JP7201062B2 - Substrate with partition wall and display device - Google Patents

Description

The present invention relates to a partition-attached substrate having patterned partitions and a display device.

A liquid crystal display device, which is one type of image display device, generally performs color display using a white light source such as an LED and a color filter that selectively allows red, green, and blue to pass through. However, color display using such color filters has a problem of poor light utilization efficiency and color reproducibility.

Therefore, as a color display device with high light utilization efficiency, a color display device including a wavelength conversion section made of a wavelength conversion phosphor, a polarization separation means, and a polarization conversion means has been proposed (see, for example, Patent Document 1). ). For example, a blue light source, a liquid crystal element, a phosphor that emits red fluorescence when excited by blue light, a phosphor that emits green fluorescence when excited by blue light, and a light scattering layer that scatters blue light. A color display device including a conversion unit has been proposed (see, for example, Patent Document 2).
However, color filters containing color-converting phosphors, such as those described in Patent Documents 1 and 2, generate fluorescence in all directions, resulting in low light extraction efficiency and insufficient brightness. In particular, in high-definition display devices called 4K and 8K, since the pixel size is small, the problem of brightness becomes significant, and higher brightness is required.

JP-A-2000-131683 JP 2009-244383 A JP-A-2000-347394 JP 2006-259421 A

In order to improve the brightness of the display device, it is effective to increase the reflectance of the barrier ribs separating the color conversion phosphors. Moreover, in order to prevent color mixture of light between adjacent pixels, it is necessary to improve the light shielding property of the partition walls. From the above, there is a demand for a barrier rib material that achieves both high reflectance and light shielding properties.

In order to form barrier ribs having both high reflectance and light shielding properties, the inventors first investigated a method of using a material obtained by adding a black pigment to a high reflectance white barrier rib material. However, in this method, the white pigment and the black pigment absorb the light during exposure, and the light does not reach the bottom of the film, resulting in poor pattern processability.

On the other hand, as described in Patent Literatures 3 and 4, a technique has been proposed in which a specific metal compound is added to the material, and the material is blackened by firing after pattern formation. However, these blackening techniques require baking at 400° C. or higher, and there is a problem that the light-shielding property cannot be improved by heating at 250° C. or lower.

Accordingly, an object of the present invention is to provide a resin composition capable of forming partition walls having both high reflectance and light shielding properties even under heating conditions of 250° C. or lower.

The present invention provides a substrate with barrier ribs having (A-1) patterned barrier ribs on a base substrate, wherein the (A-1) patterned barrier ribs comprise a resin, a white pigment, black particles or The substrate with partition walls contains yellow particles and has a reflectance per 10 μm thickness of 20% to 60% at a wavelength of 550 nm and an OD value per 10 μm thickness of 1.0 to 3.0.

The substrate with partition walls of the present invention can improve the brightness of the display device by utilizing the reflection on the side surfaces of the partition walls. On the other hand, it is possible to suppress color mixture of light between adjacent pixels by suppressing light passing through the partition wall .

1 is a cross-sectional view showing one embodiment of a substrate with partitions of the present invention having patterned partitions. FIG. 1 is a cross-sectional view showing one embodiment of a substrate with partitions of the present invention having pixels containing patterned partitions and a color-converting luminescent material; FIG. 1 is a cross-sectional view showing one embodiment of a substrate with partition walls of the present invention having a low refractive index layer; FIG. 1 is a cross-sectional view showing one embodiment of a substrate with partition walls of the present invention having a low refractive index layer and an inorganic protective layer I. FIG. 1 is a cross-sectional view showing one embodiment of a substrate with partition walls of the present invention having a low refractive index layer and an inorganic protective layer II. FIG. FIG. 2 is a cross-sectional view showing one mode of the substrate with partition walls of the present invention having a color filter. 1 is a cross-sectional view showing one embodiment of a substrate with partition walls of the present invention having a color filter, an inorganic protective layer III and/or a yellow organic protective layer; FIG. FIG. 2 is a cross-sectional view showing one embodiment of the substrate with partition walls of the present invention having a color filter, an inorganic protective layer IV and/or a yellow organic protective layer. FIG. 2 is a cross-sectional view showing one mode of the partition-attached substrate of the present invention having light-shielding partition walls. FIG. 2 is a cross-sectional view showing the configuration of a display device used for color mixture evaluation in Examples.

Hereinafter, preferred embodiments of the resin composition, the light-shielding film formed from the resin composition, the method for producing the light-shielding film, and the substrate with partition walls according to the present invention will be specifically described. It is not limited to the form of , and can be implemented with various changes depending on the purpose and application.

The resin composition of the present invention can be suitably used as a material for forming partitions separating color-converting phosphors. The resin composition of the present invention is an organometallic compound (hereinafter sometimes referred to as "organometallic compound") containing a resin and at least one metal selected from the group consisting of silver, gold, platinum and palladium. , a photopolymerization initiator or a quinonediazide compound, and a solvent.

The resin has a function of improving crack resistance and light resistance of the partition walls. The content of the resin in the solid content of the resin composition is preferably 10% by weight or more, more preferably 20% by weight or more, from the viewpoint of improving the crack resistance of the partition walls during heat treatment. On the other hand, from the viewpoint of improving light resistance, the resin content in the solid content of the resin composition is preferably 60% by weight or less, more preferably 50% by weight or less. Here, the solid content means all the components excluding volatile components such as solvent among the components contained in the resin composition. The amount of solids can be determined by heating the resin composition to evaporate volatile components and weighing the residue.

Examples of resins include polysiloxane, polyimide, polyimide precursors, polybenzoxazole, polybenzoxazole precursors, and (meth)acrylic polymers. Here, (meth)acrylic polymer means a polymer of methacrylic acid ester and/or acrylic acid ester. You may contain 2 or more types of these. Among these, polysiloxane is preferable because it is excellent in transparency, heat resistance and light resistance.

Polysiloxane is a hydrolysis/dehydration condensate of organosilane. When the resin composition of the present invention has negative photosensitivity, the polysiloxane preferably contains at least a repeating unit represented by the following general formula (2). Further, other repeating units may be included. By including repeating units derived from the bifunctional alkoxysilane compound represented by the general formula (2), excessive thermal polymerization (condensation) of polysiloxane due to heating can be suppressed, and the crack resistance of the partition walls can be improved. It is preferable that the polysiloxane contains 10 to 80 mol % of repeating units represented by the general formula (2) in all repeating units. By including 10 mol % or more of the repeating unit represented by the general formula (2), the crack resistance can be further improved. The content of the repeating unit represented by formula (2) is more preferably 15 mol % or more, and even more preferably 20 mol % or more. On the other hand, by including 80 mol % or less of the repeating unit represented by the general formula (2), the molecular weight of the polysiloxane can be sufficiently increased during polymerization, and the coatability can be improved. The content of the repeating unit represented by formula (2) is more preferably 70 mol % or less.

In general formula (2) above, R ¹ and R ² , which may be the same or different, each represent a monovalent organic group having 1 to 20 carbon atoms. R ¹ and R ² are preferably groups selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms, from the viewpoint of facilitating adjustment of the molecular weight of polysiloxane during polymerization. However, in the alkyl group and the aryl group, at least part of the hydrogen atoms may be substituted with a radically polymerizable group. In this case, the radically polymerizable group may be radically polymerized in the cured product of the negative photosensitive resin composition.

When the resin composition of the present invention has negative photosensitivity, the polysiloxane is further selected from repeating units represented by the following general formula (3) and repeating units represented by the following general formula (4) It preferably contains repeating units. By including a repeating unit derived from a fluorine-containing alkoxysilane compound represented by general formula (3) or general formula (4), the refractive index of polysiloxane is reduced, and when a white pigment described later is contained, white By enlarging the refractive index difference with the pigment, the interface reflection can be further improved, and the reflectance can be further improved. More preferably, the total content of repeating units selected from repeating units represented by formula (3) and repeating units represented by formula (4) is 20 to 80 mol % in polysiloxane. By containing a total of 20 mol% or more of the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4), when the white pigment described later is contained, the interface between the polysiloxane and the white pigment Reflection can be further improved, and reflectance can be further improved. The total content of the repeating units represented by the general formula (3) and the repeating units represented by the general formula (4) is more preferably 40 mol % or more. On the other hand, by containing a total of 80 mol% or less of the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4), excessive hydrophobization of the polysiloxane is suppressed, and The compatibility with other components can be improved, and the resolution can be improved. The total content of the repeating units represented by the general formula (3) and the repeating units represented by the general formula (4) is more preferably 70 mol % or less. Further, other repeating units may be included.

