed between a cover glass and a liquid crystal panel, an on-cell type in which a touch panel layer is formed on a liquid crystal panel, and The In-cell type of the touch panel layer is formed inside the liquid crystal panel, and the one-glass solution (OGS) type in which the touch panel layer is directly formed on the cover glass. In recent years, compared with the previous thinner and lighter, OGS-type touch panels have been vigorously developed.

In the manufacturing method of the OGS touch panel, a high-temperature treatment such as ITO film is required. Therefore, as a material for the light-shielding pattern, a material with few cracks and color changes and high heat resistance during high-temperature processing is required. Therefore, a negative photosensitive coloring composition containing a white pigment, a polysiloxane having a specific structure, a polyfunctional acrylic monomer, a photo-radical polymerization initiator, and an organic solvent has been proposed (for example, refer to Patent Document 2); A negative photosensitive white composition for a touch panel containing a white pigment, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator (for example, refer to Patent Document 3).

In addition, a photosensitive white composition containing a white pigment can easily form a high-definition and high-reflection barrier pattern on a substrate by a lithography method. Therefore, as a method for improving light extraction efficiency of a light-emitting body, research is being conducted on display devices Application of brightness enhancement technology.
[Prior Art Literature]
[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2012-242928 Patent Document 2: International Publication No. 2014/126013 Patent Document 3: International Publication No. 2015/12228

[Problems to be Solved by the Invention]
However, regarding the composition described in Patent Document 2, since the refractive index of polysiloxane is high and the refractive index difference between the polysiloxane and the white pigment is small, the reflection at the interface between the polysiloxane and the white pigment is insufficient. The reflectivity is insufficient. On the other hand, although the reflectance of the white light-shielding pattern of the composition described in Patent Document 3 is improved, further improvement is required. In addition, when the film thickness is relatively large, cracks easily occur due to high-temperature processing, and there is a problem that heat resistance is insufficient.

Therefore, an object of the present invention is to provide a negative-type photosensitive coloring composition that can form a cured film with high resolution, high reflectance, and excellent heat resistance even with a thick film.
[Means for solving problems]

In order to solve the above-mentioned problems, the present inventors have made intensive studies focusing on the structure of a siloxane resin in a negative photosensitive coloring composition containing a white pigment. As a result, it was found that the above-mentioned problem can be solved by including a siloxane resin that combines a structural unit derived from an alkoxysilane compound containing fluorine and a difunctional alkoxysilane compound. Combination of structural units. That is, the present invention has the following configuration.

A negative photosensitive coloring composition comprising (A) a white pigment, (B) a siloxane resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an organic solvent. (B) The siloxane resin contains at least a repeating unit represented by the following general formula (1) and / or a repeating unit represented by the following general formula (2), and a compound represented by the following general formula (3) The repeating unit, in which all the repeating units of the (B) siloxane resin, include a repeating unit represented by the following general formula (1) in a total of 40 mol% to 80 mol% and the following general formula (2) The repeating unit shown.

[Chemical 1]

In the general formulae (1) to (3), R ¹ represents an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms in which all or a part of hydrogen is substituted with fluorine. R ² represents a single bond, -O-, -CH ₂ -CO-, -CO-, or -O-CO-. R ³ represents a monovalent organic group having 1 to 20 carbon atoms. R ⁴ may be the same or different, and each represents a monovalent organic group having 1 to 20 carbon atoms.
[Effect of the invention]

According to the negative photosensitive coloring composition of the present invention, a hardened film having a thick film having high reflectance, high resolution, and excellent heat resistance can be formed.

The negative photosensitive coloring composition of the present invention contains (A) a white pigment, (B) a siloxane resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an organic solvent.

(A) White pigment By containing (A) white pigment, the reflectance of the hardened film obtained can be improved.

Examples of the (A) white pigment include compounds selected from titanium dioxide, zirconia, zinc oxide, barium sulfate, and composite compounds thereof. Two or more of these compounds may be contained. Among these, titanium dioxide having high reflectance and industrially easy to use is preferred.

The crystal structure of titanium dioxide is classified into anatase type, rutile type, and brookite type. Among these, rutile titanium oxide is preferable because the photocatalytic activity is low.

(A) A white pigment may be surface-treated. The surface treatment with Al, Si, and / or Zr is preferred to improve the dispersibility of the (A) white pigment in the negative photosensitive coloring composition and further improve the light resistance and heat resistance of the cured film.

From the viewpoint of further improving the reflectance, the median particle diameter of the (A) white pigment is preferably 100 nm to 500 nm, and more preferably 170 nm to 310 nm. Here, the median particle diameter refers to the average primary particle diameter of the (A) white pigment calculated from the particle size distribution measured by the laser diffraction method.

Examples of the titanium dioxide pigment that is preferably used as the (A) white pigment include: R960; manufactured by DuPont (rutile, SiO ₂ / Al ₂ O ₃ treatment, median particle diameter 210 nm), CR-97 ; Ishihara Industry (share) manufacturing (rutile, Al ₂ O ₃ / ZrO ₂ treatment, 250 nm median diameter), JR-301; Tayca (share) manufacturing (rutile, Al ₂ O ₃ treatment, median particle size 300 nm), JR-405; Tayca (strand) manufacturing (rutile type, Al ₂ O ₃ treatment, median particle size 210 nm), JR-600A; Dihua ( Tayca) (strand) (rutile, Al ₂ O ₃ treatment, 250 nm median diameter), JR-603; Tayca (strand) (rutile, Al ₂ O ₃ / ZrO ₂ treatment, Median particle size 280 nm) and so on. Two or more of these compounds may be contained.

The refractive index of the (A) white pigment at a wavelength of 587.5 nm is preferably 2.00 to 2.70. By setting the refractive index of the (A) white pigment to 2.00 or more, the interface reflection between the (A) white pigment and (B) the siloxane resin can be increased, and the reflectance can be further improved. (A) The refractive index of the white pigment is more preferably 2.40 or more. On the other hand, by setting the refractive index of the (A) white pigment to 2.70 or less, excessive interface reflection between the (A) white pigment and (B) the siloxane resin can be suppressed, and the resolution can be further improved. Here, the refractive index of the (A) white pigment can be measured using the Becke method specified in Japanese Industrial Standards (JIS) K7142-2014 (date of establishment: 2014/04/20). The measurement wavelength was set to a standard 587.5 nm. In the case where two or more (A) white pigments are contained, it is preferable that at least one kind of refractive index is within the above range.

From the viewpoint of further improving the reflectance, the content of the (A) white pigment in the negative photosensitive coloring composition of the present invention is in a solid content, preferably 20% by weight or more, more preferably 40% by weight or more, Furthermore, it is more preferably 45% by weight or more. On the other hand, from the viewpoint of suppressing the development residue to form a higher-resolution pattern, the content of the (A) white pigment in the solid content is preferably 65% by weight or less, and more preferably 60% by weight or less. The solid content as used herein refers to all components obtained by removing volatile components such as solvents from the components contained in the negative photosensitive coloring composition. The amount of the solid content can be determined by measuring the remaining components after the negative photosensitive coloring composition is heated at 170 ° C. for 30 minutes to evaporate the volatile components.

The negative photosensitive coloring composition of the present invention can contain a pigment dispersant together with the (A) white pigment, and can improve the dispersibility of the (A) white pigment in the negative photosensitive coloring composition. The pigment dispersant can be appropriately selected according to the type and surface state of the white pigment used. The pigment dispersant preferably contains an acidic group and / or a basic group. As a commercially available pigment dispersant, for example, "Disperbyk" (registered trademark) 106, 108, 110, 180, 190, 2001, 2155, 140, 145 (the above are trade names, and (By BYK-Chemie). Two or more of these compounds may be contained.

(B) Siloxane resin By containing the (B) silicone resin having the specific structure, the refractive index difference between (A) the white pigment and (B) the silicone resin can be enlarged, and the hardening obtained can be further improved. The reflectivity of the film. In addition, the (B) siloxane resin having the specific structure is excellent in heat resistance and can suppress color change or cracking of the cured film. Furthermore, a high-resolution pattern can be formed.

(B) The siloxane resin is a hydrolysis-dehydration condensation product of an organic silane. The negative photosensitive coloring composition of the present invention includes at least a repeating unit represented by the following general formula (1) and / or a repeating unit represented by the following general formula (2), and the following general formula (3) The repeating unit shown. It may further include other repeating units.

The repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) are characterized by containing fluorine. By including these repeating units, the refractive index of the (B) siloxane resin becomes smaller, so the refractive index difference with the (A) white pigment is enlarged, and (A) the white pigment and (B) the siloxane resin The light reflection at the interface can improve the reflectivity of the cured film.

Furthermore, by containing a repeating unit derived from a difunctional alkoxysilane compound represented by the general formula (3), excessive thermal polymerization (condensation) of the (B) siloxane resin during heat treatment can be suppressed, and heat resistance can be improved. Sex. This can suppress cracking or color change of the cured film during the heat treatment.

In the present invention, (B) the siloxane resin contains a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2) in a total of 40 mol% to 80 mol%. If the total content of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) is less than 40 mol%, the interface between (A) the white pigment and (B) the siloxane resin Reflection becomes insufficient and the reflectance decreases. The total content of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) is preferably 50 mol% or more. On the other hand, if the total content of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) exceeds 80 mol%, due to the hydrophobicity of the (B) siloxane resin, Since the compatibility with other components in the composition is reduced, the resolution is lowered. The total content of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) is preferably 70 mol% or less. The content of the repeating unit represented by the general formula (3) is preferably 50 mol% or less. When the content of the repeating unit represented by the general formula (3) is excessive, crosslinking of the cured film becomes insufficient, and the film characteristics are deteriorated. On the other hand, the content of the repeating unit represented by the general formula (3) is preferably 10 mol% or more. When the content of the repeating unit represented by the general formula (3) is less than 10 mol%, crosslinking of the cured film is excessively formed, and thus crack resistance is reduced. In addition, in the case where other repeating units other than the repeating units represented by the general formulae (1) to (3) are included, the content thereof is preferably 10 mol% to 50 mol%.

[Chemical 2]

In the general formulae (1) to (3), R ¹ represents an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms in which all or a part of hydrogen is substituted with fluorine. R ² represents a single bond, -O-, -CH ₂ -CO-, -CO-, or -O-CO-. R ³ represents a monovalent organic group having 1 to 20 carbon atoms. R ⁴ may be the same or different, and each represents a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of further reducing the refractive index of the siloxane resin, R ¹ is preferably an alkyl group in which all or a part of hydrogen is substituted with fluorine. The carbon number of the alkyl group at this time is preferably from 1 to 6. From the viewpoint of further reducing the refractive index of the siloxane resin, R ³ and R ⁴ are preferably a group selected from an alkyl group having 1 to 6 carbon atoms and a fluorenyl group having 2 to 10 carbon atoms.

Each of the repeating units represented by the general formulae (1) to (3) is derived from an alkoxysilane compound represented by the following general formulae (4) to (6), respectively. That is, the siloxane resin containing the repeating unit represented by the general formula (1) and / or the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3) can be borrowed. The alkoxysilane compound represented by the following general formula (4) and / or the alkoxysilane compound represented by the following general formula (5) and the alkoxy group represented by the following general formula (6) A plurality of alkoxysilane compounds based on silane compounds are obtained by hydrolysis and polycondensation. Furthermore, other alkoxysilane compounds can be used.

[Chemical 3]

In the general formulae (4) to (6), R ⁵ , R ⁶ , R ^8, and R ⁹ represent the same as R ¹ , R ² , R ^3, and R ^{4 in the} general formulae (1) to (3), respectively. Base. R ⁷ may be the same or different, and represents a monovalent organic group having 1 to 20 carbon atoms, and is preferably an alkyl group having 1 to 6 carbon atoms.

Examples of the alkoxysilane compound represented by the general formula (4) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, and perfluoropentane. Triethoxysilane, tridecyl octyl trimethoxysilane, tridecyl octyl triethoxysilane, tridecyl octyl tripropoxy silane, tridecyl octyl triisopropoxy silane , Heptafluorodecyltrimethoxysilane, heptafluorodecyltriethoxysilane, and the like. It is also possible to use two or more of these compounds.

Examples of the alkoxysilane compound represented by the general formula (5) include bis (trifluoromethyl) dimethoxysilane, bis (trifluoropropyl) dimethoxysilane, and bis (trifluoropropyl). ) Diethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldi Ethoxysilane, heptafluorodecylmethyldimethoxysilane, etc. It is also possible to use two or more of these compounds.

Examples of the alkoxysilane compound represented by the general formula (6) include dimethyldimethoxysilane, dimethyldiethoxysilane, ethylmethyldimethoxysilane, and methylpropyl Dimethoxysilane, methylpropyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldisiloxane Ethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, styryl Methyldimethoxysilane, styrylmethyldiethoxysilane, γ-methacrylfluorenylpropylmethyldimethoxysilane, γ-methacrylfluorenylpropylmethyldiethoxy Silane, γ-propenylpropylmethyldimethoxysilane, γ-propenylpropylmethyldiethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3 -Glycidyloxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl Ethyl ethyl di Silane group and the like. It is also possible to use two or more of these compounds.

Examples of other alkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, and propane Triethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3 -Isocyanatepropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyl Trifunctional alkoxysilane compounds such as triethoxysilane; tetrafunctional silane compounds such as tetramethoxysilane, tetraethoxysilane, and silicate 51 (tetraethoxysilane oligomer); three Monofunctional alkoxysilane compounds such as methylmethoxysilane and triphenylmethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Alkane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethylethyldimethoxysilane, 3-ethyl-3-{[3- (trimethoxysilyl) propoxy] methyl} oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane and other alkoxysilanes containing epoxy groups and / or oxetanyl groups Compounds; phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane Silane, tolyltrimethoxysilane, tolyltriethoxysilane, 1-phenylethyltrimethoxysilane, 1-phenylethyltriethoxysilane, 2-phenylethyltrimethoxysilane Silane, 2-phenylethyltriethoxysilane, 3-trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, 3-dimethyl Aromatic ring-containing alkoxy groups such as methoxysilylpropylphthalic anhydride and 3-dimethylethoxysilylpropylphthalic anhydride Silyl compounds; styryltrimethoxysilane, styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxy Silane, γ-propenyl propyl trimethoxysilane, γ-propenyl propyl triethoxy silane, γ-methacryl propyl trimethoxy silane, γ-methacryl propyl trimethoxy silane Radical polymerizable group-containing alkoxysilane compounds such as triethoxysilane; 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 3-dimethylmethoxysilane Propanoic acid, 3-dimethylethoxysilylpropanoic acid, 4-trimethoxysilylbutanoic acid, 4-triethoxysilylbutanoic acid, 4-dimethylmethoxysilylbutanoic acid , 4-dimethylethoxysilylbutanoic acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 5-dimethylmethoxysilylvaleric acid, 5- Dimethylethoxysilyl valeric acid, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-dimethylmethoxysilylpropyl Succinic anhydride, 3 -Dimethylethoxysilylpropylsuccinic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-triethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-dimethyl Methylmethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-dimethylethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, 3-trimethoxysilane Ethoxysilylpropylphthalic anhydride, 3-dimethylmethoxysilylpropylphthalic anhydride, 3-dimethylethoxysilylpropylphthalic anhydride, etc. A carboxyl alkoxysilane compound and the like.

From the viewpoint that the content of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) among all the repeating units of the (B) siloxane resin is within the above range Of the alkoxysilane compound represented by the general formula (4) and the alkoxysilane compound represented by the general formula (5) in a mixture of alkoxysilane compounds as a raw material of the (B) siloxane resin The total content is preferably 40 mol% or more, and more preferably 50 mol% or more. On the other hand, from the same viewpoint, the total content of the alkoxysilane compound represented by the general formula (4) and the alkoxysilane compound represented by the general formula (5) is preferably 80 mol% or less, More preferably, it is 70 mol% or less. In addition, when only one of the alkoxysilane compound represented by General formula (4) and the alkoxysilane compound represented by General formula (5) is included, as long as it is included in the said range, The alkoxysilane compound is sufficient, and when both the alkoxysilane compound represented by the general formula (4) and the alkoxysilane compound represented by the general formula (5) are included, the alkoxysilane compound is included within the above range. These totals are sufficient.

From the viewpoint of coating characteristics, the weight average molecular weight (Mw) of the (B) siloxane resin is preferably 1,000 or more, and more preferably 2,000 or more. On the other hand, from the viewpoint of developability, the Mw of the (B) silicone resin is preferably 50,000 or less, and more preferably 20,000 or less. Here, the Mw of the (B) siloxane resin in the present invention refers to a polystyrene conversion value measured by gel permeation chromatography (GPC).

(B) The refractive index of the siloxane resin at a wavelength of 587.5 nm is preferably 1.35 to 1.55. By setting the refractive index of the (B) siloxane resin to 1.35 or more, it is possible to suppress excessive interface reflection between the (A) white pigment and (B) the siloxane resin, and further improve the resolution. (B) The refractive index of the siloxane resin is more preferably 1.40 or more. On the other hand, by setting the refractive index of the (B) silicone resin to 1.55 or less, the interface reflection between the (A) white pigment and the (B) silicone resin can be increased, and the reflectance can be further improved. (B) The refractive index of the siloxane resin is more preferably 1.50 or less. Here, regarding the refractive index of the (B) siloxane resin, a hardened film of the siloxane resin formed on a silicon wafer is made of a ytterbium coupling (PC-2000 (manufactured by Metricon) )), At a temperature of 20 ° C under atmospheric pressure, the measurement was performed by irradiating light with a wavelength of 587.5 nm from a direction perpendicular to the surface of the cured film. Among them, round to the third decimal place. In addition, the cured film of the siloxane resin was produced by spin-coating the following siloxane resin solution on a silicon wafer, dried for 2 minutes using a 90 ° C hot plate, and then using an oven in the air. After being cured at 230 ° C for 30 minutes, the siloxane resin solution was prepared by dissolving the siloxane resin in an organic solvent so that the solid content concentration became 40% by weight. When the negative photosensitive coloring composition contains two or more (B) siloxane resins, it is preferable that at least one kind of refractive index is within the above range.

The difference in refractive index between (A) the white pigment and (B) the siloxane resin at a wavelength of 587.5 nm is preferably 1.16 to 1.26. By setting the refractive index difference to 1.16 or more, the interface reflection between (A) the white pigment and (B) the siloxane resin can be increased, and the reflectance can be further improved. The refractive index difference is more preferably 1.18 or more. On the other hand, by setting the refractive index difference to 1.26 or less, excessive interface reflection between the (A) white pigment and (B) the siloxane resin can be suppressed, and the resolution can be further improved. The refractive index difference is more preferably 1.24 or less.

In the negative photosensitive coloring composition of the present invention, the content of the (B) siloxane resin can be arbitrarily set according to the required film thickness or use, and it is preferably 10% by weight in the negative photosensitive coloring composition. ~ 60% by weight. The content of the (B) siloxane resin in the solid content of the negative photosensitive coloring composition is preferably 10% by weight or more, and more preferably 20% by weight or more. On the other hand, the content of the (B) siloxane resin in the solid content of the negative photosensitive coloring composition is preferably 60% by weight or less, and more preferably 50% by weight or less.

(B) The siloxane resin can be obtained by hydrolyzing the organic silane compound, and then subjecting the hydrolysate to a dehydration condensation reaction in the presence or absence of a solvent.

Various conditions for the hydrolysis can be set in consideration of the reaction scale, the size and shape of the reaction vessel, and the like, according to physical properties suitable for the intended use. Examples of the various conditions include oxygen concentration, reaction temperature, and reaction time.

In the hydrolysis reaction, acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids or their anhydrides, and ion exchange resins can be used. Among these, an acidic aqueous solution containing formic acid, acetic acid, and / or phosphoric acid is preferable.

In the case where an acid catalyst is used in the hydrolysis reaction, the amount of the acid catalyst is preferably more than 100 parts by weight of all the alkoxysilane compounds used in the hydrolysis reaction from the viewpoint of making the hydrolysis proceed more quickly. It is 0.05 parts by weight or more, and more preferably 0.1 parts by weight or more. On the other hand, from the viewpoint of appropriately adjusting the progress of the hydrolysis reaction, the addition amount of the acid catalyst is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, relative to 100 parts by weight of all the alkoxysilane compounds. . Here, the total amount of the alkoxysilane compound refers to an amount including the entire amount of the alkoxysilane compound, a hydrolyzate thereof, and a condensate thereof.

The hydrolysis reaction can be performed in an organic solvent. An organic solvent may be appropriately selected in consideration of the stability, wettability, and volatility of the negative photosensitive coloring composition. Examples of the organic solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tertiary butanol, pentanol, 4-methyl-2-pentanol, and 3-methyl-2. -Alcohols such as butanol, 3-methyl-3-methoxy-1-butanol, diacetone alcohol; glycols such as ethylene glycol, 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-third butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether, etc. Ethers; ketones such as methyl ethyl ketone, acetone acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, 2-heptanone; Amines such as dimethylformamide and dimethylacetamide; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Esters, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate and other acetates; toluene, xylene, Aromatic or aliphatic such as hexane and cyclohexane Hydrocarbons; γ-butyrolactone, N-methyl-2-pyrrolidone, dimethylsulfinium and the like. It is also possible to use two or more of these compounds.

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, and propylene glycol monobutyl ether can be preferably used. Ether, propylene glycol mono-third butyl ether, γ-butyrolactone, and the like.

When an organic solvent is generated by a hydrolysis reaction, hydrolysis may be performed without a solvent. It is also preferable to add an organic solvent to the obtained composition after the completion of the hydrolysis reaction to adjust the concentration to an appropriate concentration for use as a negative photosensitive coloring composition. In addition, after the hydrolysis, the total amount or a part of the alcohol produced can be distilled off and removed under heating and / or reduced pressure, and then an appropriate organic solvent can be added.

In the case where an organic solvent is used in the hydrolysis reaction, from the viewpoint of suppressing the formation of a gel, the amount of the organic solvent added is preferably 50 parts by weight or more relative to 100 parts by weight of all the alkoxysilane compounds. It is 80 parts by weight or more. On the other hand, from the viewpoint of allowing the hydrolysis to proceed more quickly, the amount of the organic solvent added is preferably 500 parts by weight or less, more preferably 200 parts by weight or less, relative to 100 parts by weight of all the alkoxysilane compounds.

The water used in the hydrolysis reaction is preferably ion-exchanged water. The amount of water can be arbitrarily set, and is preferably 1.0 mol to 4.0 mol relative to 1 mol of all the alkoxysilane compounds.

Examples of the method of the dehydration condensation reaction include a method of directly heating a silanol compound solution obtained by a hydrolysis reaction of an organic silane compound, and the like. 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 hour to 100 hours. In addition, in order to increase the degree of polymerization of the siloxane resin, reheating or addition of an alkali catalyst may be performed. In addition, depending on the purpose, after hydrolysis, distillation may be performed under heating and / or reduced pressure to remove an appropriate amount of generated alcohol and the like, and then a suitable solvent may be added.

From the viewpoint of storage stability of the negative photosensitive coloring composition, it is preferred that the catalyst is not contained in the siloxane resin solution after hydrolysis and dehydration condensation, and the catalyst can be removed as necessary. From the viewpoint of ease of operation and removability, as the catalyst removal method, water washing, treatment with an ion exchange resin, and the like are preferred. The water washing is a method of diluting a siloxane resin solution with an appropriate hydrophobic solvent, washing the water several times, and concentrating the obtained organic layer with an evaporator or the like. The treatment with an ion exchange resin refers to a method in which a siloxane resin solution is brought into contact with an appropriate ion exchange resin.

(C) Photopolymerization initiator contains (C) a photopolymerization initiator and (D) a photopolymerizable compound, and performs (D) light using a radical generated from (C) the photopolymerization initiator by light irradiation. The polymerizable compound is polymerized and the exposed portion of the negative photosensitive coloring composition is insolubilized with respect to the alkaline aqueous solution, so that a negative pattern can be formed.

(C) The photopolymerization initiator may be any photoradical polymerization initiator as long as radicals are generated by decomposition and / or reaction of light (including ultraviolet rays and electron beams). Examples include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane Α-Aminobenzoyl ketone compounds such as ketone-1; 2,4,6-trimethylbenzylidenephenylphosphine oxide, bis (2,4,6-trimethylbenzylidene) -benzene Phosphonium oxide compounds such as phosphine oxide, bis (2,6-dimethoxybenzylidene)-(2,4,4-trimethylpentyl) -phosphine oxide; 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzylideneoxime)], 1-phenyl-1,2-butanone-2- (O-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime) and other oxime ester compounds; benzyl di Benzyl ketal compounds such as methyl ketal; 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Α-hydroxy ketone compounds such as propane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and 1-hydroxycyclohexyl-phenyl ketone; two Methanone, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, methyl O-benzylbenzoate, 4- Phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzylmethyl-4'-methyl-diphenylsulfide, alkylated benzophenone , 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) benzophenone compounds such as benzophenone; 2,2-diethoxyacetophenone, 2,3-diethyl Acetophenone compounds such as oxyacetophenone, 4-tert-butyldichloroacetophenone, acetophenone, 4-azidophenideneacetophenone; 2-phenyl-2- Aromatic ketoester compounds such as methyl oxyacetate; ethyl 4-dimethylaminobenzoate, (2-ethyl) hexyl 4-dimethylaminobenzoate, 4-diethylaminobenzene Benzoate compounds such as ethyl formate and methyl 2-benzylidene benzoate. Two or more of these compounds may be contained.

In the case where the negative photosensitive coloring composition of the present invention does not contain a coloring agent other than (A) a white pigment, in order to suppress the coloring caused by the (C) photopolymerization initiator, it is preferably 2,4,6-tri Methylbenzylphenylphenylphosphine oxide, bis (2,4,6-trimethylbenzylfluorenyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzylmethyl)-( 2,4,4-trimethylpentyl) -phosphonium oxide and other fluorenyl phosphine oxide-based photopolymerization initiators.

From the viewpoint of efficiently performing radical curing, the content of the (C) photopolymerization initiator in the negative photosensitive coloring composition of the present invention is preferably 0.01% by weight or more in the solid content, and more preferably It is 1% by weight or more. On the other hand, the content of the (C) photopolymerization initiator in the solid content is preferably 20% by weight from the viewpoint of suppressing dissolution of the remaining (C) photopolymerization initiator and the like to further improve yellowing. Hereinafter, it is more preferably 10% by weight or less.

(D) Photopolymerizable compound The photopolymerizable compound in the present invention refers to a compound having an ethylenically unsaturated double bond in the molecule. The photopolymerizable compound preferably has two or more ethylenically unsaturated double bonds in the molecule. Considering the ease of radical polymerizability, the (D) photopolymerizable compound preferably has a (meth) acrylic group. From the viewpoint of further improving the sensitivity in pattern processing, the double bond equivalent of the (D) photopolymerizable compound is preferably 400 g / mol or less. On the other hand, from the viewpoint of further improving the resolution in pattern processing, the double bond equivalent of the (D) photopolymerizable compound is preferably 80 g / mol or more.

Examples of the (D) photopolymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, and triethylene glycol. Alcohol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylol Propane 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, Dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, three Pentaerythritol heptaacrylate, three pentaerythritol octaacrylate, four seasons pentaerythritol Alcohol Nine Acrylate, Tetrapentaerythritol Ten Acrylate, Pentaerythritol Eleven Acrylate, Pentaerythritol Dodecyl Acrylate, Tripentaerythritol Heptamethacrylate, Tripentaerythritol Octamethacrylate, Tetrapentaerythritol Nine Methacrylate, Tetraol Pentaerythritol decyl methacrylate, pentaerythritol undecyl methacrylate, pentaerythritol dodecyl methacrylate, dimethylol-tricyclodecane diacrylate, "Megafac" (registered trademark) RS -76-E, RS-56, RS-72-K, RS-75, RS-76-E, RS-76-NS, RS-76, RS-90 (The above are trade names, manufactured by DIC Corporation) Wait. Two or more of these compounds may be contained.

Among these, from the viewpoint of further improving the reflectance, a compound having a fluorine atom is preferred. It may contain a photopolymerizable compound having a fluorine atom and other photopolymerizable compounds.

From the viewpoint of efficiently performing radical curing, the content of the (D) photopolymerizable compound in the negative photosensitive coloring composition of the present invention is preferably 1% by weight or more in the solid content. On the other hand, from the viewpoint of suppressing an excess reaction of radicals and further improving the resolution, the content of the (D) photopolymerizable compound in the solid content is preferably 40% by weight or less.

(E) Organic solvent By containing (E) organic solvent, the viscosity suitable for coating a negative photosensitive coloring composition can be adjusted easily, and the uniformity of a coating film can be improved.

The organic solvent is preferably a combination of an organic solvent having a boiling point at atmospheric pressure exceeding 150 ° C and 250 ° C or lower and an organic solvent of 150 ° C or lower. The negative photosensitive coloring composition contains an organic solvent having a boiling point exceeding 150 ° C and lower than 250 ° C, and the organic solvent is moderately volatilized during coating to dry the coating film. Therefore, uneven coating can be suppressed and the uniformity of the film thickness can be improved. . Furthermore, by containing an organic solvent having a boiling point of 150 ° C. or lower at atmospheric pressure, it is possible to suppress the organic solvent from remaining in the cured film of the present invention described later. From the viewpoint of suppressing the remaining of the organic solvent in the cured film and further improving chemical resistance and adhesion over a long period of time, an organic solvent containing 50% by weight or more of the total organic solvent and having a boiling point at atmospheric pressure of 150 ° C or lower is preferred. .

Examples of the organic solvent having a boiling point of 150 ° C. or lower at atmospheric pressure include ethanol, isopropanol, 1-propanol, 1-butanol, 2-butanol, isoamyl alcohol, ethylene glycol monomethyl ether, and ethyl acetate. 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, acetone, methyl isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl lactate, toluene, cyclopentanone , Cyclohexane, n-heptane, benzene, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isoamyl acetate, amyl acetate, 3-hydroxy-3-methyl- 2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone. It is also possible to use two or more of these compounds.

Examples of the organic solvent having a boiling point at atmospheric pressure exceeding 150 ° C and below 250 ° C include ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-third butyl ether, and propylene glycol mono-n-butyl ether. , Propylene glycol mono third butyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methyl Butyl 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-methyl Pyrrolidone, cyclohexanone, cycloheptanone, diethylene glycol monobutyl ether, ethylene glycol dibutyl ether. It is also possible to use two or more of these compounds.

The content of the organic solvent can be arbitrarily set according to a coating method or the like. For example, in the case of forming a film by spin coating, the content of the organic solvent in the negative photosensitive coloring composition is preferably 50% by weight or more and 95% by weight or less.

The negative-type photosensitive coloring composition of the present invention may further contain an adhesion improver, an ultraviolet absorber, a polymerization inhibitor, a surfactant, and the like, as necessary.

By including the adhesion improving agent in the negative photosensitive coloring composition, the adhesion with the substrate is improved, and a highly reliable cured film can be obtained. Examples of the adhesion improving agent include alicyclic epoxy compounds and silane coupling agents. Among these, since the alicyclic epoxy compound has high heat resistance, the color change of the cured film after heating can be further suppressed.

Examples of the alicyclic epoxy compound include 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2,2-bis (hydroxymethyl). 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol, ε-caprolactone modified 3 ', 4'-epoxycyclohexyl Methyl 3 ', 4'-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, butane tetracarboxylic acid tetra (3,4-epoxycyclohexyl) (Methyl) modified ε-caprolactone, 3,4-epoxycyclohexyl methyl 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-cyclohexanedicarboxylic acid diglycidyl ester, 1,4-cyclo Hexane dimethanol diglycidyl ether and the like. Two or more of these compounds may be contained.

The silane coupling agent is preferably a compound represented by the following general formula (7).