In general formulas (3) and (4) above, R ³ represents an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 10 carbon atoms in which all or part of hydrogen atoms are substituted with fluorine. R ⁴ represents a single bond, -O-, -CH ₂ -CO-, -CO- or -O-CO-. R ⁵ represents a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of further reducing the refractive index of polysiloxane, R ³ is preferably an alkyl group having 1 to 6 carbon atoms in which all or part of the hydrogen atoms are substituted with fluorine. In addition, in the photocured product of the negative photosensitive resin composition, the alkenyl group may be radically polymerized.

The repeating units represented by the general formulas (2) to (4) are derived from alkoxysilane compounds represented by the following general formulas (5) to (7), respectively. That is, the polysiloxane containing repeating units represented by the general formulas (2) to (4) is hydrolyzed and alkoxysilane compounds containing alkoxysilane compounds represented by the following general formulas (5) to (7). It can be obtained by polycondensation. Other alkoxysilane compounds may also be used.

In general formulas (5) to (7), R ¹ to R ⁵ represent the same groups as R ¹ to R ⁵ in general formulas (2) to (4), respectively. R ⁶ , which may be the same or different, represents a monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.

Examples of alkoxysilane compounds represented by general formula (5) include dimethyldimethoxysilane, dimethyldiethoxysilane, ethylmethyldimethoxysilane, ethylmethyldimethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, and diphenyldimethoxysilane. , diphenyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, γ-Methacryloylpropylmethyldimethoxysilane, γ-Methacryloylpropylmethyldiethoxysilane, γ-Acryloylpropylmethyldimethoxysilane, γ-Acryloylpropylmethyldiethoxysilane, 3-Glycidoxypropylmethyldimethoxysilane, 3-Glycidoxypropyl Methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-dimethylmethoxysilylpropyl Succinic anhydride, 3-dimethylethoxysilylpropyl succinic anhydride, 3-dimethylmethoxysilylpropionic acid, 3-dimethylethoxysilylpropionic acid, 3-dimethylmethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-dimethylethoxysilylpropyl Cyclohexyldicarboxylic anhydride, 5-dimethylmethoxysilyl valeric acid, 5-dimethylethoxysilyl valeric acid, 3-dimethylmethoxysilylpropyl phthalic anhydride, 3-dimethylethoxysilylpropyl phthalic anhydride, 3-dimethylmethoxysilylpropyl phthalic anhydride, 3-dimethylethoxysilylpropyl phthalic anhydride, 4-dimethylmethoxysilylbutyric acid, 4-dimethylethoxysilylbutyric acid and the like. You may use 2 or more types of these.

Examples of the alkoxysilane compound represented by the general formula (6) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane, tridecafluorooctyltri methoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane and the like. You may use 2 or more types of these.

Examples of the alkoxysilane compound represented by the general formula (7) include bis(trifluoromethyl)dimethoxysilane, bis(trifluoropropyl)dimethoxysilane, bis(trifluoropropyl)diethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane and the like. You may use 2 or more types of these.

Other alkoxysilane compounds include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, trifunctional alkoxysilane compounds such as 3-ureidopropyltriethoxysilane; tetrafunctional alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane and silicate 51 (tetraethoxysilane oligomer); single compounds such as trimethylmethoxysilane and triphenylmethoxysilane; Functional alkoxysilane compounds; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl) Epoxy groups such as ethyltriethoxysilane, 3-ethyl-3-{[3-(trimethoxysilyl)propoxy]methyl}oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane or oxetane group-containing alkoxysilane compounds: phenyltrimethoxysilane, phenyltriethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, tolyltrimethoxysilane , tolyltriethoxysilane, 1-phenylethyltrimethoxysilane, 1-phenylethyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-trimethoxysilylpropylphthalic anhydride, 3 - aromatic ring-containing alkoxysilane compounds such as triethoxysilylpropyl phthalic anhydride; styryltrimethoxysilane, styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, γ- Acryloylpropyltrimethoxysilane, γ-Acrylo Radically polymerizable group-containing alkoxysilane compounds such as ylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane; 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 4- Trimethoxysilylbutyric acid, 4-triethoxysilylbutyric acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride , 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-triethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropyl phthalic anhydride, 3-triethoxysilylpropyl phthalic anhydride, etc. Containing alkoxysilane compounds and the like.

The content of the alkoxysilane compound represented by the general formula (5) in the alkoxysilane compound that is the raw material of the polysiloxane is the content of the repeating unit represented by the general formula (2) in all the repeating units of the polysiloxane. From the viewpoint of setting the amount within the above range, it is preferably 10 mol % or more, more preferably 15 mol % or more, and even more preferably 20 mol % or more. On the other hand, the content of the alkoxysilane compound represented by general formula (5) is preferably 80 mol % or less, more preferably 70 mol % or less, from the same viewpoint. Further, with respect to the total content of the alkoxysilane compounds represented by the general formulas (6) and (7), the total content of the repeating units represented by the general formulas (3) and (4) is is preferably 20 mol % or more, more preferably 40 mol % or more, from the viewpoint of making the range of On the other hand, the total content of the alkoxysilane compounds represented by general formulas (6) and (7) is preferably 80 mol % or less, more preferably 70 mol % or less, from the same viewpoint.

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

Polysiloxane can be obtained by hydrolyzing the aforementioned organosilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction in the presence or absence of a solvent.

Various conditions for hydrolysis can be set according to physical properties suitable for the intended use, taking into consideration the reaction scale, the size and shape of the reaction vessel, and the like. Various conditions include, for example, acid concentration, reaction temperature, and reaction time.

Acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acids and their anhydrides, and ion exchange resins can be used for the hydrolysis reaction. Among these, an acidic aqueous solution containing an acid selected from formic acid, acetic acid and phosphoric acid is preferred.

When an acid catalyst is used for the hydrolysis reaction, the amount of the acid catalyst added is 0.05 parts by weight with respect to 100 parts by weight of all the alkoxysilane compounds used in the hydrolysis reaction, from the viewpoint of making the hydrolysis proceed more rapidly. part or more is preferable, and 0.1 part by weight or more is more preferable. On the other hand, from the viewpoint of appropriately adjusting the progress of the hydrolysis reaction, the amount of the acid catalyst to be added is preferably 20 parts by weight or less, more preferably 10 parts by weight or less with respect to 100 parts by weight of all the alkoxysilane compounds. Here, the total amount of alkoxysilane compound means the amount including all of the alkoxysilane compound, its hydrolyzate and its condensate. The same shall apply hereinafter.

A hydrolysis reaction can be performed in a solvent. The solvent can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition.

When a solvent is generated by the hydrolysis reaction, hydrolysis can be performed without a solvent. When used in a resin composition, it is also preferable to adjust the resin composition to an appropriate concentration by further adding a solvent after the hydrolysis reaction is completed. It is also possible to distill off and remove all or part of the alcohol produced by heating and/or under reduced pressure after hydrolysis, and then add a suitable solvent.

When a solvent is used for the hydrolysis reaction, the amount of the solvent to be added is preferably 50 parts by weight or more, more preferably 80 parts by weight or more, based on 100 parts by weight of all the alkoxysilane compounds, from the viewpoint of suppressing gel formation. . On the other hand, the amount of the solvent to be added is preferably 500 parts by weight or less, more preferably 200 parts by weight or less with respect to 100 parts by weight of all the alkoxysilane compounds, from the viewpoint of accelerating the hydrolysis.

Moreover, ion-exchanged water is preferable as the water used for the hydrolysis reaction. Although the amount of water can be set arbitrarily, it is preferably 1.0 to 4.0 mol with respect to 1 mol of all alkoxysilane compounds.