[Chemical 4]

In the general formula (7), each R ¹⁰ independently represents an alkyl group having 1 to 6 carbon atoms. From the viewpoint of reducing the refractive index, R ^{10 is} preferably an alkyl group having 1 to 3 carbon atoms. p represents 0 or 1. From the viewpoint of further improving the adhesion with the substrate, p is preferably 0. R ¹¹ represents a trivalent organic group having 3 to 30 carbon atoms, and is preferably a trivalent hydrocarbon group having 3 to 10 carbon atoms. R ¹² 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. From the viewpoint of reducing the refractive index, R ^{12 is} preferably an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms.

Examples of the silane coupling agent represented by the general formula (7) include 3- (third butylaminomethylamino) -6- (trimethoxysilyl) hexanoic acid, 2- (2- ( Third butylamino) -2-oxoethyl) -5- (trimethoxysilyl) valeric acid, 3- (isopropylaminemethylmethyl) -6- (trimethoxysilyl) hexyl Acid, 2- (2- (isopropylamino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (isobutylaminemethylmethyl) -6- ( Trimethoxysilyl) hexanoic acid, 3- (thirdpentylaminomethylamino) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (thirdpentylamino) -2- (Oxoethyl) -5- (trimethoxysilyl) pentanoic acid, 6- (dimethoxymethylsilyl) -3- (third butylaminomethylmethyl) hexanoic acid, 5- (di Methoxy (methyl) silyl-2- (2- (third butylamino) -2-oxoethyl) pentanoic acid, 3- (third butylaminomethyl) -6- ( Trimethoxysilyl) valeric acid, 2- (2- (thirdbutylamino) -2-oxoethyl) -5- (trimethoxysilyl) butanoic acid, 2- (thirdbutyl Aminemethyl) -4- (2- (trimethoxysilyl) ethyl) cyclohexanecarboxylic acid, 2- (third butylaminomethylmethyl) -5- (2- (trimethoxysilane) (Yl) ethyl) cyclohexanecarboxylic acid, etc. It may also contain two or more of these compounds.

From the viewpoint of further improving the adhesion with the substrate, the content of the adhesion improver in the negative photosensitive coloring composition is preferably 0.1% by weight or more, and more preferably 1% by weight or more, in the solid content. On the other hand, from the viewpoint of further suppressing color change due to heating, the content of the adhesion improver in the solid content is preferably 20% by weight or less, and more preferably 10% by weight or less.

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, 2- (2H-benzotriazol-2-yl) phenol and 2- (2H-benzotriazole-2) can be preferably used from the viewpoint of further suppressing color change due to heating. -Yl) -4,6-third pentylphenol, 2- (2Hbenzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H -Benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzene Benzotriazole compounds such as benzotriazole; benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone; 2- (4,6-diphenyl-1,3,5 triazine Triazine-based compounds such as 2-yl) -5-[(hexyl) oxy] -phenol. Two or more of these compounds may be contained.

By including a polymerization inhibitor in the negative photosensitive coloring composition, the resolution of the obtained cured film can be improved. Examples of the polymerization inhibitor include di-third butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, and third butyl catechin. phenol. In addition, as commercially available polymerization inhibitors, "IRGANOX" (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, 295 (the above are trade names, manufactured by Japan BASF). Two or more of these compounds may be contained.

By including a surfactant in the negative photosensitive coloring composition, the fluidity at the time of coating can be improved. Examples of the surfactant include fluorine-based compounds such as "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (the above are the trade names, manufactured by DIC). Surfactants; silicones such as "BYK" (registered trademark) F-333, 301, 331, 345, 307 (the above are trade names, manufactured by BYK-Chemie Japan) Surfactants; polyalkylene oxide surfactants; poly (meth) acrylate surfactants, etc. Two or more of these compounds may be contained.

The solid content concentration of the negative photosensitive coloring composition can be arbitrarily set according to a coating method or the like. For example, when film formation is performed by spin coating as described later, the solid content concentration is preferably set to 5% by weight or more and 50% by weight or less.

Next, the manufacturing method of the negative photosensitive coloring composition of this invention is demonstrated below. The negative photosensitive coloring composition of the present invention can be obtained by mixing the components (A) to (E) and other components as necessary. More specifically, it is preferable to first disperse the mixed liquid of (A) white pigment, (B) silicone resin, and (E) organic solvent using a mill-type disperser filled with zirconia beads to obtain pigment dispersion. liquid. On the other hand, it is preferable to stir and dissolve (B) a siloxane resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, (E) an organic solvent, and other components as necessary. Instead, a dilution is obtained. Furthermore, it is preferable to mix and stir the pigment dispersion liquid and the diluent, and then perform filtration.

Next, the cured film of the present invention will be described. The cured film of the present invention is a cured product of the negative photosensitive coloring composition of the present invention. The cured film of the present invention can be suitably used as a light-shielding pattern in an OGS-type touch panel and a partition wall pattern of an image display device. The film thickness of the cured film is preferably 10 μm or more.

The manufacturing method of the cured film of this invention is demonstrated with an example. The method for producing a cured film of the present invention preferably includes: (I) a step of applying the negative photosensitive coloring composition of the present invention on a substrate to form a coating film; (II) exposing and developing the coating film And (III) a step of heating the developed coating film. Each step will be described below.

(I) The step of applying the negative-type photosensitive coloring composition of the present invention to a substrate to form a coating film includes, for example, a glass substrate such as soda lime glass or alkali-free glass.

The negative photosensitive coloring composition of the present invention is coated on these substrates to form a coating film. Examples of the coating method include spin coating, slit coating, screen printing, inkjet coating, and bar coating.

After the formation of the coating film, the substrate coated with the negative photosensitive coloring composition is preferably dried (pre-baked). Examples of the drying method include reduced-pressure drying and heat-drying. Examples of the heating device include a hot plate and an oven. The heating temperature is preferably 60 ° C to 150 ° C, and the heating time is preferably 30 seconds to 3 minutes. The film thickness of the pre-baking coating film is preferably 5 μm to 20 μm.

(II) Step of exposing and developing the coating film By exposing and developing the coating film obtained in the manner described above, a substrate having a patterned coating film is obtained.

Exposure can be performed with or without the required mask. Examples of the exposure machine include a stepper, a Mirror Project Mask Aligner (MPA), a parallel light mask aligner (hereinafter referred to as "PLA"), etc. . The exposure intensity is preferably about 10 J / m ² to 4000 J / m ² (equivalent to 365 nm wavelength exposure). Examples of the exposure light source include ultraviolet rays such as i-rays, g-rays, and h-rays, KrF (wavelength 248 nm) laser, and ArF (wavelength 193 nm) laser.

Examples of the development method include methods such as showering, dipping, and coating. The immersion time in the developer is preferably 5 seconds to 10 minutes. Examples of the developer include inorganic bases such as hydroxides, carbonates, phosphates, silicates, and borates of alkali metals; amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine; hydrogen Aqueous solutions of quaternary ammonium salts such as tetramethylammonium and choline. It is preferable to rinse with water after image development. Then, drying and baking can be performed at 50 ° C to 140 ° C.

(III) The step of heating the developed coating film By heating the substrate having the patterned coating film obtained in the manner described above, the coating film is hardened to obtain a patterned processed substrate. Here, the patterned processing substrate refers to a substrate having a patterned cured film.

Examples of the heating device include a hot plate and an oven. The heating temperature is preferably 120 ° C to 250 ° C, and the heating time is preferably 15 minutes to 2 hours.

Next, a patterned processed substrate of the present invention will be described. The patterned processing substrate of the present invention has a pattern including the cured film of the present invention on a substrate. The pattern has a high resolution and a high reflectance, and thus can be suitably used as a white light-shielding pattern of a touch panel.

Examples of the substrate include substrates exemplified in the method for producing a cured film of the present invention.

In the case where a cured film pattern is used as, for example, a light-shielding pattern for a touch panel, the total reflection of the light-shielding pattern (incident angle 8 °, light source: D-65 (2 ° field of view)) is preferably from the International Commission on Illumination (CIE) 1976 (L *, a *, b *) color space is 82 ≦ L * ≦ 99, -5 ≦ b * ≦ 5, -5 ≦ a * ≦ 5, and more preferably 82.5 ≦ L * ≦ 97, -2 ≦ b * ≦ 2, -2 ≦ a * ≦ 2. The cured film pattern having the color characteristics can be obtained, for example, by using the negative photosensitive coloring composition of the present invention to perform pattern processing using the preferred manufacturing method.

Next, a substrate with a partition wall of the present invention will be described. The substrate with a partition wall of the present invention has a patterned partition wall (hereinafter, sometimes referred to as a “partition wall (F-1)”) including the cured film on the substrate.

The partition wall in the present invention refers to a partition wall having a repeated pattern corresponding to the number of pixels of the image display device. Examples of the number of pixels of the image display device include 4000 vertical and 2000 horizontal. The number of pixels affects the resolution (fineness) of the displayed image. Therefore, it is necessary to form a number of pixels corresponding to the required resolution of the image and the screen size of the image display device, and it is preferable to determine the pattern formation size of the partition wall together with the number of pixels.

The substrate has a function as a support in a substrate with a partition wall. The partition wall has a function of preventing light mixing between adjacent pixels when a layer containing a color conversion luminescent material described later is formed between adjacent partition walls and pixels containing the color conversion luminescent material are formed. . In the present invention, the partition wall (F-1) preferably has a reflectance of 60% to 90% per 10 μm in thickness at a wavelength of 550 nm. By setting the reflectance to 60% or more, it is possible to increase the brightness of the display device by using (F-1) reflection on the side of the partition wall. On the other hand, from the viewpoint of improving the accuracy of pattern formation, the reflectance is preferably 90% or less.

FIG. 1 is a cross-sectional view showing one aspect of a substrate with a partition wall of the present invention having a partition wall formed by patterning. A patterned partition wall 2 is provided on the substrate 1.

<Substrate>
Examples of the substrate include a glass plate, a resin plate, and a resin film. The material of the glass plate is preferably alkali-free glass. As a material of a resin plate and a resin film, polyester, (meth) acrylic polymer, transparent polyimide, polyether fluorene, etc. are preferable. 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.

＜ Separation wall (F-1) ＞
The partition wall (F-1) preferably has a reflectance of 60% to 90% per 10 μm in thickness at a wavelength of 550 nm. Here, the thickness of the partition wall (F-1) refers to the length of the partition wall (F-1) in a direction (height direction) perpendicular to the substrate. In the case of the substrate with a partition wall shown in FIG. 1, the thickness of the partition wall 2 is represented by the symbol X. The length of the partition wall (F-1) in the horizontal direction of the substrate is the width of the partition wall (F-1). In the case of the substrate with a partition wall shown in FIG. 1, the width of the partition wall 2 is represented by a symbol L. In the present invention, it is considered that the reflection on the side surface of the partition wall contributes to the improvement of the brightness of the display device. On the other hand, since the reflectance per thickness unit is considered to be the same regardless of the thickness direction and the width direction, the present invention focuses on the reflectance per thickness unit of the partition wall. In addition, as described later, the thickness of the partition wall (F-1) is preferably 0.5 μm to 50 μm, and the width is preferably 5 μm to 40 μm. Therefore, in the present invention, 10 μm is selected as a representative value of the thickness of the partition wall (F-1), and the reflectivity per 10 μm of the thickness is considered. If the reflectance is less than 60% per 10 μm of the thickness, the reflection on the side of the partition wall becomes small, and the brightness of the display device becomes insufficient. The higher the reflectance, the greater the reflection on the side of the partition wall, so the brightness of the display device can be improved, so the reflectance is preferably 70% or more. On the other hand, from the viewpoint of improving the accuracy of pattern formation, the reflectance is preferably 90% or less. Regarding the reflectance per 10 μm thickness of the partition wall (F-1) at a wavelength of 550 nm, for a partition wall (F-1) with a thickness of 10 μm in the height direction, a spectrophotometer (for example, Ke CM-2600d (manufactured by Konica Minolta Co., Ltd.) was measured by a specular component included (SCI) mode. Among them, when it is not possible to ensure a sufficient area for measurement, or when a measurement sample with a thickness of 10 μm cannot be taken, and when the composition of the partition wall (F-1) is known, it is also possible to produce and isolate Instead of the partition wall (F-1), an overall film with a thickness of 10 μm having the same composition as the wall (F-1) was measured for the overall film. For example, except that the material forming the partition wall (F-1) is used, and the thickness is set to 10 μm without patterning, the entire film is produced under the same processing conditions as the formation of the partition wall (F-1). About the obtained whole film, the reflectance can also be measured from the upper surface similarly. In addition, as a method of making the reflectance within the range, for example, it can be obtained by patterning the partition wall by using the preferred manufacturing method using the negative photosensitive coloring composition of the present invention.

Regarding the thickness of the partition wall (F-1), the substrate with the partition wall has a layer (G) containing a color-converting luminescent material described later (hereinafter, sometimes referred to as "layer (G) containing a color-converting luminescent material"). In the case of P, the thickness of the layer (G) containing the color conversion light-emitting material is preferably larger. Specifically, the thickness of the partition wall (F-1) is preferably 0.5 μm or more, and more preferably 10 μm or more. On the other hand, the thickness of the partition wall (F-1) is preferably 50 μm or less, and more preferably 20 μm from the viewpoint of efficiently extracting light emission from the bottom of the layer (G) containing the color conversion luminescent material. the following. In addition, as long as the width of the partition wall (F-1) is sufficient to increase the brightness by using light reflection on the side surface of the partition wall and suppress the color mixing of the adjacent color conversion luminescent material-containing layer (G) due to light leakage, can. Specifically, the width of the partition wall is preferably 5 μm or more, and more preferably 15 μm or more. On the other hand, the width of the partition wall (F-1) is preferably 50 μm or less, from the viewpoint of more ensuring the light-emitting area of the layer (G) containing the color-converting light-emitting material and further improving the brightness. Below 40 μm.

From the viewpoint of improving the inkjet coating property and facilitating the separation coating of the color conversion luminescent material, the surface contact angle of the partition wall (F-1) with propylene glycol monomethyl ether acetate is preferably 10 ° or more, It is more preferably 20 ° or more, and even more preferably 40 ° or more. On the other hand, from the viewpoint of improving the adhesion between the partition wall and the substrate, the surface contact angle of the partition wall (F-1) is preferably 70 ° or less, and more preferably 60 ° or less. Here, the surface contact angle of the partition wall (F-1) can be measured on the upper part of the partition wall according to the wettability test method of the substrate glass surface specified in JIS R3257 (date of establishment: 1999/04/20). In addition, as a method of making the surface contact angle of the partition wall (F-1) within the range, for example, in the negative photosensitive coloring composition of the present invention, it is possible to use the preferable manufacturing method A method of patterning a partition wall to obtain a negative photosensitive coloring composition containing a photopolymerizable compound having a fluorine atom.

＜ Light-shielding partition (F-2) ＞
The substrate with a partition wall of the present invention is preferably formed by patterning with an optical concentration of 0.1 to 4.0 per 1.0 μm in thickness (F-2) between the substrate and the partition wall (F-1). (Hereinafter referred to as "light shielding partition (F-2)"). By having a light-shielding partition wall (F-2), the light-shielding property can be improved, and the light leakage of the backlight in the display device can be suppressed to obtain a high-contrast and sharp image. Here, the light shielding partition wall (F-2) is preferably formed in the same pattern shape as the partition wall (F-1).

FIG. 9 is a cross-sectional view showing an aspect of the substrate with a partition wall of the present invention having a light-shielding partition wall. A patterned partition wall 2 and a patterned light-shielding partition wall 10 are provided on the substrate 1. A layer 3 containing a color conversion light-emitting material is arranged in a region separated by the partition wall 2 and the light-shielding partition wall 10.

The thickness of the light-shielding partition wall (F-2) is 0.1 to 4.0 per 1.0 μm. Here, the thickness of the light shielding partition wall (F-2) is preferably 0.5 μm to 10 μm as described later. Therefore, in the present invention, 1.0 μm is selected as a representative value of the thickness of the light-shielding partition wall (F-2), and the optical density per 1.0 μm of the thickness is considered. By setting the optical density per thickness of 1.0 μm or more to 0.1, the light-shielding property can be further improved, and a higher contrast and vivid image can be obtained. The optical density per thickness of 1.0 μm is more preferably 0.5 or more. On the other hand, by setting the optical density per thickness of 1.0 μm to 4.0 or less, pattern processability can be improved. The optical density per thickness of 1.0 μm is more preferably 3.0 or less. The optical density (optical density (OD) value) of the light-shielding partition wall (F-2) can be measured with an optical densitometer (361T (visual); manufactured by X-rite) And the intensity of transmitted light is calculated by the following formula (11).

OD value = log10 （I ₀ / I） ··· Equation (11)
I ₀ : incident light intensity
I: transmitted light intensity.

In addition, as a method for making an optical density into the said range, the light-shielding partition wall (F-2) is mentioned as the preferable composition mentioned later, for example.

From the viewpoint of improving the light-shielding property, the thickness of the light-shielding partition wall (F-2) is preferably 0.5 μm or more, and more preferably 1.0 μm or more. On the other hand, from the viewpoint of improving flatness, the thickness of the light shielding partition (F-2) is preferably 10 μm or less, and more preferably 5 μm or less. In addition, the width of the light shielding partition wall (F-2) is preferably the same as that of the partition wall (F-1).

The light-shielding partition wall (F-2) preferably contains a resin and a black pigment. The resin has a function of improving crack resistance and light resistance of the partition wall. The black pigment has a function of absorbing incident light and reducing outgoing light.

Examples of the resin include epoxy resin, (meth) acrylic polymer, polyurethane, polyester, polyimide, polyolefin, and polysiloxane. Two or more of these compounds may be contained. Among these, polyimide is preferable in terms of excellent heat resistance and solvent resistance.

Examples of the black pigment include a black organic pigment, a mixed color organic pigment, and an inorganic pigment. Examples of the black organic pigment include carbon black, perylene black nigrosine, and benzofuranone-based pigments. These may also be coated with a resin. Examples of the mixed-color organic pigment include pigments obtained by mixing two or more kinds of pigments such as red, blue, green, purple, yellow, magenta, and / or cyan, and blackening them. Examples of the black inorganic pigment include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; metal oxides; metal composite oxides; metal sulfides; metal nitrogen Compounds; metal oxynitrides; metal carbides, etc.

As a method of patterning the light-shielding partition wall (F-2) on the substrate, it is preferable to use a method such as the photosensitive material described in Japanese Patent Laid-Open No. 2015-1654 and the partition wall (F -1) Similarly, pattern formation is performed by a photosensitive paste method.

In the substrate with a partition wall of the present invention, it is preferable that a layer (G) containing a color conversion light emitting material is formed between the adjacent partition walls (F-1). The layer containing a color conversion luminescent material has a function of performing color display by converting at least a part of a wavelength region of incident light and emitting outgoing light in a wavelength region different from the incident light. Moreover, when using the board | substrate with a partition wall of this invention for an image display device, the layer (G) containing a color conversion light emitting material is generally called a pixel.

FIG. 2 is a cross-sectional view showing one aspect of a substrate with a partition wall according to the present invention, which includes a partition wall patterned and a layer (G) containing a color conversion luminescent material. A patterned partition wall 2 is provided on the substrate 1, and a layer 3 containing a color-converting light-emitting material is arranged in an area separated by the partition wall 2.

The color conversion light-emitting material preferably contains an inorganic phosphor and / or an organic phosphor. For example, in the case of the following display device, it is preferable to include a red phosphor that emits red fluorescent light by being excited by blue excitation light in a region corresponding to a red pixel. The area corresponding to the green pixels contains a green phosphor that emits green fluorescent light when excited by blue excitation light. It is preferable that the area corresponding to the blue pixels does not contain a phosphor. The display device is a combination of a backlight emitting blue light, a liquid crystal cell driven by a thin film transistor (TFT), and a color filter having a layer (G) containing a color conversion light emitting material. On the other hand, the substrate with a partition wall of the present invention can also be used for a display device in which a blue micro LED corresponding to each pixel separated by a white partition wall is used as a backlight. use. The on / off of each pixel can be realized by turning on / off the blue micro LED, and no liquid crystal is required. In this case, it is preferable to have two types of partition walls, such as a partition wall that separates each pixel on the substrate, and a partition wall that separates the blue micro LED from the backlight.

Inorganic phosphors emit various colors such as green or red depending on the peak wavelength of the emission spectrum. Examples of the inorganic phosphor include phosphors that are excited by excitation light having a wavelength of 400 nm to 500 nm, and have emission peaks in the region of 500 nm to 700 nm; inorganic semiconductor fine particles called quantum dots. Examples of the shape of the former inorganic phosphor include a spherical shape and a columnar shape. Examples of the inorganic phosphor include yttrium aluminum garnet (YAG) based phosphors, terbium aluminum garnet (TAG) based phosphors, and silicon aluminum nitride oxide ( Sialon) -based phosphors, Mn ⁴⁺ active fluoride complex phosphors, and the like. It is also possible to use two or more of these compounds.

Among these, quantum dots are preferred. Compared with other phosphors, the average particle size of the quantum dots is small, so that the surface of the layer (G) containing the color conversion luminescent material can be smoothed and the light scattering on the surface can be suppressed. Therefore, the light extraction efficiency can be further improved, and Increase brightness.

Examples of the material of the quantum dot include semiconductors of group II-IV, group III-V, group IV-VI, and group IV. Examples of such 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, Si ₃ N ₄ , Ge ₃ N ₄ , Al ₂ O ₃ and the like. It is also possible to use two or more of these compounds.

The quantum dots may also include a p-type dopant or an n-type dopant. In addition, the quantum dots may have a core-shell structure. In the core-shell structure, any appropriate functional layer (single or multiple layers) can be formed around the shell according to the purpose, and the surface of the shell can also be surface-treated and / or chemically modified.

Examples of the shape of the quantum dot include a spherical shape, a columnar shape, a scaly shape, a plate shape, and an irregular shape. The average particle diameter of the quantum dots can be selected according to the required emission wavelength, and is preferably 1 nm to 30 nm. When the average particle diameter of the quantum dot is 1 nm to 10 nm, the peak in the emission spectrum can be made sharper in each of blue, green, and red. For example, blue light is emitted when the average particle diameter of the quantum dot is about 2 nm, green light is emitted when it is about 3 nm, and red light is emitted when it is about 6 nm. The average particle diameter of the quantum dots is preferably 2 nm or more, and more preferably 8 nm or less. The average particle size of the quantum dots can be measured by a dynamic light scattering method. Examples of the measurement device for the average particle diameter include a dynamic light scattering photometer DLS-8000 (manufactured by Otsuka Electronics Co., Ltd.) and the like.

Examples of the organic phosphor include a pyrromethene derivative having a basic skeleton represented by the following structural formula (8). Examples of the phosphor which is excited by blue excitation light and emits green fluorescence include a pyrrole methylene derivative having a basic skeleton represented by the following structural formula (9). Other examples include fluorene-based derivatives, porphyrin-based derivatives, oxazine-based derivatives, and pyrazine-based derivatives that emit red or green fluorescence by selection of a substituent. Two or more of these compounds may be contained. Among these, since a quantum yield is high, a pyrrole methylene derivative is also preferable. The pyrrole methylene derivative can be obtained, for example, by a method described in Japanese Patent Laid-Open No. 2011-241160.

[Chemical 5]

The organic phosphor is soluble in a solvent, and therefore a layer (G) containing a color conversion light-emitting material having a desired thickness can be easily formed.

From the viewpoint of improving color characteristics, the thickness of the layer (G) containing the color conversion light-emitting material is preferably 0.5 μm or more, and more preferably 1 μm or more. On the other hand, the thickness of the layer (G) containing the color conversion light-emitting material is preferably 30 μm or less, and more preferably 20 μm or less, from the viewpoint of thinning of the display device and workability of the curved surface.

In an image display device, the size of the layer containing the color conversion luminescent material is usually about 20 μm to 200 μm.

The layer (G) containing the color conversion luminescent material is preferably aligned by being partitioned by the partition wall (F-1). By providing a partition wall between adjacent layers (G) containing a color conversion luminescent material, it is possible to further suppress diffusion or color mixing of emitted light.

Examples of the method for forming the layer (G) containing a color-converting luminescent material include a method of filling a color-converting luminescent material coating liquid containing the color-converting luminescent material into a space partitioned by the partition wall (F-1). The color conversion luminescent material coating liquid may further contain a resin or a solvent.

As a method for filling the color-converting luminescent material coating liquid, an inkjet coating method or the like is preferred from the viewpoint that it is easy to separately apply different types of color-converting luminescent materials to each pixel.

The obtained coating film may be dried under reduced pressure and / or heat-dried. In the case of performing reduced pressure drying, in order to prevent the drying solvent from re-condensing on the inner wall of the reduced pressure chamber, the reduced pressure drying temperature is preferably 80 ° C or lower. 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 more preferably 1 Pa to 1000 Pa. The reduced-pressure drying time is preferably from 10 seconds to 600 seconds. When heat-drying is performed, examples of the heat-drying device include an oven and a hot plate. The heating and drying temperature is preferably 60 ° C to 200 ° C. The heating and drying time is preferably 1 minute to 60 minutes.

The substrate with a partition wall of the present invention preferably further has a low-refractive-index layer having a refractive index of 1.20 to 1.35 at a wavelength of 550 nm (H) on the layer (G) containing the color conversion light-emitting material (hereinafter, sometimes described "Low refractive index layer (H)"). By having the low refractive index layer (H), the light extraction efficiency can be further improved, and the brightness of the display device can be further improved.

FIG. 3 is a cross-sectional view showing an embodiment of the substrate with a partition wall of the present invention having a low refractive index layer. The substrate 1 has a patterned partition wall 2 and a layer 3 containing a color-converting luminescent material, and further has a low-refractive index layer 4 thereon.

In the display device, the refractive index of the low-refractive index layer (H) is preferably 1.20 from the viewpoint of appropriately suppressing light reflection of the backlight and efficiently making light incident on the layer (G) containing the color conversion light-emitting material. The above is more preferably 1.23 or more. On the other hand, from the viewpoint of improving the brightness, the refractive index of the low refractive index layer (H) is preferably 1.35 or less, and more preferably 1.30 or less. Here, as for the refractive index of the low refractive index layer (H), a pseudo-coupling (PC-2000 (manufactured by Metricon)) can be used to self-phase under atmospheric pressure and 20 ° C. The measurement was performed by irradiating light with a wavelength of 550 nm in a direction perpendicular to the cured film surface.

The low-refractive index layer (H) preferably contains polysiloxane and silicon dioxide particles having no hollow structure. Polysiloxane has high compatibility with inorganic particles such as silica particles, and functions as a binder that can form a transparent layer. In addition, by containing silicon dioxide particles, minute voids can be efficiently formed in the low refractive index layer (H) and the refractive index can be reduced, and the refractive index can be easily adjusted within the above range. Furthermore, by using silicon dioxide particles that do not have a hollow structure as the silicon dioxide particles, since they do not have a hollow structure that is prone to cracks during hardening shrinkage, cracks can be suppressed. Moreover, in the low refractive index layer (H), polysiloxane and silicon dioxide particles without a hollow structure may be contained independently, and may also be contained in polysiloxane and silicon dioxide particles without a hollow structure. Contained in a bound state. From the viewpoint of the uniformity of the low-refractive index layer (H), it is preferably contained in a state where the polysiloxane is combined with silicon dioxide particles having no hollow structure.

The polysiloxane contained in the low refractive index layer (H) preferably contains fluorine. Since the polysiloxane contains fluorine, the refractive index of the low refractive index layer (H) can be easily adjusted to 1.20 to 1.35. The fluorine-containing polysiloxane is obtained by hydrolyzing and polycondensing an alkoxysilane compound containing a fluorine-containing alkoxysilane compound represented by the following general formula (10). Furthermore, other alkoxysilane compounds can be used.

[Chemical 6]

In the general formula (10), R ¹³ represents a fluoroalkyl group having 3 to 17 fluorine atoms. R ⁷ represents the same group as R ⁷ in the general formulae (4) to (6). m represents 1 or 2. 4-m R ⁷ and m R ¹³ may be the same or different.

Examples of the fluorine-containing alkoxysilane compound represented by the general formula (10) include trifluoroethyltrimethoxysilane, trifluoroethyltriethoxysilane, and trifluoroethyltriisopropoxysilane. , Trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, heptafluorodecyltrimethoxysilane, heptafluorodecyltriethoxy Silane, heptafluorodecyltriisopropoxysilane, tridecanefluorooctyltriethoxysilane, tridecanefluorooctyltrimethoxysilane, tridecyloctyltriisopropoxysilane, trifluoroethyl Methylmethyldimethoxysilane, trifluoroethylmethyldiethoxysilane, trifluoroethylmethyldiisopropoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropyl Methyldiethoxysilane, trifluoropropylmethyldiisopropoxysilane, heptafluorodecylmethyldimethoxysilane, heptafluorodecylmethyldiethoxysilane, heptafluoro Decylmethyldiisopropoxysilane, tridecylfluorooctylmethyldimethoxysilane, tridecylfluorooctylmethyldiethoxysilane, tridecylfluorooctylmethyldiisopropoxy Alkane, trifluoroethylethyldimethoxysilane, trifluoroethylethyldiethoxysilane, trifluoroethylethyldiisopropoxysilane, trifluoropropylethyldimethoxysilane , Trifluoropropylethyldiethoxysilane, trifluoropropylethyldiisopropoxysilane, heptafluorodecylethyldimethoxysilane, heptafluorodecylethyldiethoxy Silane, heptafluorodecylethyldiisopropoxysilane, tridecyloctylethyldiethoxysilane, tridecylfluorooctylethyldimethoxysilane, tridecylfluorooctylethyldi Isopropoxysilane and so on. It is also possible to use two or more of these compounds.

From the viewpoint of suppressing cracks, the content of polysiloxane in the low refractive index layer (H) is preferably 4% by weight or more. On the other hand, from the viewpoint of ensuring the thixotropy of the network between the silica particles, maintaining the air layer moderately in the low refractive index layer (H), and further reducing the refractive index, the content of polysiloxane is preferably 32% by weight or less.

As the silica particles having no hollow structure in the low refractive index layer (H), there are, for example, "SNOWTEX" (registered trademark) or "organic silica gel" manufactured by Nissan Chemical Industry Co., Ltd. "(Registered trademark) series (isopropanol dispersion, ethylene glycol dispersion, methyl ethyl ketone dispersion, dimethylacetamide dispersion, methyl isobutyl ketone dispersion, propylene glycol monomethyl ethyl Ester dispersion, propylene glycol monomethyl ether dispersion, methanol dispersion, ethyl acetate dispersion, butyl acetate dispersion, xylene-n-butanol dispersion, toluene dispersion, etc. Examples include product numbers PGM-ST, PMA-ST, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, etc. It may contain two or more of these compounds.

The low refractive index layer (H) does not have a hollow structure in terms of ensuring the thixotropy of the network between the silicon dioxide particles, maintaining a moderate air layer in the low refractive index layer (H), and further reducing the refractive index. The content of silica particles is preferably 68% by weight or more. On the other hand, from the viewpoint of suppressing cracks, the content of the silicon dioxide particles having no hollow structure is preferably 96% by weight or less.

The thickness of the low-refractive-index layer (H) is preferably 0.1 μm or more, more preferably 0.5 μm or more, from the viewpoint of covering the step of the layer (G) containing the color conversion light-emitting material and suppressing the occurrence of defects. On the other hand, the thickness of the low-refractive index layer (H) is preferably 20 μm or less, and more preferably 10 μm or less, from the viewpoint of reducing the stress that causes cracks in the low-refractive index layer (H).

As a method for forming the low-refractive index layer (H), a coating method is preferred in terms of the ease of formation. For example, a low refractive index resin composition containing polysiloxane and silicon dioxide particles is coated on a layer (G) containing a color conversion light-emitting material, dried, and then heated to form a low refractive index. Rate layer (H).

In addition, the substrate with a partition wall according to the present invention preferably further has (I-1) an inorganic protective layer I having a thickness of 50 nm to 1,000 nm on the low refractive index layer (H). By having the inorganic protective layer I, it is difficult for moisture in the atmosphere to reach the low-refractive index layer (H), so it is possible to suppress the refractive index variation of the low-refractive index layer (H) and suppress the deterioration of brightness.