Examples of the dehydration-condensation reaction method include a method of directly heating a silanol compound solution obtained by a hydrolysis reaction of an organosilane compound. The heating temperature is preferably 50° C. or higher and the boiling point of the solvent or lower, and the heating time is preferably 1 to 100 hours. Further, reheating or addition of a base catalyst may be performed in order to increase the degree of polymerization of polysiloxane. Depending on the purpose, after the dehydration condensation reaction, an appropriate amount of the alcohol produced may be distilled off under heating and/or under reduced pressure, and then a suitable solvent may be added.

From the viewpoint of storage stability of the resin composition, it is preferable that the siloxane resin solution after hydrolysis and dehydration condensation does not contain the catalyst, and the catalyst can be removed as necessary. As the method for removing the catalyst, washing with water, treatment with an ion-exchange resin, and the like are preferable from the viewpoint of ease of operation and removability. Water washing is a method of diluting a polysiloxane solution with a suitable hydrophobic solvent, washing with water several times, and then concentrating the resulting organic layer using an evaporator or the like. Ion exchange resin treatment is a method of contacting a polysiloxane solution with a suitable ion exchange resin.

When patterning the partition walls (A-1) described below, the organometallic compound decomposes and aggregates in the exposure step and/or the heating step to become black particles or yellow particles, and the OD of the partition walls (A-1) described below. It has the ability to improve value. Since the OD value is low before exposure and the OD value increases after pattern formation, the exposed light can be sufficiently transmitted to the bottom in the exposure process to cause photocuring or photodecomposition. For example, in the case of a resin composition having negative type photosensitivity, in order to form a partition wall (A-1) with a high OD value, if a pattern is formed in advance using a resin composition containing a large amount of black pigment, Photocuring tends to be insufficient. As a result, the shape of the obtained partition (A-1) tends to be a reverse tapered shape. When a pattern is formed using the resin composition of the present invention containing the aforementioned organometallic compound, the taper angle can be easily set within the preferred range described later, since sufficient photocuring is performed up to the bottom.

Examples of organometallic compounds include silver-containing organometallic compounds such as silver neodecanoate, silver octylate, and silver salicylate; Organometallic compounds; Organometallic compounds containing platinum such as bis(acetylacetonato)platinum, dichlorobis(triphenylphosphine)platinum, dichlorobis(benzonitrile)platinum; bis(acetylacetonato)palladium, dichlorobis(triphenylphosphine) Organometallic compounds containing palladium such as palladium, dichlorobis(benzonitrile)palladium, tetrakis(triphenylphosphine)palladium, dibenzylideneacetone palladium, and the like. You may contain 2 or more types of these.

Of these, when an organometallic compound containing silver such as silver neodecanoate, silver octylate, and silver salicylate is contained, it decomposes and aggregates in the exposure process to turn black, and further decomposes and aggregates in the subsequent heating process. yellowing.

On the other hand, organometallic compounds containing platinum such as bis(acetylacetonato)platinum, dichlorobis(triphenylphosphine)platinum, dichlorobis(benzonitrile)platinum; bis(acetylacetonato)palladium, dichlorobis(triphenylphosphine)palladium, If an organometallic compound selected from palladium such as dichlorobis(benzonitrile)palladium, tetrakis(triphenylphosphine)palladium, and dibenzylideneacetonepalladium is contained, blackening occurs due to decomposition and aggregation during the exposure process and/or heating process. do.

Among these, an organic metal compound selected from bis(acetylacetonato)palladium, dichlorobis(triphenylphosphine)palladium, dichlorobis(benzonitrile)palladium and tetrakis(triphenylphosphine)palladium from the viewpoint of further improving the OD value is preferred.

In the resin composition of the present invention, the content of the organometallic compound in the solid content is preferably 0.2 to 5% by weight. By setting the content of the organometallic compound to 0.2% by weight or more, the OD value of the obtained partition wall can be further improved. The content of the organometallic compound is more preferably 1.5% by weight or more. On the other hand, by setting the content of the organometallic compound to 5% by weight or less, the reflectance can be further improved.

The resin composition of the present invention preferably has negative or positive photosensitivity when used for pattern formation of partition walls (A-1) described below. When imparting negative photosensitivity, it is preferable to contain a photopolymerization initiator, and partition walls having a highly precise pattern can be formed. The negative photosensitive resin composition preferably further contains a photopolymerizable compound. On the other hand, when imparting positive photosensitivity, it is preferable to contain a quinonediazide compound.

Any photopolymerization initiator may be used as long as it decomposes and/or reacts with irradiation of light (including ultraviolet rays and electron beams) to generate radicals. For example, 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl α-Aminoalkylphenone compounds such as -phenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; 2,4,6-trimethylbenzoylphenyl Acylphosphine oxide compounds such as phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide ; 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], 1- Phenyl-1,2-butadione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, ethanone-1-[9-ethyl-6-(2- oxime ester compounds such as methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime); benzyl ketal compounds such as benzyl dimethyl ketal; 2-hydroxy-2-methyl-1-phenylpropane-1 -one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl - α-hydroxyketone compounds such as phenyl ketone; benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4- Benzophenone compounds such as dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenylsulfide, alkylated benzophenones, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone;2,2 - Acetophenone compounds such as diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, 4-azidobenzalacetophenone ; aromatic ketoester compounds such as methyl 2-phenyl-2-oxyacetate; ethyl 4-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, 2-benzoylbenzoic acid Examples include benzoic acid ester compounds such as methyl. You may contain 2 or more types of these.

From the viewpoint of effectively promoting radical curing, the content of the photopolymerization initiator in the resin composition of the present invention is preferably 0.01% by weight or more, more preferably 1% by weight or more, based on the solid content. On the other hand, from the viewpoint of suppressing the elution of the remaining photopolymerization initiator and the like and further improving yellowing, the content of the photopolymerization initiator is preferably 20% by weight or less, more preferably 10% by weight or less, in the solid content. preferable.

The photopolymerizable compound in the present invention refers to a compound having two or more ethylenically unsaturated double bonds in its molecule. Considering the easiness of radical polymerization, the photopolymerizable compound preferably has a (meth)acrylic group.

Examples of photopolymerizable compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane. triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetra Acrylates, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapenta Erythritol undecaacrylate, pentapentaerythritol dodecaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nona methacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol dodecamethacrylate, dimethylol- and tricyclodecane diacrylate. You may contain 2 or more types of these.

From the viewpoint of effectively promoting radical curing, the content of the photopolymerizable compound in the resin composition of the present invention is preferably 1% by weight or more based on the solid content. On the other hand, from the viewpoint of suppressing excessive reaction of radicals and improving resolution, the content of the photopolymerizable compound is preferably 40% by weight or less in the solid content.

As the quinonediazide compound, a compound in which a sulfonic acid of naphthoquinonediazide is bonded to a compound having a phenolic hydroxyl group via an ester is preferable. Compounds having a phenolic hydroxyl group used here include, for example, BIs-Z, TekP-4HBPA (tetrakis P-DO-BPA), TrIsP-HAP, TrIsP-PA, BIsRS-2P, BIsRS-3P (the above, commercial products name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-PC, BIR-PTBP, BIR-BIPC-F (trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.), 4,4'-sulfonyldiphenol, BPFL (trade name, manufactured by JFE Chemical Co., Ltd.). As the quinonediazide compound, those obtained by introducing 4-naphthoquinonediazide sulfonic acid or 5-naphthoquinonediazide sulfonic acid into these compounds having a phenolic hydroxyl group via an ester bond are preferable. manufactured by Toyo Gosei Co., Ltd.), SBF-525 (trade name, manufactured by AZ Electronic Materials Co., Ltd.), and the like.

From the viewpoint of improving sensitivity, the content of the quinonediazide compound in the resin composition of the present invention is preferably 0.5% by weight or more, more preferably 1% by weight or more, based on the solid content. On the other hand, the content of the quinonediazide compound is preferably 25% by weight or less, more preferably 20% by weight or less, based on the solid content, from the viewpoint of improving resolution.

The solvent has the function of adjusting the viscosity of the resin composition to a range suitable for application and improving the uniformity of the partition walls. As the solvent, it is preferable to combine a solvent having a boiling point of more than 150° C. and 250° C. or less under atmospheric pressure and a solvent having a boiling point of 150° C. or less.