FIG. 4 is a cross-sectional view showing one aspect of the substrate with a partition wall of the present invention having a low refractive index layer and an inorganic protective layer I. FIG. The substrate 1 has a patterned partition wall 2 and a layer 3 containing a color-converting luminescent material, and further has a low refractive index layer 4 and an inorganic protective layer I (5) in this order.

In addition, the substrate with a partition wall of the present invention preferably further has (I-2) an inorganic protective layer II having a thickness of 50 nm to 1,000 nm under the low refractive index layer (H). By having the inorganic protective layer II, it is difficult for the raw material for forming the layer (G) containing the color-converting luminescent material to move from the layer (G) containing the color-converting luminescent material to the low-refractive-index layer, so that the low-refractive-index layer (H) can be suppressed Refractive index variation, suppresses deterioration in brightness.

FIG. 5 is a cross-sectional view showing one aspect of the substrate with a partition wall of the present invention having a low refractive index layer and an inorganic protective layer II. The substrate 1 has a patterned partition wall 2 and a layer 3 containing a color conversion light-emitting material, and further has an inorganic protective layer II (6) and a low refractive index layer 4 in this order.

In addition, the substrate with a partition wall of the present invention preferably further has (J) a color filter having a thickness of 1 μm to 5 μm (hereinafter, sometimes described between the substrate and the layer (G) containing the color conversion luminescent material) "Color filter (J)"). The color filter (J) has a function of transmitting visible light in a specific wavelength region and setting the transmitted light to a desired hue. By having a color filter (J), color purity can be improved. By setting the thickness of the color filter (J) to 1 μm or more, color purity can be further improved. On the other hand, by setting the thickness of the color filter (J) to 5 μm or less, the brightness of the display device can be further improved.

FIG. 6 is a cross-sectional view showing an embodiment of the substrate with a partition wall of the present invention having a color filter. A patterned partition wall 2 and a color filter 7 are provided on the substrate 1, and a layer 3 containing a color-converting luminescent material is provided on the color filter 7.

As the color filter, for example, a color filter used in a flat-panel display such as a liquid crystal display, and a pigment-dispersed material in which a pigment is dispersed in a photoresist can be used. More specifically, a blue color filter that selectively transmits a wavelength of 400 nm to 550 nm, a green color filter that selectively transmits a wavelength of 500 nm to 600 nm, and a selective transmission 500 A yellow color filter having a wavelength of at least nm, a red color filter selectively transmitting a wavelength of at least 600 nm, and the like. In addition, the color filter may be laminated separately from the layer (G) containing the color conversion luminescent material, or may be laminated integrally.

In addition, the substrate with a partition wall of the present invention preferably has a thickness of (I-3) between 50 and 1,000 nm between the color filter (J) and the layer (G) containing a color conversion luminescent material. Inorganic protective layer III. With the inorganic protective layer III, it is difficult for the raw material for forming the color filter (J) to reach the layer (G) containing the color conversion luminescent material from the color filter (J). Therefore, it is possible to suppress the layer containing the color conversion luminescent material ( G) Deterioration of brightness.

FIG. 7 is a cross-sectional view showing one aspect of the substrate with a partition wall of the present invention including a color filter and an inorganic protective layer III. The substrate 1 is provided with a patterned partition wall 2 and a color filter 7, and an inorganic protective layer III (8) and a partition wall 2 covered with the inorganic protective layer III (8) are arranged on the substrate 1. Layer 3 containing a color-converting luminescent material.

In addition, the substrate with a partition wall according to the present invention preferably further has an (I-4) inorganic protective layer IV having a thickness of 50 nm to 1,000 nm on the substrate. The inorganic protective layer IV functions as a refractive index adjustment layer, and can more efficiently extract light appearing from the layer (G) containing a color conversion light emitting material, and further improve the brightness of the display device. More preferably, an inorganic protective layer IV is provided between the substrate and the partition wall (F) and the layer (G) containing the color conversion luminescent material.

FIG. 8 is a cross-sectional view showing one aspect of the substrate with a partition wall of the present invention having the inorganic protective layer IV. An inorganic protective layer IV (9) is provided on the substrate 1, and there are patterned partition walls 2 and color filters 7 on the substrates 1, and patterned partition walls 2 and color-converting luminescent materials are included on these Layer 3.

Examples of the material constituting the inorganic protective layer I to the inorganic protective layer IV include metal oxides such as silicon oxide, indium tin oxide, and gallium zinc oxide; metal nitrides such as silicon nitride; and fluorides such as magnesium fluoride. Two or more of these compounds may be contained. Among these, in terms of low water vapor permeability and high permeability, one or more members selected from silicon nitride and silicon oxide are more preferred.

From the viewpoint of sufficiently suppressing the transmission of substances such as water vapor, the thickness of the inorganic protective layer I to the inorganic protective layer IV is preferably 50 nm or more, and more preferably 100 nm or more. On the other hand, from the viewpoint of suppressing a decrease in transmittance, the thickness of the inorganic protective layer I to the inorganic protective layer IV is preferably 800 nm or less, and more preferably 500 nm or less.

The thickness of the inorganic protective layer I to the inorganic protective layer IV can be measured by using a polishing device such as a cross-section polisher to expose the cross-section perpendicular to the substrate, and magnifying the cross-section using a scanning electron microscope or a transmission electron microscope. .

Examples of a method for forming the inorganic protective layer I to the inorganic protective layer IV include a sputtering method and the like.

Next, a display device of the present invention will be described. A display device according to the present invention includes the substrate with a partition wall, and a light source. As the light emitting light source, a light source selected from a liquid crystal cell, an organic EL unit, a micro LED unit, and a micro LED unit is preferable. In terms of excellent light emission characteristics, an organic EL unit is more preferred.

The manufacturing method of the display device of this invention is demonstrated using an example of the display device which has the board | substrate with a partition wall of this invention, and an organic EL unit. A photosensitive polyimide resin was coated on a glass substrate, and an insulating film was formed by a photolithography method. As a back electrode layer, after sputtering aluminum, patterning was performed by a photolithography method to form a back electrode layer in an opening portion without an insulating film. Next, as an electron transport layer, tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq ₃ ) was formed into a film by a vacuum evaporation method, and then as a light-emitting layer, Alq ₃ was doped with diamine. White light-emitting layer of methylenepyran, quinacridone, 4,4'-bis (2,2-diphenylvinyl) biphenyl. Next, as the hole transport layer, N, N'-diphenyl-N, N'-bis (α-naphthyl) -1,1'-biphenyl-4,4'-di Amine forms a film. Finally, as a transparent electrode, an ITO film was formed by sputtering to produce an organic EL unit having a white light-emitting layer. The organic EL unit obtained in the above-mentioned manner is opposed to the substrate with a partition wall and bonded with a sealant to produce a display device.

Next, the touch panel of the present invention will be described. A touch panel of the present invention includes the patterned substrate of the present invention, a transparent electrode, a metal wiring, and a transparent film.

FIG. 10 shows an example of a cross section of a touch panel according to the present invention. The white light-shielding cured film 12 and the transparent electrode 13 including the cured film of the present invention are provided on the glass substrate 11, and the transparent insulating film 14 and the metal wiring 15 are provided on the transparent electrode 13.

As a transparent electrode, an ITO electrode etc. are preferable at the point which is hard to recognize.

Examples of the material constituting the metal wiring include low-resistance materials such as copper, MAM (Molybdenum / Aluminum / Molybdenum Multilayer Film), and silver.

The transparent film is preferably a transparent insulating film that prevents conduction due to contact between metal wirings. Examples include inorganic films such as silicon oxide and silicon nitride; alkali-soluble resins, polyfunctional monomers, and photopolymerization initiators are included. A cured film of a negative photosensitive transparent resin composition.

Examples of the method for manufacturing the touch panel of the present invention include a method of forming a transparent electrode, a transparent insulating film, and a metal wiring on the patterned processed substrate of the present invention. Hereinafter, a representative manufacturing method will be described.

11a to 11d illustrate an example of a method for manufacturing a touch panel of the present invention. FIG. 11 a is a plan view of a patterned processing substrate of the present invention having a white light-shielding cured film 12 on a glass substrate 11. A transparent electrode 13 is formed on the glass substrate 11. Examples of a method for forming the transparent electrode 13 include a method of forming a photoresist by forming a film of ITO by a sputtering method, forming a photoresist by etching, and peeling the photoresist. Fig. 11b shows a plan view after the transparent electrode is formed. Next, a transparent insulating film 14 is formed at a predetermined position. As a manufacturing method of a transparent insulating film, when a transparent insulating film is an inorganic film, a chemical vapor deposition (CVD) method is mentioned, for example. When the transparent insulating film is a cured film of a negative photosensitive transparent resin composition, for example, a method using a photolithography method may be mentioned. FIG. 11c shows a plan view after the transparent insulating film is formed. Thereafter, the metal wiring 15 is formed. Examples of the method for forming the metal wiring include a method of forming a photoresist after forming a metal film of the wiring by a vapor deposition method or a sputtering method, and forming a pattern by etching to remove the photoresist, and a silver paste. Printing, lithography, etc. FIG. 11d shows a plan view after the metal wiring is formed.
[Example]

Hereinafter, the present invention will be described more specifically with examples, but the present invention is not limited to these examples. The compounds using the abbreviation among the compounds used in the synthesis examples and examples are shown below.
PGMEA: propylene glycol monomethyl ether acetate
DAA: Diacetone alcohol
BHT: dibutylhydroxytoluene.

The solid content concentration of the siloxane resin solution in Synthesis Examples 1 to 9 and the acrylic resin in Synthesis Example 10 was determined by the following method. Weigh 1.5 g of the siloxane resin solution or acrylic resin solution into an aluminum cup, and use a hot plate to heat at 250 ° C for 30 minutes to evaporate the liquid component. The weight of the solid content remaining in the aluminum cup after heating was measured, and the solid content concentration of the siloxane resin solution or the acrylic resin solution was obtained from the ratio to the weight before heating.

The weight average molecular weights of the siloxane resins in Synthesis Examples 1 to 9 and the acrylic resin in Synthesis Example 10 were determined by the following methods. GPC analysis was performed using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation), using tetrahydrofuran as a mobile layer, and measuring polystyrene based on "JIS K7252-3 (date of establishment: 2008/03/20)" Converted weight average molecular weight.

The content ratio of each repeating unit in the siloxane resin in Synthesis Examples 1 to 9 was determined by the following method. The siloxane resin solution was poured into a 10 mm diameter "Teflon" (registered trademark) nuclear magnetic resonance (NMR) sample tube, and ²⁹ Si-NMR measurement was performed. The ratio of the integrated value of Si of the organosilane to the integrated value of the entire Si derived from the organosilane was calculated as the content ratio of each repeating unit. The ²⁹ Si-NMR measurement conditions are shown below.
Device: Nuclear magnetic resonance device (JNM-GX270; manufactured by Japan Electronics Co., Ltd.)
Measurement method: gated decoupling method to determine nuclear frequency: 53.6693 MHz ( ²⁹ Si core)
Spectral width: 20000 Hz
Pulse width: 12 μs (45 ° pulse)
Pulse wave repeat time: 30.0 seconds Solvent: Acetone-d6
Reference material: Tetramethylsilane Measurement temperature: 23 ° C
Sample speed: 0.0 Hz.

Synthesis Example 1 A solution of a siloxane resin (B-1) was charged into a 1000 ml three-necked flask with trifluoropropyltrimethoxysilane 147.32 g (0.675 mol) and 3-methacryloxypropylmethyldi Methoxysilane 40.66 g (0.175 mol), 3-trimethoxysilylpropyl succinic anhydride 26.23 g (0.1 mol), 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane 12.32 g (0.05 mol), BHT 0.808 g, PGMEA 171.62 g, and while stirring at room temperature for 30 minutes, 2.265 g of phosphoric acid dissolved in 52.65 g of water (1.0% by weight relative to the monomer content) was added. Aqueous solution. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 90 minutes, and then the oil bath was heated to 115 ° C. for 30 minutes. One hour after the start of temperature rise, the solution temperature (internal temperature) reached 100 ° C, and then heating and stirring (internal temperature of 100 ° C to 110 ° C) for 2 hours to obtain a siloxane resin solution. In addition, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liters / minute while heating and stirring. A total of 131.35 g of methanol and water were distilled off as a by-product during the reaction. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration became 40% by weight, thereby obtaining a siloxane resin (B-1) solution. The weight average molecular weight of the obtained siloxane resin (B-1) was 4,000 (in terms of polystyrene). In addition, based on the measurement results of ²⁹ Si-NMR, trifluoropropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxy group derived from the siloxane resin (B-1) Molar ratios of the repeating units of silane, 3-trimethoxysilylpropylsuccinic anhydride, and 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane are 67.5 mol% and 17.5 mol, respectively %, 10 mol%, 5 mol%.

Synthesis Example 2 Siloxane resin (B-2) solution A 1000 ml three-necked flask was charged with 81.84 g (0.375 mol) of trifluoropropyltrimethoxysilane and 60.66 g of trifluoropropylmethyldimethoxysilane. (0.3 mol), 3-methacryloxypropylmethyldimethoxysilane 40.66 g (0.175 mol), 3-trimethoxysilylpropyl succinic anhydride 26.23 g (0.1 mol), 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane 12.32 g (0.05 mol), BHT 0.78 g, PGMEA 174.95 g, dissolved in 44.55 g of water while stirring at room temperature for 30 minutes A phosphoric acid aqueous solution of 2.217 g of phosphoric acid (1.0% by weight based on the monomer content). Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. A total of 128.40 g of methanol and water were distilled off as a by-product during the reaction. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration became 40% by weight, thereby obtaining a siloxane resin (B-2) solution. The weight average molecular weight of the obtained siloxane resin (B-2) was 3,200 (in terms of polystyrene). In addition, based on the measurement results of ²⁹ Si-NMR, trifluoropropyltrimethoxysilane, trifluoropropylmethyldimethoxysilane, and 3-methyl in the siloxane resin (B-2) were derived. Acrylic methoxypropylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane repeating unit The molar ratios are 37.5 mol%, 30 mol%, 17.5 mol%, 10 mol%, and 5 mol%.

Synthesis Example 3 Siloxane resin (B-3) solution A 1000 ml three-necked flask was charged with 103.67 g (0.475 mol) of trifluoropropyltrimethoxysilane and 3-methacryloxypropylmethyldi Methoxysilane 40.66 g (0.175 mol), 3-trimethoxysilylpropyl succinic anhydride 26.23 g (0.1 mol), 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane 12.32 g (0.05 mol), methyltrimethoxysilane 27.24 g (0.2 mol), BHT 0.808 g, PGMEA 155.37 g, while stirring at room temperature for 30 minutes, add 2.101 g of phosphoric acid dissolved in 52.65 g of water (relatively A 1.0% by weight) phosphoric acid aqueous solution was charged into the monomer. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. A total of 131.35 g of methanol and water were distilled off as a by-product during the reaction. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration became 40% by weight, thereby obtaining a siloxane resin (B-3) solution. The weight average molecular weight of the obtained siloxane resin (B-3) was 3,500 (in terms of polystyrene). In addition, according to the measurement results of ²⁹ Si-NMR, trifluoropropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxy group derived from the siloxane resin (B-3) Molar ratios of repeating units of silane, 3-trimethoxysilylpropylsuccinic anhydride, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, and methyltrimethoxysilane, respectively It is 47.5 mol%, 17.5 mol%, 10 mol%, 5 mol%, 20 mol%.

Synthesis Example 4 A solution of a siloxane resin (B-4) was charged into a 1000 ml three-necked flask with 103.67 g (0.475 mol) of trifluoropropyltrimethoxysilane and 24.04 g (0.20 mol of dimethyldimethoxysilane). ), 3-methacryloxypropyltrimethoxysilane 43.46 g (0.175 mol), 3-trimethoxysilylpropyl succinic anhydride 26.23 g (0.1 mol), 3- (3,4-cyclo Oxycyclohexyl) propyltrimethoxysilane 12.32 g (0.05 mol), BHT 0.736 g, PGMEA 161.28 g, while stirring at room temperature for 30 minutes, added in water 50.85 g, 2.097 g of phosphoric acid is dissolved (relative to The monomer was charged to a 1.0% by weight) phosphoric acid aqueous solution. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. A total of 130.05 g of methanol and water were distilled off as a by-product during the reaction. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration became 40% by weight, thereby obtaining a siloxane resin (B-4) solution. The weight average molecular weight of the obtained siloxane resin (B-4) was 3,800 (in terms of polystyrene). In addition, according to the measurement results of ²⁹ Si-NMR, trifluoropropyltrimethoxysilane, dimethyldimethoxysilane, and 3-methacrylic acid were derived from the siloxane resin (B-4). Molar ratios of the repeating units of propyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, and 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane 47.5 mol%, 20 mol%, 17.5 mol%, 10 mol%, 5 mol%.