Examples of solvents include alcohols such as ethanol, propanol, isopropanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl. Ethers such as ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; Ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclopentanone; Dimethylformamide, dimethylacetamide, etc. amides; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate , acetates such as butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, cyclohexane; γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide; You may contain 2 or more types of these. Among these, it is preferable to combine diacetone alcohol as a solvent with a boiling point of more than 150° C. and 250° C. or less under atmospheric pressure and propylene glycol monomethyl ether as a solvent with a boiling point of 150° C. or less from the viewpoint of coating properties.

The content of the solvent can be arbitrarily set according to the coating method and the like. For example, when forming a film by spin coating, the content of the solvent is generally 50% by weight or more and 95% by weight or less in the resin composition.

The resin composition of the present invention preferably further contains a coordinating compound having a phosphorus atom (hereinafter sometimes referred to as "coordinating compound"). The coordinating compound coordinates to the organometallic compound in the resin composition, improves the solubility of the organometallic compound in a solvent, promotes the decomposition of the organometallic compound, and further improves the OD value of the obtained partition walls. can be made Coordinating compounds include, for example, triphenylphosphine, tri-t-butylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-t-butylphosphine tetrafluoroborate, tri(2-furyl)phosphine, tris(1- adamantyl)phosphine, tris(diethylamino)phosphine, tris(4-methoxyphenyl)phosphine, tris(O-tolyl)phosphine and the like. You may contain 2 or more types of these. The content of the coordinating compound in the resin composition of the present invention is preferably 0.5 to 3.0 molar equivalents relative to the organometallic compound.

The resin composition of the invention preferably further contains a white pigment and/or a black pigment. A white pigment has a function of further improving the reflectance of the partition wall. A black pigment has the function of adjusting the OD value.

Examples of white pigments include titanium dioxide, zirconium oxide, zinc oxide, barium sulfate, and composite compounds thereof. You may contain 2 or more types of these. Among these, titanium dioxide is preferable because of its high reflectance and easy industrial use.

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

The white pigment may be surface-treated. Surface treatment with a metal selected from Al, Si and Zr is preferable, and the light resistance and heat resistance of the formed partition walls can be improved.

The median diameter of the white pigment is preferably 100 to 500 nm from the viewpoint of further improving the reflectance of the partition walls. Here, the median diameter of the white pigment can be calculated from the particle size distribution measured by laser diffraction using a particle size distribution analyzer (N4-PLUS; manufactured by Beckman Coulter, Inc.) or the like.

Titanium dioxide pigments preferably used as white pigments include, for example, R960 manufactured by DuPont (rutile type, SiO ₂ /Al ₂ O ₃ treatment, average primary particle size 210 nm), CR-97 manufactured by Ishihara Sangyo Co., Ltd. (rutile type, Al ₂ O ₃ /ZrO ₂ treatment, average primary particle size 250 nm), JR-301; Teika Co., Ltd. (rutile type, Al ₂ O ₃ treatment, average primary particle size 300 nm), JR-405 Tayca Co., Ltd. (rutile type, Al ₂ O ₃ treatment, average primary particle size 210 nm), JR-600A; Tayca Co., Ltd. (rutile type, Al ₂ O ₃ treatment, average primary particle size 250 nm), JR- 603; Teika Co., Ltd. (rutile type, Al ₂ O ₃ /ZrO ₂ treatment, average primary particle size 280 nm), and the like. You may contain 2 or more types of these.

From the viewpoint of further improving the reflectance, the content of the white pigment in the resin composition is preferably 20% by weight or more, more preferably 30% by weight or more, based on the solid content. On the other hand, from the viewpoint of improving the surface smoothness of the partition walls, the content of the white pigment is preferably 60% by weight or less, more preferably 55% by weight or less in the solid content.

Examples of black pigments include black organic pigments, mixed-color organic pigments, and black inorganic pigments.

Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone pigments. These may be coated with a resin.

Mixed organic pigments include, for example, pseudo-black pigments obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, magenta, cyan, and the like. Among these, a mixed pigment of a red pigment and a blue pigment is preferable from the viewpoint of achieving both a moderately high OD value and pattern workability. The weight ratio of the red pigment and the blue pigment in the mixed pigment is preferably 20/80 to 80/20, more preferably 30/70 to 70/30. Specific examples of representative pigments are shown below by color index (CI) number. Examples of red pigments include Pigment Red (hereinafter abbreviated as PR) 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, and PR220. , PR223, PR224, PR226, PR227, PR228, PR240, PR254, and the like. You may contain 2 or more types of these. Examples of blue pigments include Pigment Blue (hereinafter abbreviated as PB) 15, PB15:3, PB15:4, PB15:6, PB22, PB60 and PB64. You may contain 2 or more types of these.

Black inorganic pigments include, for example, graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, gold, platinum, and palladium; metal oxides; metal composite oxides; Metal sulfides; metal nitrides; metal oxynitrides; metal carbides and the like. You may contain 2 or more types of these.

Among the above black pigments, pigments selected from titanium nitride, zirconium nitride, carbon black, and mixed pigments having a weight ratio of 20/80 to 80/20 of red and blue pigments are preferred because they have high light-shielding properties. preferable. Furthermore, from the viewpoint of easily adjusting the taper angle of the partition wall (A-1) to the preferable range described later, titanium nitride, zirconium nitride, and a mixed pigment of a red pigment and a blue pigment at a weight ratio of 20/80 to 80/20 Selected pigments are more preferred.

The content of the black pigment in the resin composition is preferably 0.01% by weight or more in the solid content, from the viewpoint of further suppressing color mixing of light in adjacent pixels by adjusting the reflectance and OD to the ranges described above. 05% by weight or more is more preferred. On the other hand, from the viewpoint of adjusting the reflectance and OD within the ranges described above, the content of the black pigment is preferably 5% by weight or less, more preferably 3% by weight or less, based on the solid content.

The resin composition of the present invention preferably further contains a photobase generator. By containing a photobase generator, a base is generated in the exposure step, promoting decomposition and aggregation of the organometallic compound in the resin composition, so that the organometallic compound is more efficiently converted into black particles or yellow particles. It is possible to further improve the OD value of the barrier ribs obtained by conversion.

Any photobase generator can be used as long as it decomposes and/or reacts with irradiation of light (including ultraviolet rays and electron beams) to generate a base. For example, 2-(9-oxoxanthen-2-yl)propionate 1,5,7-triazacyclo[4,4,0]dec-5-ene, N-cyclohexylcarbamate 1-(anthraquinon-2-yl) ethyl, 9-anthrylmethyl N,N-diethylcarbamate, 9-anthrylmethyl N-cyclohexylcarbamate, 9-anthrylmethylpiperidine 1-carboxylate, 9-anthrylmethyl N,N-dicyclohexylcarbamate, 1-(anthraquinon-2-yl)ethyl N,N-dicyclohexylcarbamate, cyclohexylammonium 2-(3-benzoylphenyl)propionate, 1,2-dicyclohexyl-4,4,5,5 butyltriphenylboronate, -tetramethylbiguanidinium, 2-(3-benzoylphenyl)propionate 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium, (2-nitrophenyl)methyl 4-hydroxypiperidine-1- carboxylic acid, guanidinium 2-(3-benzoylphenyl)propionate, and the like. You may use 2 or more types of these.

From the viewpoint of further improving the OD value, the content of the photobase generator in the resin composition of the present invention is preferably 0.5% by weight or more based on the solid content. On the other hand, the content of the photobase generator is preferably 2.0% by weight or less in the solid content from the viewpoint of improving resolution.

The resin composition of the present invention may contain a liquid-repellent compound. A liquid-repellent compound is a compound that imparts the property of repelling water and organic solvents (liquid-repellent performance) to a resin composition. The compound is not particularly limited as long as it has such properties, but specifically, a compound having a fluoroalkyl group is preferably used. By containing the liquid-repellent compound, liquid-repellent performance can be imparted to the top of the partition wall (A-1) after the partition wall (A-1) is formed. As a result, for example, when forming pixels containing the (B) color-converting light-emitting material described later, color-converting light-emitting materials having different compositions can be easily applied to each pixel.

Examples of liquid-repellent compounds include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, and octaethylene. glycol di(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di(1,1,2, 2-tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8, 9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N-[3-(perfluorooctanesulfonamido)propyl]-N,N'-dimethyl- N-carboxymethylene ammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycine salt, bis(N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkyl Examples thereof include compounds having fluoroalkyl or fluoroalkylene groups at the terminal, main chain and/or side chain such as ethyl phosphate. In addition, commercially available liquid-repellent compounds include "Megafac" (registered trademark) F142D, F172, F173, F183, F444, and F477 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), F-top EF301, 303, and 352. (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC-430, FC-431 (manufactured by Sumitomo 3M Co., Ltd.), “Asahi Guard” (registered trademark) AG710, “Surflon” (registered trademark) S-382, SC -101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusho Co., Ltd.), NBX-15, Examples include FTX-218 and DFX-18 (manufactured by Neos Co., Ltd.). You may contain 2 or more types of these. Among these, those having a photopolymerizable group are more preferable because they are highly reactive and can form a strong bond with the resin. Liquid-repellent compounds having a fluorine atom and a photopolymerizable group include, for example, "Megafac" (registered trademark) RS-76-E, RS-56, RS-72-k, RS-75, RS-76-E , RS-76-NS, RS-76, and RS-90 (these are trade names, manufactured by DIC Corporation). In this case, the photopolymerizable group may be photopolymerized in the partition walls (A-1) made of the photocured product of the negative photosensitive resin composition.

From the viewpoint of improving the liquid-repellent performance of the partition wall and improving the inkjet applicability, the content of the liquid-repellent compound in the resin composition is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, based on the solid content. more preferred. On the other hand, from the viewpoint of improving compatibility with resins and white pigments, the content of the liquid-repellent compound is preferably 10% by weight or less, more preferably 5% by weight or less, based on the solid content.

Moreover, the resin composition of the present invention may contain an ultraviolet absorber, a polymerization inhibitor, a surfactant, an adhesion improver, and the like, if necessary.

By including an ultraviolet absorber in the resin composition of the present invention, the light resistance can be improved and the resolution can be further improved. UV absorbers include 2-(2H-benzotriazol-2-yl)phenol and 2-(2H-benzotriazol-2-yl)-4,6-tert-pentyl from the viewpoint of transparency and non-coloring properties. Phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazol-2-yl)-6-dodecyl-4- benzotriazole compounds such as methylphenol, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole; benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone; 2-(4, Triazine compounds such as 6-diphenyl-1,3,5triazin-2-yl)-5-[(hexyl)oxy]-phenol are preferably used.

By including a polymerization inhibitor in the resin composition of the present invention, the resolution can be further improved. Examples of polymerization inhibitors include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone and t-butylcatechol. In addition, commercially available polymerization inhibitors include "IRGANOX" (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, 295 (trade names, BASF Japan Ltd.) and the like. You may contain 2 or more types of these.

By including a surfactant in the resin composition of the present invention, it is possible to improve flowability during application. Surfactants include, for example, "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477 (trade names, manufactured by Dainippon Ink & Chemicals, Inc.), NBX- 15, fluorine-based surfactants such as FTX-218 (trade name, manufactured by Neos Co., Ltd.); Japan Co., Ltd.), polyalkylene oxide surfactants, poly(meth)acrylate surfactants, and the like. You may contain 2 or more types of these.

By including an adhesion improving agent in the resin composition of the present invention, the adhesion to the underlying substrate is improved, and highly reliable partition walls can be obtained. Examples of adhesion improvers include alicyclic epoxy compounds and silane coupling agents. Among these, alicyclic epoxy compounds have high heat resistance, and can further suppress color change after heating.

Examples of alicyclic epoxy compounds include 3′,4′-epoxycyclohexymethyl-3,4-epoxycyclohexanecarboxylate, 2,2-bis(hydroxymethyl)-1-butanol and 1,2-epoxy- 4-(2-oxiranyl)cyclohexane adduct, ε-caprolactone-modified 3′,4′-epoxycyclohexylmethyl 3′,4′-epoxycyclohexane carboxylate, 1,2-epoxy-4-vinylcyclohexane, butanetetracarboxylic acid Tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone, 3,4-epoxycyclohexylmethyl methacrylate, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, water Added bisphenol A bis(propylene glycol glycidyl ether) ether, hydrogenated bisphenol A bis(ethylene glycol glycidyl ether) ether, diglycidyl 1,4-cyclohexanedicarboxylate, diglycidyl 1,4-cyclohexanedimethanol, and the like. You may contain 2 or more types of these.

The content of the adhesion improving agent in the resin composition of the present invention is preferably 0.1% by weight or more, more preferably 1% by weight or more, based on the solid content, from the viewpoint of further improving the adhesion to the underlying substrate. . On the other hand, the content of the adhesion improver is preferably 20% by weight or less, more preferably 10% by weight or less in the solid content, from the viewpoint of further suppressing color change due to heating.

The resin composition of the present invention can be produced, for example, by mixing the aforementioned resin, organometallic compound, photopolymerization initiator or quinonediazide compound, solvent and, if necessary, other components.

Next, the light shielding film of the present invention will be explained. The light-shielding film of the present invention is obtained by curing the resin composition of the present invention described above. The light-shielding film of the present invention can be suitably used as a light-shielding pattern in an OGS type touch panel, such as a decorative pattern for a cover base material, in addition to the barrier ribs (A-1) described later. The film thickness of the light shielding film is preferably 10 μm or more.

Next, the method for producing the light-shielding film of the present invention will be described with an example. The method for producing a light-shielding film of the present invention includes a film-forming step of applying the resin composition of the present invention on a base substrate and drying to obtain a dry film, an exposure step of pattern-exposing the obtained dry film, and a It is preferable to have a developing step of dissolving and removing a portion of the dry film that is soluble in a developer and a heating step of heating and curing the dry film after development.

In the method for producing a light-shielding film of the present invention, in the heating step, the film after development is heated at a temperature of 120° C. or more and 250° C. or less, thereby increasing the OD value per 10 μm of film thickness by 0.3 or more. Characterized by From the viewpoint of further improving the OD value, the heating temperature in the heating step is preferably 150° C. or higher, more preferably 180° C. or higher. The heating temperature during the heating step is preferably 250° C. or lower, more preferably 240° C. or lower, from the viewpoint of suppressing crack generation in the heated film. The heating time is preferably 15 minutes to 2 hours. The film formed from the resin composition of the present invention has a low OD value at the time of exposure, and the OD value increases after pattern formation. Angular diaphragms can be obtained. In addition, since the OD value after pattern formation is high, it is possible to obtain partition walls having both high reflectance and light shielding properties.

Examples of the method of applying the resin composition in the film-forming step include a slit coating method and a spin coating method. Examples of the drying device include a hot air oven and a hot plate. The drying time is preferably 80 to 120° C., preferably 1 to 15 minutes.

The exposure step is a step of photocuring the necessary portion of the dry film by exposure or photolyzing the unnecessary portion of the dry film to make any portion of the dry film soluble in the developer. . In the exposure step, exposure may be performed through a photomask having a predetermined opening, or an arbitrary pattern may be directly drawn using a laser beam or the like without using a photomask.

Examples of the exposure device include a proximity exposure machine. The actinic rays irradiated in the exposure step include, for example, near-infrared rays, visible rays, and ultraviolet rays, and ultraviolet rays are preferred. Examples of the light source include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, halogen lamps, germicidal lamps, etc. Ultra-high-pressure mercury lamps are preferred.

Exposure conditions can be appropriately selected depending on the thickness of the dry film to be exposed. In general, it is preferable to perform exposure using an ultra-high pressure mercury lamp with an output of 1 to 100 mW/cm ² and an exposure amount of 1 to 10,000 mJ/cm ² .

In the development process, the developer-soluble portion of the dry film after exposure is dissolved and removed with the developer, leaving only the developer-insoluble portion, and the dry film patterned in an arbitrary pattern shape (hereinafter referred to as , which is called a pre-heating pattern). Examples of the pattern shape include shapes such as a lattice shape and a stripe shape.

The developing method includes, for example, an immersion method, a spray method, a brush method, and the like.