Synthesis Example 5 Siloxane resin (B-5) solution was charged into a 1000 ml three-necked flask with trifluoropropyltrimethoxysilane 147.32 g (0.675 mol) and 3-methacryloxypropyltrimethoxy Silane 43.46 g (0.175 mol), 3-trimethoxysilylpropylsuccinic anhydride 26.23 g (0.1 mol), 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane 12.32 g (0.05 mol), BHT 0.810 g, PGMEA 172.59 g, and while stirring at room temperature for 30 minutes, 2.293 g of phosphoric acid (1.0% by weight based on the monomer content) dissolved in 54.45 g of water was added. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. A total of 140.05 g of methanol and water were distilled off as a by-product during the reaction. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration became 40% by weight, thereby obtaining a siloxane resin (B-5) solution. The weight average molecular weight of the obtained siloxane resin (B-5) was 4,100 (in terms of polystyrene). In addition, according to the measurement results of ²⁹ Si-NMR, trifluoropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 derived from the siloxane resin (B-5), 3 The molar ratios of the repeating units of -trimethoxysilylpropylsuccinic anhydride and 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane are 67.5 mol%, 17.5 mol%, 10 mol%, 5 mol%.

Synthesis Example 6 A solution of a siloxane resin (B-6) was put in a 1000 ml three-necked flask, and trifluoropropyltrimethoxysilane 76.93 g (0.35 mol) and 3-propenyloxypropyltrimethoxysilane 41.00 were charged. g (0.175 mol), 3-trimethoxysilylpropylsuccinic anhydride 26.23 g (0.1 mol), methyltrimethoxysilane 51.08 g (0.375 mol), BHT 0.375 g, PGMEA 136.95 g, while at room temperature While stirring, 2.070 g of phosphoric acid (1.0% by weight based on the monomer content) dissolved in 58.50 g of water was added over 30 minutes. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. A total of 139.50 g of methanol and water were distilled off as a by-product during the reaction. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration became 40% by weight, thereby obtaining a siloxane resin (B-6) solution. The weight average molecular weight of the obtained siloxane resin (B-6) was 5,000 (in terms of polystyrene). In addition, according to the measurement results of ²⁹ Si-NMR, trifluoropropyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, and 3-trimethylsilane derived from the siloxane resin (B-6) The molar ratios of the repeating units of oxysilylpropylsuccinic anhydride and methyltrimethoxysilane are 35 mol%, 17.5 mol%, 10 mol%, and 37.5 mol%, respectively.

Synthesis Example 7 A solution of a siloxane resin (B-7) was placed in a 1000 ml three-necked flask, and trifluoropropyltrimethoxysilane 76.39 g (0.35 mol) and 3-methacryloxypropylmethyldi Methoxysilane 40.66 g (0.175 mol), 3-trimethoxysilylpropyl succinic anhydride 26.23 g (0.1 mol), 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane 12.32 g (0.05 mol), methyltrimethoxysilane 44.27 g (0.325 mol), BHT 0.673 g, PGMEA 145.22 g, while stirring at room temperature for 30 minutes, added in water 52.65 g dissolved phosphoric acid 1.999 g (relatively A 1.0% by weight) phosphoric acid aqueous solution was charged into the monomer. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. A total of 130.25 g of methanol and water were distilled off as a by-product during the reaction. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration became 40% by weight, thereby obtaining a siloxane resin (B-7) solution. The weight average molecular weight of the obtained siloxane resin (B-7) was 3,900 (in terms of polystyrene). In addition, according to the measurement results of ²⁹ Si-NMR, trifluoropropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxy group derived from the siloxane resin (B-7) Molar ratios of repeating units of silane, 3-trimethoxysilylpropylsuccinic anhydride, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, and methyltrimethoxysilane, respectively It is 35 mol%, 17.5 mol%, 10 mol%, 5 mol%, and 32.5 mol%.

Synthesis Example 8 A silanol resin (B-8) solution was charged into a 1000 ml three-necked flask with trifluoropropyltrimethoxysilane 185.51 g (0.85 mol) and 3-methacryloxypropylmethyldi 17.43 g (0.075 mol) of methoxysilane, 19.67 g (0.075 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 0.779 g of BHT, 166.39 g of PGMEA, added while stirring at room temperature for 30 minutes. In 54.00 g of water, 2.226 g of phosphoric acid (1.0% by weight based on the monomer content) was dissolved in an aqueous phosphoric acid solution. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. A total of 136.90 g of methanol and water were distilled off as a by-product during the reaction. PGMEA was added to the obtained silicone resin solution so that the solid content concentration became 40% by weight, thereby obtaining a silicone resin (B-8) solution. The weight average molecular weight of the obtained siloxane resin (B-8) was 4,600 (in terms of polystyrene). In addition, based on the measurement results of ²⁹ Si-NMR, trifluoropropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxy group derived from the siloxane resin (B-8) The molar ratios of the repeating units of silane and 3-trimethoxysilylpropylsuccinic anhydride were 85 mol%, 7.5 mol%, and 7.5 mol%, respectively.

Synthesis Example 9 Siloxane resin (B-9) solution A 1000 ml three-necked flask was charged with 164.94 g (0.675 mol) of diphenyldimethoxysilane and 3-methacryloxypropylmethyldioxane. Methoxysilane 40.66 g (0.175 mol), 3-trimethoxysilylpropyl succinic anhydride 26.23 g (0.1 mol), 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane 12.32 g (0.05 mol), BHT 0.974 g, PGMEA 201.22 g, and while stirring at room temperature for 30 minutes, 2.442 g of phosphoric acid (1.0% by weight based on monomer content) dissolved in 40.50 g of water was added. Aqueous solution. Thereafter, a siloxane resin solution was obtained in the same manner as in Synthesis Example 1. A total of 136.90 g of methanol and water were distilled off as a by-product during the reaction. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration became 40% by weight, thereby obtaining a siloxane resin (B-9) solution. The weight average molecular weight of the obtained siloxane resin (B-9) was 2,800 (in terms of polystyrene). In addition, according to the measurement results of ²⁹ Si-NMR, in the siloxane resin (B-9), diphenyldimethoxysilane and 3-methacryloxypropylmethyldimethoxy group were derived. Molar ratios of the repeating units of silane, 3-trimethoxysilylpropylsuccinic anhydride, and 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane are 67.5 mol% and 17.5 mol, respectively %, 10 mol%, 5 mol%.

The raw material compositions of the siloxane resins of Synthesis Examples 1 to 9 are shown in Tables 1 to 2.

[Table 1]

[Table 1]

[Table 2]

[Table 2]

Synthesis Example 10 An acrylic resin (b) solution was charged into a 500 ml three-necked flask, and 3 g of 2,2'-azobis (isobutyronitrile) and 50 g of PGMEA were charged. Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate were charged, and the mixture was temporarily stirred at room temperature. After replacing the inside of the flask with nitrogen, heating and stirring were performed at 70 ° C for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and heating and stirring were performed at 90 ° C for 4 hours to obtain Acrylic resin solution. PGMEA was added to the obtained acrylic resin solution so that the solid content concentration became 40% by weight, to obtain an acrylic resin (b) solution. The weight average molecular weight of the acrylic resin (b) was 10,000 (polystyrene equivalent).

Synthesis Example 11 A solution of a silane coupling agent (G-1) was added to 200 g of PGMEA. 41.97 g (0.16 mol) of 3-trimethoxysilylpropylsuccinic anhydride and 11.70 g (0.16 mol) of tertiary butylamine were temporarily added. After stirring at room temperature, it was stirred at 40 ° C for 2 hours. Thereafter, the temperature was raised to 80 ° C, and the mixture was heated and stirred for 6 hours. PGMEA was added so that the obtained solution had a solid content concentration of 20% by weight to obtain 3- (third butylaminomethylamino) -6- (trimethoxysilyl) hexanoic acid, 2- (2- Silane coupling agent (G-1) in a mixed solution of (third butylamino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid.

Synthesis Example 12 The green organic phosphor was 3,5-dibromobenzaldehyde (3.0 g), 4-tert-butylphenylboronic acid (5.3 g), and tetrakis (triphenylphosphine) palladium (0) (0.4 g ), Potassium carbonate (2.0 g) was placed in the flask, and replaced with nitrogen. To this were added degassed toluene (30 mL) and degassed water (10 mL), and refluxed for 4 hours. The reaction solution was cooled to room temperature, the organic layer was separated, and then washed with saturated brine. The organic layer was dried with magnesium sulfate and filtered, and then the solvent was distilled off. The obtained reaction product was purified by silica gel column chromatography to obtain 3,5-bis (4-thirdbutylphenyl) benzaldehyde (3.5 g) as a white solid. Next, put 3,5-bis (4-third-butylphenyl) benzaldehyde (1.5 g) and 2,4-dimethylpyrrole (0.7 g) in a flask, and add dehydrated dichloromethane (200 mL) ) And trifluoroacetic acid (1 drop), and stirred under a nitrogen atmosphere for 4 hours. A solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.85 g) in dehydrated dichloromethane was added, followed by stirring for 1 hour. After the reaction, boron trifluoride diethyl ether complex (7.0 mL) and diisopropylethylamine (7.0 mL) were added, and after stirring for 4 hours, water (100 mL) was added to stir, and the organic layer was stirred. Perform liquid separation. The organic layer was dried with magnesium sulfate and filtered, and then the solvent was distilled off. The obtained reaction product was purified by silica gel column chromatography to obtain 0.4 g of a green powder (yield: 17%). The ¹ H-NMR analysis result of the obtained green powder was as follows, and it was confirmed that the obtained green powder was [G-1] represented by the following structural formula.
¹ H-NMR (CDCl ₃ (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).

[Chemical 7]

Synthesis Example 13 Polysiloxane Solution (LS-1) Containing Silicon Dioxide Particles
In a 500 ml three-necked flask, 0.05 g (0.4 mmol) of methyltrimethoxysilane, 0.66 g (3.0 mmol) of trifluoropropyltrimethoxysilane, and 0.10 g of trimethoxysilylpropylsuccinic anhydride (0.4 mmol), γ-propenyloxypropyltrimethoxysilane, 7.97 g (34 mmol), 15.6% by weight of silicon dioxide particles in an isopropanol dispersion (IPA-ST-UP: manufactured by Nissan Chemical Industries, Ltd.) ) 224.37 g, adding 163.93 g of ethylene glycol mono-tertiary butyl ether. While stirring at room temperature, a phosphoric acid aqueous solution in which 0.088 g of phosphoric acid was dissolved in 4.09 g of water was added over 3 minutes. Thereafter, the flask was immersed in an oil bath at 40 ° C and stirred for 60 minutes, and then the oil bath was heated to 115 ° C over 30 minutes. The internal temperature of the solution reached 100 ° C after 1 hour from the start of heating, and then heated and stirred for 2 hours (internal temperature was 100 ° C to 110 ° C) to obtain a polysiloxane solution (LS-1) containing silicon dioxide particles. In addition, nitrogen was circulated at 0.05 l (liter) / minute while heating and stirring. A total of 194.01 g of methanol and water were distilled off as a by-product during the reaction. The solid content concentration of the obtained polysiloxane solution (LS-1) containing silicon dioxide particles was 24.3% by weight, and the content of the polysiloxane and the silicon dioxide particles in the solid content were 15% by weight and 85% by weight, respectively. weight%. Polysiloxane derived from the obtained polysiloxane solution (LS-1) containing silicon dioxide particles, derived from methyltrimethoxysilane, trifluoropropyltrimethoxysilane, 3-trimethoxy The molar ratios of the repeating units of silane-based succinic anhydride and γ-acryloxypropyltrimethoxysilane were 1.0 mol%, 8.0 mol%, 1.0 mol%, and 90.0 mol%, respectively.

Preparation Example 1 Negative photosensitive coloring composition (P-1)
To 5.00 g of a titanium dioxide pigment (R-960; manufactured by Japan BASF Co., Ltd.) as a (A) white pigment, a siloxane obtained in Synthesis Example 1 as a (B) siloxane resin was mixed. Resin (B-1) solution was 5.00 g. The dispersion was performed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion liquid (MW-1).

Next, 10.00 g of the pigment dispersion liquid (MW-1), 1.15 g of the siloxane resin (B-1) solution, and 2-methyl-1- (4-methylthio) as the (C) photopolymerization initiator. Phenyl) -2-morpholinopropane-1-one ("Irgacure" (registered trademark) -907 (trade name), manufactured by Japan BASF (stock)) 0.100 g, bis ( 2,4,6-trimethylbenzyl) -phenylphosphine oxide ("Irgacure" -819 (trade name), manufactured by Japan BASF (stock)) 0.20 g, as (D) Pentaerythritol acrylate ("Light Acrylate" (registered trademark) PE-3A (trade name), manufactured by Kyoeisha Chemical Co., Ltd.) 1.50 g of photopolymerizable compound, containing photopolymerizable fluorine 1.00 g of a 40 wt% PGMEA diluted solution of a compound ("Megafac" (registered trademark) RS-76-E (trade name) manufactured by DIC Corporation), 20 wt% PGMEA of a silane coupling agent (G1) Diluted solution 0.500 g, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylic acid ester ("Celloxide" (registered trademark) -2021P (Trade name), Daicel (manufactured) 0.200 g, ethylene bis (oxyethylene) bis [3- (5-third butyl-4-hydroxy-m-toluene) propionate] (" "IRGANOX" (registered trademark) -1010 (trade name), Japan BASF (made in Japan) 0.300 g, acrylic surfactant (trade name "BYK" (registered trademark) ) -352, 0.100 g of PGMEA 10% by weight diluted solution (made by BYK-Chemie Japan) is dissolved in a mixed solvent of 1.000 g of DAA and 4.200 g of PGMEA Stir. Then, it filtered with the filter of 5.0 micrometers, and obtained the negative photosensitive coloring composition (P-1).

Production Example 2 to Production Example 4 Negative-type photosensitive coloring composition (P-2) to Negative-type photosensitive coloring composition (P-4)
Except that the siloxane resin (B-2) to siloxane resin (B-4) solution was used instead of the siloxane resin (B-1) solution, the same procedure as in Production Example 1 was performed to obtain a negative ion. Type photosensitive coloring composition (P-2) to negative type photosensitive coloring composition (P-4).

Preparation Example 5 Negative Photosensitive Coloring Composition (P-5)
Instead of using 1.00 g of a 40% by weight PGMEA dilution of pentaerythritol acrylate ("Light Acrylate" (registered trademark) PE-3A) instead of the photopolymerizable fluorine-containing compound ("Megafac" ( Registered trademark) RS-76-E) was carried out in the same manner as in Production Example 1 except that the 40% by weight PGMEA diluted solution was 1.00 g to obtain a negative photosensitive coloring composition (P-5).

Preparation Example 6 Negative Photosensitive Coloring Composition (P-6)
1.00 g of a 40% by weight PGMEA diluted solution of 2,2,2-trifluoroethyl acrylate ("Biscoat" (registered trademark)-3F (trade name), manufactured by Osaka Organic Chemicals Co., Ltd.)) Instead of 1.00 g of a 40 wt% PGMEA diluted solution containing a photoreactive fluorine-containing compound ("Megafac" (registered trademark) RS-76-E (trade name) manufactured by DIC (Stock)), and the preparation example 1 was performed in the same manner to obtain a negative photosensitive coloring composition (P-6).