As the developer, a solvent capable of dissolving unnecessary portions in the dry film after exposure can be appropriately selected, and an aqueous solution containing water as a main component is preferable. For example, when the resin composition contains a polymer having a carboxyl group, the developer is preferably an alkaline aqueous solution. Examples of alkaline aqueous solutions include inorganic alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, and calcium hydroxide; organic alkaline aqueous solutions such as tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine; is mentioned. Among these, a potassium hydroxide aqueous solution or a tetramethylammonium hydroxide aqueous solution is preferable from the viewpoint of improving resolution. From the viewpoint of improving developability, the concentration of the alkaline aqueous solution is preferably 0.05% by weight or more, more preferably 0.1% by weight or more. On the other hand, the concentration of the alkaline aqueous solution is preferably 5% by weight or less, more preferably 1% by weight or less, from the viewpoint of suppressing peeling and corrosion of the pattern before heating. The developing temperature is preferably 20 to 50° C. in order to facilitate process control.

The heating step is a step of heating and curing the preheated pattern formed in the developing step. Examples of heating devices include hot plates and ovens. Preferred heating temperature and heating time are as described above.

Next, the board|substrate with a partition of this invention is demonstrated. The substrate with partition walls of the present invention has (A-1) patterned partition walls (hereinafter sometimes referred to as “partition walls (A-1)”) formed on an underlying substrate. The underlying substrate functions as a support for the substrate with partition walls. When pixels containing a color-converting luminescent material, which will be described later, are included, the partition has a function of suppressing color mixture of light between adjacent pixels.

In the substrate with partition walls of the present invention, the partition walls (A-1) have a reflectance of 20% to 60% per 10 μm thickness at a wavelength of 550 nm and an OD value of 1.0 to 3.0 per 10 μm thickness. Characterized by By setting the reflectance to 20% or more and the OD value to 3.0 or less, (A-1) the luminance of the display device can be improved by utilizing the reflection on the side surface of the partition wall. On the other hand, by setting the reflectance to 60% or less and the OD value to 1.0 or more, it is possible to suppress light passing through the partition wall (A-1) and suppress color mixture of light between adjacent pixels.

FIG. 1 shows a cross-sectional view of one mode of the substrate with partitions of the present invention having patterned partitions. A base substrate 1 has partition walls 2 patterned thereon.

<Underlying substrate>
Examples of the base substrate include a glass plate, a resin plate, and a resin film. Non-alkali glass is preferable as the material of the glass plate. Polyester, (meth)acrylic polymer, transparent polyimide, polyethersulfone and the like are preferable as materials for the resin plate and the resin film. The thickness of the glass plate and the resin plate is preferably 1 mm or less, more preferably 0.8 mm or less. The thickness of the resin film is preferably 100 μm or less.

<Partition (A-1)>
The barrier rib (A-1) has a reflectance of 20 to 60% per 10 μm thickness at a wavelength of 550 nm and an OD value of 1.0 to 3.0. Here, the thickness of the partition wall (A-1) refers to the length of the partition wall (A-1) in the direction perpendicular to the base substrate (height direction). In the case of the substrate with partition walls shown in FIG. The length of the partition wall (A-1) in the horizontal direction with respect to the underlying substrate is the width of the partition wall (A-1). In the case of the substrate with partition walls shown in FIG. 1, the width of the partition walls 2 is represented by symbol L.

In the present invention, it is considered that the reflectance on the side surface of the partition wall contributes to the improvement of the brightness of the display device, and the light shielding property of the partition wall contributes to the suppression of color mixture. On the other hand, since the reflectance per thickness and the OD value are considered to be the same regardless of the thickness direction and the width direction, the present invention focuses on the reflectance per thickness and the OD value of the partition walls. As will be described later, the partition wall (A-1) preferably has a thickness of 0.5 to 50 μm and a width of 5 to 40 μm. Therefore, in the present invention, 10 μm is selected as a representative value of the thickness of the partition (A-1), and the reflectance and OD value per 10 μm of thickness are focused on.

If the reflectance per 10 μm of thickness is less than 20%, the reflection on the side surface of the partition wall becomes small, resulting in insufficient luminance of the display device. The reflectance per 10 μm thickness is preferably 30% or more, more preferably 35% or more. The higher the reflectance, the greater the reflection on the side walls of the partition wall, so that the brightness of the display device can be improved. However, if the reflectance exceeds 60%, color mixture of light occurs between adjacent pixels. More preferably, the reflectance per 10 μm thickness is 44% or less.

Further, when the OD value per 10 μm of thickness is less than 1.0, color mixture of light occurs between adjacent pixels. The OD value per 10 µm of thickness is preferably 1.5 or more, more preferably 2.0 or more. On the other hand, if the OD value per 10 μm of thickness exceeds 3.0, the reflection on the side surface of the partition wall becomes small, resulting in insufficient brightness of the display device. The OD value per 10 µm of thickness is more preferably 2.5 or less.

The reflectance per 10 μm thickness of the partition wall (A-1) at a wavelength of 550 nm was measured using a spectrophotometer (for example, CM-2600d manufactured by Konica Minolta Co., Ltd.) from the top of the partition wall (A-1) with a thickness of 10 μm. can be measured by SCI mode. However, when a sufficient area for measurement cannot be secured, or when a measurement sample with a thickness of 10 μm cannot be collected, and the composition of the partition wall (A-1) is known, the same composition as the partition wall (A-1) A solid film having a thickness of 10 μm may be prepared, and the reflectance per 10 μm thickness may be obtained by similarly measuring the reflectance of the solid film instead of the partition wall (A-1). For example, using the material for forming the partition wall (A-1), a solid film was prepared under the same processing conditions as for the formation of the partition wall (A-1) except that the thickness was 10 μm and no pattern was formed. Reflectance may be similarly measured from the top surface of the film.

The OD value per 10 μm thickness of the partition wall (A-1) is obtained by measuring the incident light and the It can be calculated by measuring the intensity of transmitted light and using the following formula (1). However, when a sufficient area for measurement cannot be secured, or when a measurement sample with a thickness of 10 μm cannot be collected, and the composition of the partition (A-1) is known, the partition (A-1) A 10 μm-thick solid film having the same composition as A-1) may be prepared, and the OD value per 10 μm thickness may be obtained by similarly measuring the OD value of the solid film instead of the partition wall (A-1). .
OD value = log10( _I0 /I) (1)
I ₀ : incident light intensity I : transmitted light intensity.

In addition, as means for adjusting the reflectance and the OD value within the above ranges, for example, the partition (A-1) is made to have a preferable composition described later.

The taper angle of the partition wall (A-1) is preferably 45° to 110°. The taper angle of the partition wall (A-1) refers to the angle formed by the side and bottom sides of the cross section of the partition wall. In the case of the substrate with partition walls shown in FIG. 1, the taper angle of the partition walls 2 is represented by the symbol θ. By setting the taper angle to 45° or more, the difference in width between the upper portion and the bottom portion of the partition wall (A-1) is reduced, and the width of the partition wall (A-1) can be easily formed within the preferable range described later. . More preferably, the taper angle is 70° or more. On the other hand, by setting the taper angle to 110° or less, when pixels containing the (B) color-converting light-emitting material described later are formed by inkjet coating, it is possible to suppress the breakdown of the ink and improve the inkjet coating properties. can be done. Here, the collapse of ink refers to a phenomenon in which ink crosses over a partition and mixes into an adjacent pixel portion. The taper angle is more preferably 95° or less. The taper angle of the partition wall (A-1) is measured using an optical microscope (FE-SEM (eg, S-4800 manufactured by Hitachi, Ltd.)) at an acceleration voltage of 3. It can be obtained by observing at 0 kV and a magnification of 2,500 times and measuring the angle formed by the side and base of the cross section of the partition wall (A-1).

As means for adjusting the taper angle of the partition wall (A-1) within the above range, for example, the partition wall (A-1) is made to have a preferable composition described later, or the resin composition of the present invention described above is used. forming.

When the substrate with partition walls has pixels containing (B) a color-converting luminescent material described later, the thickness of the partition walls (A-1) is preferably larger than the thickness of the pixels. Specifically, the thickness of the partition wall (A-1) is preferably 0.5 μm or more, more preferably 10 μm or more. On the other hand, the thickness of the partition wall (A-1) is preferably 50 μm or less, more preferably 20 μm or less, from the viewpoint of extracting light emitted from the bottom of the pixel more efficiently. In addition, the width of the partition (A-1) is preferably sufficient to further improve the brightness by utilizing light reflection on the side of the partition and to further suppress color mixture of light in adjacent pixels due to light leakage. Specifically, the width of the partition is preferably 5 μm or more, more preferably 15 μm or more. On the other hand, the width of the partition wall (A-1) is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of securing a large light-emitting region of the pixel and further improving luminance.