Preparation Example 7 Negative-type photosensitive coloring composition (P-7)
A negative type was obtained in the same manner as in Preparation Example 1 except that a titanium dioxide pigment (CR-97: manufactured by Ishihara Industry Co., Ltd.) was used instead of the titanium dioxide pigment (R-960; manufactured by Japan BASF). Photosensitive coloring composition (P-7).

Preparation Example 8 Negative photosensitive coloring composition (P-8)
In addition to using 0.100 g of "Irgacure" (registered trademark) -MBF (trade name) (manufactured by Japan BASF) in place of 2-methyl-1- (4-methylthiobenzene) A negative photosensitive coloring composition (P-8) was obtained in the same manner as in Production Example 1 except for the base) -2-morpholinopropane-1-one ("Irgacure" 127).

Preparation Example 9 to Preparation Example 13 Negative-type photosensitive coloring composition (P-9)-Negative-type photosensitive coloring composition (P-13)
Except that the siloxane resin (B-5) to the siloxane resin (B-9) solution were used instead of the siloxane resin (B-1) solution, the same procedure as in Production Example 1 was performed to obtain a negative photosensitive A negative coloring composition (P-9) to a negative photosensitive coloring composition (P-13).

Preparation Example 14 Negative Photosensitive Coloring Composition (P-14)
A negative-type photosensitive coloring composition (P-14) was obtained in the same manner as in Production Example 1 except that the acrylic resin (b) solution was used instead of the resin (B-1) solution.

Preparation Example 15 Negative-type photosensitive coloring composition (P-15)
The pigment dispersion liquid (MW-1) was 8.00 g, the polysiloxane (B-1) solution obtained in Synthesis Example 1 was 1.615 g, and ethyl acetate as a photopolymerization initiator was 1- [9-ethyl -6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamoxime) ("Irgacure" (registered trademark) OXE-02 (Brand name) Made by Japan BASF Co., Ltd. (hereinafter "OXE-2")) 0.160 g, bis (2,4,6-trimethylbenzyl) -phenylphosphine oxide ("Brilliant "Irgacure" 819 (trade name), Japan BASF Co., Ltd. (hereinafter "IC-819")) 0.160 g, dipentaerythritol hexaacrylate ("Kayala" as a photopolymerizable compound) (KAYARAD) (registered trademark) DPHA (trade name), manufactured by Shin Nippon Pharmaceutical Co., Ltd. (hereinafter "DPHA")), 1.20 g of a photopolymerizable fluorine-containing compound as a liquid repellent compound ("Meiga ( Megafac) "(registered trademark) RS-76-E (trade name) manufactured by DIC Corporation (hereinafter" RS-76-E ")) 40% by weight PGMEA diluted solution 0.100 g, 3 ', 4'-epoxy Cyclohexylmethyl-3,4-epoxy Alkyl carboxylate ("Celloxide" (registered trademark) 2021P (trade name), Daicel (stock) manufactured (hereinafter "Celloxide 2021P")) 0.160 g, Ethylene bis (oxyethylene) bis [3- (5-third butyl-4-hydroxy-m-toluene) propionate] ("IRGANOX" (registered trademark) 1010 (trade name), Japan Manufactured by BASF (Japan) (hereinafter "IRGANOX 1010")) 0.024 g, acrylic surfactant ("BYK" (registered trademark)) 352 (trade name), Japan 0.100 g of a 10% by weight diluted solution of PGMEA (manufactured by BYK-Chemie Japan) was dissolved in a mixed solvent of 1.200 g of DAA and 7.281 g of PGMEA, and stirred. Then, it filtered with a 5.0 micrometer filter, and obtained the negative photosensitive coloring composition (P-15).

Preparation Example 16 Negative-type photosensitive coloring composition (P-16)
A negative-type photosensitive coloring composition (P-16) was obtained in the same manner as in Production Example 15 except that a polysiloxane (B-5) solution was used instead of the polysiloxane (B-1) solution.

Preparation Example 17 Negative-type photosensitive coloring composition (P-17)
A negative-type photosensitivity was obtained in the same manner as in Preparation Example 15 except that the addition amount of the 40% by weight PGMEA diluted solution of RS-76-E was changed to 0.01 g and the amount of the polysiloxane (B-1) solution was 1.705 g. Sexually colored composition (P-17).

Preparation Example 18 Negative photosensitive coloring composition (P-18)
A negative-type photosensitive coloring composition was obtained in the same manner as in Preparation Example 15 except that 0.100 g of a 40% by weight PGMEA diluted solution without RS-76-E was added and the amount of the polysiloxane (B-1) solution was set to 1.715 g. (P-18).

Preparation Example 19 Negative photosensitive coloring composition (P-19)
In addition to changing the amount of pigment dispersion (MW-1) to 4.00 g, the amount of polysiloxane (B-1) solution to 8.615 g, and using a mixed solvent of 1.200 g of DAA and 1.881 g of PGMEA, A negative-type photosensitive coloring composition (P-19) was obtained in the same manner as in Production Example 15.

Preparation Example 20 Negative photosensitive coloring composition (P-20)
In addition to changing the amount of pigment dispersion (MW-1) to 3.20 g, the amount of polysiloxane (B-1) solution to 10.015 g, and using a mixed solvent of 1.200 g of DAA and 3.681 g of PGMEA, A negative-type photosensitive coloring composition (P-20) was obtained in the same manner as in Production Example 15.

Preparation Example 21 Negative photosensitive coloring composition (P-21)
In addition to changing the amount of pigment dispersion (MW-1) to 1.60 g, the amount of polysiloxane (B-1) solution to 12.815 g, and using a mixed solvent of 1.200 g of DAA and 2.481 g of PGMEA, A negative-type photosensitive coloring composition (P-21) was obtained in the same manner as in Production Example 15.

The compositions of Production Examples 1 to 21 are summarized in Tables 3, 4, and 5.

[table 3]

[table 3]

[Table 4]

[Table 4]

[table 5]

[table 5]

Preparation Example 22 Color conversion luminescent material composition (CL-1)
20 parts by weight of 0.5% by weight toluene solution of green quantum dot material (Lumidot 640 CdSe / ZnS, average particle size 6.3 nm: manufactured by Aldrich), 45 parts by weight of DPHA, Solid (Irgacure) "(registered trademark) 907 (manufactured by Japan BASF) 5 parts by weight of acrylic resin (SPCR-18 (trade name), Showa Denko Corporation) 30 wt% PGMEA solution 166 parts by weight and 97 parts by weight of toluene were mixed and stirred to dissolve uniformly. Filtration was performed using a 0.45 μm syringe filter to prepare a color conversion luminescent material composition (CL-1).
Preparation Example 23 Color conversion luminescent material composition (CL-2)
A color conversion light-emitting material was prepared in the same manner as in Preparation Example 22 except that 0.4 parts by weight of the green phosphor G-1 obtained in Synthesis Example 12 was used instead of the green quantum dot material, and the amount of toluene was changed to 117 parts by weight. Composition (CL-2).

Preparation Example 24 Color filter forming material (CF-1)
CI Pigment Green (Pigment Green) 59 90 g, CI Pigment Yellow (Pigment Yellow) 150 60 g, polymer dispersant ("BYK" (registered trademark)-6919 (trade name) BYK Chemical (BYK -Manufactured by Chemie) 75 g, adhesive resin ("ADEKA ARKLS" (registered trademark) WR301 (trade name) manufactured by ADEKA), 100 g, PGMEA 675 g was mixed to prepare a slurry. A tube was used to connect the beaker containing the slurry to a Dyno-Mill, and a zirconia bead with a diameter of 0.5 mm was used as a medium to perform a dispersion treatment at a peripheral speed of 14 m / s for 8 hours. Pigment Green 59 dispersion (GD-1).

Pigment green 59 dispersion (GD-1) 56.54 g, acrylic resin ("Cyclomer" (registered trademark) P (ACA) Z250 (trade name) manufactured by Daicel-allnex (stock) (Hereinafter "P (ACA) Z250")) 3.14 g, DPHA 2.64 g, photopolymerization initiator ("Optomer" (registered trademark) NCI-831 (trade name) ADEKA (Stock) (hereinafter "NCI-831")) 0.330 g, surfactant ("BYK" (registered trademark) -333 (trade name) manufactured by BYK-Chemie)) 0.04 g 0.01 g of BHT as a polymerization inhibitor and 37.30 g of PGMEA as a solvent, and a color filter forming material (CF-1) was produced.

Preparation Example 25 Resin composition for light-shielding partition wall Carbon black (MA100 (trade name) manufactured by Mitsubishi Chemical Corporation) 150 g, polymer dispersant BYK (registered trademark) -6919 75 g, P (ACA ) Z250 100 g and PGMEA 675 g are mixed to make a slurry. The beaker containing the slurry was connected to the Deno mill using a tube. The zirconia beads with a diameter of 0.5 mm were used as a medium, and the dispersion treatment was performed at a peripheral speed of 14 m / s for 8 hours to prepare a pigment dispersion liquid (MB -1).

Added pigment dispersion (MB-1) 56.54 g, P (ACA) Z250 3.14 g, DPHA 2.64 g, NCI-831 0.330 g, BYK (registered trademark) -333 0.04 g, as the polymerization inhibitor Tributyl catechol 0.01 g and PGMEA 37.30 g were used to prepare a resin composition for a light-shielding partition.

Preparation Example 26 A low-refractive index layer forming material was 5.350 g of a polysiloxane solution (LS-1) containing silicon dioxide particles obtained in Synthesis Example 13, 1.170 g of ethylene glycol mono-third butyl ether, and DAA. After mixing 3.48 g, it was filtered with a 0.45 μm syringe filter to prepare a low refractive index layer forming material.

Evaluation methods in Examples and Comparative Examples are shown below.

<Refractive index of white pigment>
Regarding the (A) white pigment used in each of the examples and comparative examples, the refractive index measurement method of plastics specified in JIS K7142-2014 (date of establishment: 2014/04/20) uses the B method (using a microscope) The liquid immersion method (Becke's line method) was used to measure the refractive index. The measurement wavelength was set to 587.5 nm. The "contact liquid" manufactured by Shimadzu Corporation was used instead of the JIS K7142-2014. The immersion liquid was measured at a temperature of immersion liquid: 20 ° C. As a microscope, a polarizing microscope "OPTIPHOTO" (manufactured by Nikon Corporation) was used. 30 samples of (A) white pigment were prepared each Each refractive index was measured, and the average value was made into a refractive index.

<Refractive index of silicone resin or acrylic resin>
The refractive index of the siloxane resin or acrylic resin used in each Example and Comparative Example was determined by the following method. The siloxane resin solution in Synthesis Examples 1 to 9 or the acrylic resin solution in Synthesis Example 10 was applied to a silicon wafer by a spinner, and dried on a 90 ° C. hot plate for 2 minutes. Thereafter, an oven (IHPS-222; manufactured by Espec Co., Ltd.) was used, and it was aged in air at 230 ° C for 30 minutes to produce a cured film. Using a europium coupler (PC-2000 (manufactured by Metricon)) at 20 ° C under atmospheric pressure, light at a wavelength of 587.5 nm was irradiated from a direction perpendicular to the surface of the cured film to measure refraction. Rate, rounded to the third decimal place.

<Resolution>
Using a spin coater (trade name: 1H-360S, manufactured by Mikasa), the negative photosensitive coloring composition obtained in each example and comparative example was cured to a film thickness of 10 A μm method was spin-coated on a 10 cm square alkali-free glass substrate, and a heating plate (trade name SCW-636, manufactured by Dainippon Screen Manufacturing Co., Ltd.) was used to pre-bake at 90 ° C for 2 minutes to prepare a film. 10 μm thick pre-baked film.

For the prepared pre-baking film, a parallel light mask alignment exposure machine (brand name PLA-501F, manufactured by Cannon) was used, and an ultra-high pressure mercury lamp was used as a light source with a 100 μm, 80 μm distance Masks with line and space patterns of widths of 60 μm, 50 μm, 40 μm, and 30 μm are exposed with a gap of 100 m in an exposure amount of 150 mJ / cm ² (i-ray). Thereafter, using an automatic developing device ("AD-2000 (trade name)" manufactured by Takizawa Industries Co., Ltd.), spray development was performed using a 0.045 wt% potassium hydroxide aqueous solution for 100 seconds, and then water was used for 30 seconds to rinse.

Using a microscope adjusted to a magnification of 100 times, the developed pattern was enlarged and observed, and the narrowest line width in the pattern in which no residue was not found in the unexposed portion was set as the resolution. Among them, the case where there is residue in the unexposed portion near the 100 μm wide pattern is set to “> 100 μm”.

<Visual reflectance>
Using a spin coater (trade name: 1H-360S, manufactured by Mikasa), the negative photosensitive coloring composition obtained in each example and comparative example was cured to a film thickness of 10 The method of μm was spin-coated on a 10 cm square alkali-free glass substrate, and a heating plate (SCW-636) was used to pre-bake at 90 ° C for 2 minutes to form a pre-baking film. The prepared pre-baking film was exposed, developed, and rinsed in the same manner as the evaluation method of <Resolution> except that the mask was not cut off. Furthermore, using an oven (trade name: IHPS-222, manufactured by Espec Corporation), it was aged in air at a temperature of 230 ° C for 30 minutes to produce a cured film.

Regarding the alkali-free glass substrate having a cured film, a spectrophotometer (trade name CM-2600d, manufactured by Konica Minolta) was used to measure the reflection chromaticity of the cured film from the glass substrate side. Evaluation was performed based on the C value of Y (visual reflectance). Among them, when cracks occur in the cured film, accurate values cannot be obtained due to cracks or the like, and thus the measurement of visual reflectance is not performed.

＜ Reflectivity ＞
Using a spin coater (trade name: 1H-360S, manufactured by Mikasa), the negative photosensitive coloring composition obtained in each example and comparative example was cured to a film thickness of 10 The method of μm was spin-coated on a 10 cm square alkali-free glass substrate, and a heating plate (SCW-636) was used to pre-bake at 90 ° C for 2 minutes to form a pre-baking film. The prepared pre-baking film was exposed, developed, and rinsed in the same manner as the evaluation method of <Resolution> except that the mask was not cut off. Furthermore, using an oven (trade name: IHPS-222, manufactured by Espec Corporation), it was aged in air at a temperature of 230 ° C for 30 minutes to produce a cured film.

Regarding the alkali-free glass substrate with a cured film, a spectrophotometer (trade name: CM-2600d, manufactured by Konica Minolta) was used to measure the wavelength at 550 nm using the SCI mode from the entire film side. Reflectivity. Among them, when a crack occurs in the entire film, since a correct value cannot be obtained due to cracks or the like, the measurement of the reflectance is not performed.

＜ heat resistance-1 crack resistance ＞
Using a spin coater (1H-360S; manufactured by Mikasa Co., Ltd.), the negative-type photosensitive coloring composition obtained in each Example and Comparative Example was cured to a film thickness of 5 μm, 10 μm, 15 μm, and 20 μm were coated on a 10 cm square alkali-free glass substrate, respectively, using a hot plate (SCW-636) and pre-baking at 90 ° C for 2 minutes to form a pre-baking film. The prepared pre-baking film was exposed, developed, and rinsed in the same manner as the evaluation method of <Resolution> except that the mask was not cut off. Furthermore, using an oven (trade name: IHPS-222, manufactured by Espec Corporation), it was aged in air at a temperature of 230 ° C for 30 minutes to produce a cured film.

The produced cured film was visually observed, and the presence or absence of cracks was evaluated. When one crack was confirmed, it was judged that there was no crack resistance of the said film thickness. For example, when there are no cracks in the film thickness of 15 μm and there are cracks in the film thickness of 20 μm, the crack-resistant film thickness is determined to be “≦ 15 μm”. In addition, the crack-resistant film thickness when no cracks even at 20 μm was determined to be “≧ 20 μm”, and the crack-resistant film thickness when cracks were even at 5 μm was determined to be “<5 μm”, and set as Added crack resistance before aging.

The hardened film without cracks was further cured using an oven (IHPS-222) in the air at a temperature of 240 ° C for 2 hours, and then the presence or absence of cracks was similarly evaluated. Sex.