The partition wall (A-1) has a repeating pattern for a predetermined number of pixels corresponding to the screen size of the image display device. The number of pixels of the image display device is, for example, 4000 horizontally and 2000 vertically. The number of pixels affects the resolution (fineness) of the displayed image. Therefore, it is necessary to form the number of pixels corresponding to the required image resolution and the screen size of the image display device, and it is preferable to determine the partition pattern formation dimensions accordingly.

The partition wall (A-1) is made of a resin, a white pigment, and at least one metal oxide or metal selected from the group consisting of palladium oxide, platinum oxide, gold oxide, silver oxide, palladium, platinum, gold and silver. It is preferable to contain particles (hereinafter sometimes referred to as “metal oxide particles or metal particles”). The resin has a function of improving crack resistance and light resistance of the partition walls. A white pigment has a function of further improving the reflectance of the partition wall. Metal oxide particles or metal particles have the function of adjusting the OD value and suppressing color mixture of light in adjacent pixels.

The resin and the white pigment are as described above as materials constituting the resin composition. The resin content in the partition walls (A-1) is preferably 10% by weight or more, more preferably 20% by weight or more, from the viewpoint of improving the crack resistance of the partition walls during heat treatment. On the other hand, from the viewpoint of improving light resistance, the resin content in the partition (A-1) is preferably 60% by weight or less, more preferably 50% by weight or less.

The content of the white pigment in the partition wall (A-1) is preferably 20% by weight or more, more preferably 30% by weight or more, from the viewpoint of further improving the reflectance. On the other hand, from the viewpoint of improving the surface smoothness of the partition walls, the content of the white pigment in the partition walls (A-1) is preferably 60% by weight or less, more preferably 55% by weight or less.

Metal oxide particles or metal particles refer to black particles or yellow particles generated by decomposition/aggregation of the organometallic compound in the resin composition described above in the exposure step and/or the heating step. The content of the metal oxide particles or metal particles in the partition wall (A-1) is 0.2% by weight from the viewpoint of further suppressing color mixing of light in adjacent pixels by adjusting the reflectance and OD within the ranges described above. 0.5% by weight or more is more preferable. On the other hand, from the viewpoint of adjusting the reflectance and OD to the ranges described above, the content of the metal oxide particles or metal particles in the partition wall (A-1) is preferably 5% by weight or less, more preferably 3% by weight or less. .

The partition (A-1) preferably further contains a liquid-repellent compound. By containing the liquid-repellent compound, liquid-repellent performance can be imparted to the partition wall (A-1). In addition, color-converting light-emitting materials having different compositions can be easily applied separately. The liquid-repellent compound is as described above as a material constituting the resin composition.

From the viewpoint of improving the liquid-repellent performance of the partition walls and improving the inkjet applicability, the content of the liquid-repellent compound in the partition walls (A-1) is preferably 0.01% by weight or more, more preferably 0.1% by weight or more. more preferred. On the other hand, from the viewpoint of improving compatibility with resins and white pigments, the content of the liquid-repellent compound in the partition wall (A-1) is preferably 10% by weight or less, more preferably 5% by weight or less.

The surface contact angle of the partition wall (A-1) with respect to propylene glycol monomethyl ether acetate is preferably 10° or more, more preferably 20° or more, from the viewpoint of improving inkjet applicability and facilitating separate coating of the color-converting luminescent material. More preferably, 40° or more is even more preferable. On the other hand, from the viewpoint of improving the adhesion between the partition wall and the underlying substrate, the surface contact angle of the partition wall (A-1) is preferably 70° or less, more preferably 60° or less. Here, the surface contact angle of the partition wall (A-1) conforms to the substrate glass surface wettability test method specified in JIS R3257 (enacted date = 1999/04/20) for the upper part of the partition wall. can be measured by As a method for adjusting the surface contact angle of the partition wall (A-1) to the above range, for example, a method using the liquid-repellent compound described above can be used.

As a method for patterning the barrier ribs (A-1) on the base substrate, a photosensitive paste method is preferable because the pattern shape can be easily adjusted. As a method for patterning barrier ribs by a photosensitive paste method, for example, the above-mentioned resin composition is applied onto a base substrate and dried to obtain a dry film. A method comprising an exposure step of pattern-wise exposing according to the shape, a developing step of dissolving and removing portions soluble in the developer in the dry film after exposure, and a heating step of curing the barrier ribs after development is preferred. The resin composition preferably has positive or negative photosensitivity. Pattern exposure may be performed through a photomask having a predetermined opening, or an arbitrary pattern may be directly drawn using a laser beam or the like without using a photomask. When the substrate with partition walls has a light-shielding partition wall (A-2), which will be described later, the partition wall (A-1) can be similarly patterned on the light-shielding partition wall (A-2). Each step is as described above for the method of manufacturing the light shielding film.

<Light shielding partition (A-2)>
In the substrate with partition walls of the present invention, (A-1) between the underlying substrate and the patterned partition walls, and (A-2) an OD value per 1.0 μm of thickness of 0.5 or more. It is preferable to have a pattern-formed partition (hereinafter sometimes referred to as a “light-shielding partition (A-2)”). By having the light-shielding partition (A-2), it is possible to improve light-shielding properties, suppress light leakage from the backlight in the display device, and obtain a high-contrast and clear image.

FIG. 6 shows a cross-sectional view showing one mode of the partition-attached substrate of the present invention having light-shielding partitions. It has partition walls 2 and light-shielding partition walls 7 patterned on a base substrate 1 , and pixels 3 are arranged in regions separated by the partition walls 2 and the light-shielding partition walls 7 .

The light-shielding partition (A-2) has an OD value of 0.5 or more per 1.0 μm of thickness. Here, the thickness of the light shielding partition (A-2) is preferably 0.5 to 10 μm, as will be described later. Therefore, in the present invention, 1.0 μm is selected as a representative value of the thickness of the partition wall (A-2), and attention is paid to the OD value per 1.0 μm of thickness. By setting the OD value per 1.0 μm of thickness to 0.5 or more, the light shielding property can be further improved, and a clearer image with higher contrast can be obtained. The OD value per 1.0 μm of thickness is more preferably 1.0 or more. On the other hand, the OD value per 1.0 μm of thickness is preferably 4.0 or less, which can improve pattern workability. The OD value per 1.0 μm of thickness is more preferably 3.0 or less. The OD value of the light-shielding partition wall (A-2) can be measured in the same manner as the OD value of the partition wall (A-1) described above. Incidentally, as a means for setting the OD value within the above range, for example, the light-shielding partition (A-2) is made to have a preferable composition described later.

The thickness of the light-shielding partition (A-2) is preferably 0.5 μm or more, more preferably 1.0 μm or more, from the viewpoint of improving light-shielding properties. On the other hand, from the viewpoint of improving flatness, the thickness of the light shielding partition (A-2) is preferably 10 μm or less, more preferably 5 μm or less. Further, the width of the light-shielding partition (A-2) is preferably approximately the same as that of the above-described partition (A-1).

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

Examples of resins include epoxy resins, (meth)acrylic polymers, polyurethanes, polyesters, polyimides, polyolefins, and polysiloxanes. You may contain 2 or more types of these. Among these, polyimide is preferable because it is excellent in heat resistance and solvent resistance.

Examples of the black pigment include those exemplified as the black pigment in the resin composition described above, palladium oxide, platinum oxide, gold oxide, silver oxide, and the like. A black pigment selected from titanium nitride, zirconium nitride, carbon black, palladium oxide, platinum oxide, gold oxide and silver oxide is preferred because it has high light-shielding properties.

As a method for patterning the light-shielding partition (A-2) on the underlying substrate, for example, a photosensitive material described in JP-A-2015-1654 is used, and the above-described partition (A-1) is photosensitive. A method of forming a pattern by a transparent paste method is preferred.

The substrate with partition walls of the present invention further includes pixels (hereinafter sometimes referred to as “pixels (B)”) containing (B) color-converting luminescent materials arranged separated by the partition walls (A-1). It is preferred to have The pixel (B) has a function of enabling color display by converting at least part of the wavelength range of incident light and emitting output light in a wavelength range different from that of the incident light.