＜ heat resistance-2 color change ＞
Using a spin coater (1H-360S; manufactured by Mikasa Co., Ltd.), the negative photosensitive coloring composition obtained in each Example and Comparative Example was cured to a film thickness of 10 μm. The method was applied to a 10 cm square alkali-free glass substrate, and a cured film was produced in the same manner as in the above-mentioned evaluation method of "heat resistance-1 crack resistance". However, when cracks occurred in the cured film, the remaining evaluation was not performed.

Regarding the obtained alkali-free glass substrate having a cured film, a spectrophotometer (trade name: CM-2600d, manufactured by Konica Minolta) was used to measure the reflection color of the cured film from the glass substrate side. Degree, the yellow hue is evaluated by the b * value when displayed in the CIE1976 (L *, a *, b *) color space, and is set as the color characteristic before maturation. As the light source, a C light source was used.

Regarding the cured film for evaluating color characteristics, an oven (IHPS-222) was further used to perform additional curing in the air at a temperature of 240 ° C for 2 hours, and then the reflection chromaticity was measured in the same manner. *) The value displayed in the color space is compared with the color characteristics before the additional curing, and the excellent difference is calculated by the following formula (I) (hereinafter, "ΔEab"). The smaller the ΔEab, the better the heat resistance. ΔEab is preferably 1.0 or less, and more preferably 0.7 or less.

ΔEab = (X1 ² + X2 ² + X3 ² ) ^0.5 Formula (I)

Here, X1, X2, and X3 are as follows.
X1: {L * (0)}-{L * (1)}
X2: {a * (0)}-{a * (1)}
X3: {b * (0)}-{b * (1)}
Among them, L * (0), a * (0), and b * (0) respectively represent the values of L *, a *, and b * before additional ripening, and L * (1), a * (1), and b * (1) Respective values of L *, a *, and b * after additional ripening.

＜ OD value ＞
As a model of the partition wall of the substrate with a partition wall obtained by each of the examples and comparative examples, the entire film was produced on a glass substrate in the same manner as the evaluation method of the <reflectance>. About the obtained glass substrate with an integral film, the intensity of incident light and transmitted light was measured using an optical densitometer (361T (vision); manufactured by X-rite), and the optical value was calculated according to the following formula (10) Concentration (OD value).

OD value = log10 （I ₀ / I） ··· Formula (10)

I ₀ : incident light intensity
I: transmitted light intensity.

＜ Surface contact angle ＞
As a model of the partition wall of the substrate with a partition wall obtained by each of the examples and comparative examples, the entire film was produced on a glass substrate in the same manner as the evaluation method of the <reflectance>. As for the obtained integral membrane, DM-700 manufactured by Kyowa Interface Science Co., Ltd. and a microinjector: Teflon (registered trademark) coated needle 22G for a contact angle meter manufactured by Kyowa Interface Science Co., Ltd., The surface contact angle with respect to propylene glycol monomethyl ether acetate was measured at 25 ° C in the air in accordance with the wettability test method of the substrate glass surface specified in JIS R3257 (date of establishment: 1999/04/20).

<Inkjet coating properties>
In the substrate with a partition wall obtained before forming the layer (G) containing a color conversion luminescent material obtained in each of the examples and comparative examples, PGMEA was used as the ink for the pixel portion surrounded by the grid-shaped partition wall. Inkjet coating was performed using an inkjet coating device (InkjetLabo, Cluster Technology (Stock)). 160 pL of PGMEA was applied to each grid pattern, and the presence or absence of breakage (the phenomenon that the ink crosses the partition wall and mixed into the adjacent pixel portion) was observed, and the inkjet coating property was evaluated by the following criteria. The less breakout, the higher the liquid repellency, and the better the inkjet coatability.
A: The ink does not overflow from the pixels.
B: In some parts, the ink overflowed from the pixels to the upper surface of the partition wall.
C: The ink overflowed from the pixels on the entire surface to the upper surface of the partition wall.

＜ Thickness ＞
With respect to the substrate with a partition wall obtained in each of the examples and comparative examples, a SURFCOM stylus-type film thickness measuring device was used to measure the structure of the structure before and after the layer (G) containing the color conversion light-emitting material was formed. The difference in thickness is calculated, and the thickness of the layer (G) containing the color conversion luminescent material is measured. The thickness of the low refractive index layer (H) was measured in the same manner as in Examples 20 to 22, the thickness of the color filter was measured in the same manner as in Examples 23 to 24, and the shading was measured in the same manner as in Example 26. Wall thickness (height).

In addition, regarding Examples 21 to 22 and Examples 24 to 25, a cross section perpendicular to the substrate was exposed using a polishing device such as a cross section polisher, and the cross section was enlarged using a scanning electron microscope or a transmission electron microscope. By observation, the thicknesses of the inorganic protective layer I to the inorganic protective layer IV were measured.

<Brightness>
A planar light-emitting device equipped with a commercially available LED backlight (peak wavelength of 465 nm) was used as a light source, and the bands obtained in the respective examples and comparative examples were isolated so that the layer containing the color-converting light-emitting material became the light source side The wall substrate is provided on the planar light-emitting device. A current of 30 mA was passed through the planar light-emitting device to illuminate the LED element, and a spectroradiance meter (CS-1000, manufactured by Konica Minolta) was used to measure the brightness (unit: CIE1931) : Cd / cm ² ) and set the initial brightness. Here, the evaluation of the brightness was performed by setting the initial brightness of Comparative Example 9 to a relative value of 100 as a standard. In addition, in the case where a crack occurs in the partition wall, an accurate value cannot be obtained due to a crack or the like, and therefore, the evaluation was not performed.

In addition, at room temperature (23 ° C) conditions, after the LED element was turned on for 48 hours, the brightness was measured in the same manner, and the change in brightness over time was evaluated. Here, the evaluation of the brightness was performed by setting the initial brightness of Comparative Example 9 to a relative value of 100.

＜ Color characteristics ＞
On the commercially available white reflecting plate, a substrate with a partition wall obtained in each of Examples and Comparative Examples was provided so that a layer containing a color conversion light-emitting material was arranged on the white reflecting plate side. A spectrophotometer (CM-2600d, manufactured by Konica Minolta, measuring diameter f8 mm) was used to irradiate light from the substrate side, and the spectrum including regular reflection light was measured.

The color gamut defined by the color standard BT.2020, which can almost reproduce the colors of nature, is defined as the three primary colors of red, green and blue on the spectral locus shown in the chromaticity diagram. The wavelengths of red, green and blue are equivalent to 630. nm, 532 nm, and 467 nm. Based on the reflectance (R) of three wavelengths of 470 nm, 530 nm, and 630 nm of the obtained reflection spectrum, the light emission color of the layer containing the color conversion light emitting material was evaluated according to the following criteria.
A: R ₅₃₀ / (R ₆₃₀ + R ₅₃₀ + R ₄₇₀ ) ≧ 0.55
B: 0.55> R ₅₃₀ / (R ₆₃₀ + R ₅₃₀ + R ₄₇₀ ).

＜ Display characteristics ＞
The display characteristics of a display device produced by combining a substrate with a partition wall obtained in each Example and Comparative Example and an organic EL element were evaluated based on the following criteria.
A: The green display is very bright, and it is a bright and excellent display device.
B: Although a slightly unnatural color was observed, it was a display device without a problem.

Examples 1 to 13 and Comparative Examples 1 to 7
Regarding the negative-type colored photosensitive composition of Production Examples 1 to 20, the resolution, visual reflectance, and heat resistance were evaluated according to the evaluation method. The evaluation results are shown in Tables 6 to 8.

[TABLE 6]

[TABLE 6]

[TABLE 7]

[TABLE 7]

[TABLE 8]

[TABLE 8]

Examples 14 to 26, Comparative Examples 8 to 9
Regarding the substrate with a partition wall obtained by the negative-type colored photosensitive composition of Preparation Example 15 to Preparation Example 21, the reflectance, OD value, surface contact angle, inkjet coating property, and thickness were evaluated according to the evaluation method. , Brightness, color characteristics and display characteristics. However, in Comparative Example 8, cracks occurred in the cured film and the partition wall, and accurate values could not be obtained. Therefore, evaluation was not performed. Table 9 shows the configurations of the respective examples and comparative examples, and Table 10 shows the evaluation results.

[TABLE 9]
[TABLE 9]

[TABLE 10]
[TABLE 10]

1‧‧‧ substrate

2‧‧‧ wall

3‧‧‧ Layer containing color-converting luminescent material

4‧‧‧ low refractive index layer

5‧‧‧Inorganic protective layer I

6‧‧‧ Inorganic protective layer II

7‧‧‧ color filter

8‧‧‧ Inorganic protective layer III

9‧‧‧ Inorganic protective layer IV

10‧‧‧ Shading partition

11‧‧‧ glass substrate

12‧‧‧white light-shielding hardened film

13‧‧‧ transparent electrode

14‧‧‧ transparent insulating film

15‧‧‧Metal wiring

L‧‧‧ Width of the wall

X‧‧‧Thickness of the wall

FIG. 1 is a cross-sectional view showing one aspect of a substrate with a partition wall of the present invention having a partition wall patterned.

FIG. 2 is a cross-sectional view showing one aspect of a substrate with a partition wall of the present invention, which includes a patterned partition wall and a layer containing a color-converting luminescent material.

3 is a cross-sectional view showing an aspect of the substrate with a partition wall of the present invention having a low refractive index layer.

FIG. 4 is a cross-sectional view showing an aspect of the substrate with a partition wall of the present invention having a low refractive index layer and an inorganic protective layer I. FIG.

5 is a cross-sectional view showing an aspect of the substrate with a partition wall of the present invention having a low refractive index layer and an inorganic protective layer II.

FIG. 6 is a cross-sectional view showing an embodiment of the substrate with a partition wall of the present invention having a color filter.

FIG. 7 is a cross-sectional view showing an aspect of the substrate with a partition wall of the present invention including a color filter and an inorganic protective layer III.

FIG. 8 is a cross-sectional view showing an aspect of the substrate with a partition wall of the present invention having an inorganic protective layer IV.

9 is a cross-sectional view showing an aspect of the substrate with a partition wall of the present invention having a light-shielding partition wall.

FIG. 10 is a schematic view showing an example of a cross section of a touch panel of the present invention.

11a to 11d are schematic views showing an example of a method for manufacturing a touch panel of the present invention.

Claims (28)

A negative photosensitive coloring composition comprising (A) a white pigment, (B) a siloxane resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an organic solvent. (B) The siloxane resin contains at least a repeating unit represented by the following general formula (1) and / or a repeating unit represented by the following general formula (2), and a compound represented by the following general formula (3) The repeating unit, in which all the repeating units of the (B) siloxane resin, include a repeating unit represented by the following general formula (1) in a total of 40 mol% to 80 mol% and the following general formula (2) The repeating unit indicated; In the general formulae (1) to (3), R ¹ represents an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms in which all or a part of hydrogen is substituted with fluorine; R ² Represents a single bond, -O-, -CH ₂ -CO-, -CO-, or -O-CO-; R ³ represents a monovalent organic group having 1 to 20 carbon atoms; R ⁴ may be the same or different, respectively, representing carbon A monovalent organic group of 1 to 20. The negative photosensitive coloring composition according to item 1 of the scope of application, wherein the (D) photopolymerizable compound includes a compound having an ethylenically unsaturated double bond and a fluorine atom. The negative photosensitive coloring composition according to item 1 or item 2 of the scope of the patent application, wherein the refractive index of the (B) siloxane resin at a wavelength of 587.5 nm is 1.35 to 1.55. The negative photosensitive coloring composition according to any one of claims 1 to 3, wherein the refractive index of the (A) white pigment at a wavelength of 587.5 nm is 2.00 to 2.70. The negative photosensitive coloring composition according to any one of claims 1 to 4, in which the refractive index of the (A) white pigment and (B) the siloxane resin at a wavelength of 587.5 nm The difference is 1.16 to 1.26. The negative photosensitive coloring composition according to any one of claims 1 to 5, wherein the (A) white pigment contains a material selected from the group consisting of titanium dioxide, zirconia, zinc oxide, barium sulfate, and these Particles of a compound in a composite compound, and the median diameter of the particles is 100 nm to 500 nm. The negative photosensitive coloring composition according to any one of claims 1 to 6 in the scope of the patent application, wherein the content of the (B) siloxane resin in the solid content is 10% by weight to 60% by weight, and the content of the (A) white pigment is 20% to 60% by weight. The negative photosensitive coloring composition according to any one of claims 1 to 7 of the scope of patent application, which is used to form an isolation having a reflectance of 60% to 90% per 10 μm thickness at a wavelength of 550 nm wall. A cured film which is a cured film of the negative photosensitive coloring composition according to any one of claims 1 to 7 in the scope of patent application. A method for manufacturing a hardened film, which manufactures the hardened film according to item 9 of the scope of patent application, the manufacturing method includes: (I) a step of applying a negative photosensitive coloring composition as described in any one of claims 1 to 8 on a substrate to form a coating film; (II) a step of exposing and developing the coating film; and (III) a step of heating the developed coating film. A patterned processed substrate has a patterned hardened film as described in item 9 of the scope of patent application on the substrate. A substrate with a partition wall, which has a patterned partition wall including a hardened film as described in item 9 of the patent application scope on the substrate, and the reflectance of the partition wall with a thickness of 10 μm at a wavelength of 550 nm 60% to 90%. The substrate with a partition wall according to item 12 of the scope of application for a patent, wherein the patterned partition wall has a surface contact angle with respect to propylene glycol monomethyl ether acetate of 10 ° to 70 °. The substrate with a partition wall according to item 12 or 13 of the scope of patent application, further comprising a pattern with an optical concentration of 0.1 to 4.0 per 1.0 μm in thickness between the substrate and the patterned partition wall. The formed light-shielding partition. The substrate with a partition wall according to any one of claims 12 to 14 in the scope of the patent application, which has a layer containing a color-converting luminescent material between adjacent partition walls. The substrate with a partition wall according to item 15 of the scope of patent application, wherein the color conversion light-emitting material contains an inorganic phosphor and / or an organic phosphor. The substrate with a partition wall according to item 16 of the scope of the patent application, wherein the color-converting luminescent material contains a phosphor that emits red or green fluorescent light when excited by blue excitation light. The substrate with a partition wall according to item 16 or item 17 of the scope of patent application, wherein the color conversion light-emitting material contains quantum dots. The substrate with a partition wall according to item 16 or 17 of the scope of application for a patent, wherein the color conversion light-emitting material contains a pyrrole methylene derivative. The substrate with a partition wall according to any one of claims 15 to 19, wherein the layer containing the color conversion light-emitting material further has a refractive index at a wavelength of 550 nm of 1.20 to 1.35 Low refractive index layer. The substrate with a partition wall according to item 20 of the scope of application for a patent, wherein the low-refractive index layer having a refractive index of 1.20 to 1.35 at the wavelength of 550 nm further includes an inorganic protective layer having a thickness of 50 nm to 1,000 nm. I. The substrate with a partition wall according to item 20 or 21 of the scope of patent application, wherein the low refractive index layer having a refractive index of 1.20 to 1.35 at the wavelength of 550 nm further has a thickness of 50 nm to 1,000 nm Inorganic protective layer II. The substrate with a partition wall according to any one of claims 15 to 22, wherein a color filter having a thickness of 1 μm to 5 μm is further provided between the substrate and a layer containing a color conversion luminescent material. Light film. The substrate with a partition wall according to item 23 of the scope of application for a patent, further comprising an inorganic protective layer III having a thickness of 50 nm to 1,000 nm between the color filter and a layer containing a color conversion luminescent material. The substrate with a partition wall according to any one of claims 12 to 24, wherein the substrate further has an inorganic protective layer IV with a thickness of 50 nm to 1,000 nm. The substrate with a partition wall according to any one of claims 20 to 25, wherein the inorganic protective layer I, the inorganic protective layer II, the inorganic protective layer III, and the inorganic protective layer IV include a member selected from nitrogen One or more of silicon oxide and silicon oxide. A display device having the substrate with a partition wall according to any one of claims 12 to 26 in the scope of application for a patent; and a display device selected from a liquid crystal cell, an organic electroluminescence unit, a micro light emitting diode unit, and a micro Light source in a light emitting diode unit. A touch panel includes the patterned processing substrate, transparent electrodes, metal wiring, and a transparent film according to item 11 of the scope of patent application.