FIG. 2 shows a cross-sectional view of one mode of the partition-provided substrate of the present invention having patterned partitions (A-1) and pixels (B) containing a color-converting luminescent material. A base substrate 1 has partition walls 2 patterned thereon, and pixels 3 are arranged in regions separated by the partition walls 2 .

The color conversion material preferably contains a phosphor selected from inorganic phosphors and organic phosphors.

The substrate with partition walls of the present invention can be used as a display device by combining, for example, a backlight that emits blue light, liquid crystals formed on TFTs, and pixels (B). In this case, the region corresponding to the red pixel preferably contains a red phosphor that emits red fluorescence when excited by blue excitation light. Similarly, the region corresponding to the green pixel preferably contains a green phosphor that emits green fluorescence when excited by blue excitation light. A region corresponding to a blue pixel preferably does not contain a phosphor.

The substrate with barrier ribs of the present invention can also be used in a display device using blue micro-LEDs as a backlight, in which a large number of blue LEDs corresponding to each pixel are arranged and separated by white barrier ribs on the substrate. ON/OFF of each pixel is enabled by ON/OFF of the blue micro-LED, and no liquid crystal is required. The partition-attached substrate of the present invention can be used both as a partition separating pixels and a partition separating blue micro LEDs in a backlight.

The inorganic phosphor is preferably one that emits green or red light by blue excitation light, that is, one that is excited by excitation light with a wavelength of 400 to 500 nm and has a peak emission spectrum in the region of 500 to 700 nm. . Examples of such inorganic phosphors include YAG-based phosphors, TAG-based phosphors, sialon-based phosphors, Mn ⁴⁺ -activated fluoride complex phosphors, and inorganic semiconductors called quantum dots. You may use 2 or more types of these. Among these, quantum dots are preferred. Since quantum dots have a smaller average particle size than other phosphors, (B) the surface of the pixel can be smoothed to suppress light scattering on the surface, so that the light extraction efficiency is further improved. Brightness can be further improved.

Quantum dots include, for example, particles made of group II-IV, III-V, IV-VI, IV group semiconductors, and the like. Examples of these 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, _Si3N4 , _{Ge3N4 , Al2O3} and the like. You may use 2 or more types of these.

Quantum dots may contain p-type dopants or n-type dopants. Quantum dots may also have a core-shell structure. In the core-shell structure, any appropriate functional layer (single layer or multiple layers) may be formed around the shell depending on the purpose, and the shell surface may be surface-treated and/or chemically modified. .

Examples of the shape of the quantum dots include spherical, columnar, scaly, plate-like, and irregular shapes. The average particle size of the quantum dots can be arbitrarily selected according to the desired emission wavelength, and is preferably 1 to 30 nm. If the average particle size of the quantum dots is 1 to 10 nm, the peaks in the emission spectrum can be made sharper in each of blue, green and red. The average particle size of the quantum dots is preferably 2 nm or more, and preferably 8 nm or less. For example, when the average particle size of the quantum dots is about 2 nm, they emit blue light, when they are about 3 nm, they emit green light, and when they are about 6 nm, they emit red light. The average particle size of quantum dots can be measured by a dynamic light scattering method. A dynamic light scattering photometer DLS-8000 (manufactured by Otsuka Electronics Co., Ltd.) can be used as an apparatus for measuring the average particle size.

As the organic phosphor, one that emits green, red, or other colors by blue excitation light is preferable. A pyrromethene derivative having a basic skeleton represented by the following structural formula (8) as a phosphor emitting red fluorescence, and a pyrromethene derivative having a basic skeleton represented by the following structural formula (9) as a phosphor emitting green fluorescence derivatives and the like. Other examples include perylene-based derivatives, porphyrin-based derivatives, oxazine-based derivatives, and pyrazine-based derivatives that emit red or green fluorescence depending on the selection of substituents. You may contain 2 or more types of these. Among these, pyrromethene derivatives are preferred because of their high quantum yield. A pyrromethene derivative can be obtained, for example, by the method described in JP-A-2011-241160.

Since the organic phosphor is soluble in a solvent, it is possible to easily form pixels (B) with a desired thickness.

From the viewpoint of improving color characteristics, the thickness of the pixel (B) is preferably 0.5 μm or more, more preferably 1 μm or more. On the other hand, the thickness of the pixel (B) is preferably 30 μm or less, more preferably 20 μm or less, from the viewpoint of thinning the display device and curved surface processing.

The size of each pixel (B) is generally about 20 to 200 μm.

The pixels (B) are preferably arranged separated by partitions (A-1). By providing a partition between pixels, diffusion and color mixture of emitted light can be further suppressed.

As a method for forming the pixel (B), for example, a method of filling a space separated by a partition (A-1) with a coating liquid containing a color-converting luminescent material (hereinafter referred to as a color-converting luminescent material coating liquid) can be mentioned. be done. The color-converting luminescent material coating liquid may further contain a resin and a solvent.

As a method for filling the color-converting luminescent material coating liquid, an inkjet coating method or the like is preferable from the viewpoint of easily separately coating different types of color-converting luminescent materials on each pixel.

The obtained coating film may be dried under reduced pressure and/or dried by heating. When drying under reduced pressure, the drying temperature under reduced pressure is preferably 80° C. or less in order to prevent the drying solvent from re-condensing on the inner wall of the reduced pressure chamber. The pressure for drying under reduced pressure is preferably lower than the vapor pressure of the solvent contained in the coating film, and preferably 1 to 1000 Pa. The drying time under reduced pressure is preferably 10 to 600 seconds. In the case of heat drying, the heat drying apparatus includes, for example, an oven and a hot plate. The heat drying temperature is preferably 60 to 200°C. The heat drying time is preferably 1 to 60 minutes.

The substrate with partition walls of the present invention further comprises (C) a low refractive index layer having a refractive index of 1.20 to 1.35 at a wavelength of 550 nm (hereinafter referred to as “low refractive index layer (C) ”) is preferred. By having the low refractive index layer (C), the light extraction efficiency can be further improved, and the luminance of the display device can be further improved.

FIG. 3 shows a cross-sectional view of one embodiment of the substrate with partition walls of the present invention having a low refractive index layer. It has patterned partition walls 2 and pixels 3 on an underlying substrate 1 and further has a low refractive index layer 4 thereon.

In the display device, the refractive index of the low refractive index layer (C) is preferably 1.20 or more from the viewpoint of appropriately suppressing the reflection of light from the backlight and allowing light to enter the pixels (B) efficiently. 23 or more is more preferable. On the other hand, from the viewpoint of improving brightness, the refractive index of the low refractive index layer (C) is preferably 1.35 or less, more preferably 1.30 or less. Here, the refractive index of the low refractive index layer (C) is measured by irradiating light with a wavelength of 550 nm from a direction perpendicular to the cured film surface under atmospheric pressure and at 20° C. using a prism coupler. can be done.

The low refractive index layer (C) preferably contains polysiloxane and silica particles having no hollow structure. Polysiloxane has high compatibility with inorganic particles such as silica particles and functions as a binder capable of forming a transparent layer. In addition, by containing silica particles, minute voids can be efficiently formed in the low refractive index layer (C) to reduce the refractive index, and the refractive index can be easily adjusted within the above range. can be done. Furthermore, by using silica particles that do not have a hollow structure, cracks can be suppressed because they do not have a hollow structure that tends to cause cracks during curing shrinkage. In the low refractive index layer (C), the polysiloxane and the silica particles having no hollow structure may be contained independently, or the polysiloxane and the silica particles having no hollow structure are combined. may be contained in From the viewpoint of uniformity of the low refractive index layer (C), it is preferable that the polysiloxane and the silica particles having no hollow structure are contained in a state of bonding.

Polysiloxane contained in the low refractive index layer (C) preferably contains fluorine. By containing fluorine, the refractive index of the low refractive index layer (C) can be easily adjusted to 1.20 to 1.35. Fluorine-containing polysiloxane can be obtained by hydrolyzing and polycondensing a plurality of alkoxysilane compounds including at least a fluorine-containing alkoxysilane compound represented by the following general formula (10). Other alkoxysilane compounds may also be used.

In general formula (10) above, R ⁷ represents a fluoroalkyl group having 3 to 17 fluorine atoms. R ⁶ represents the same group as R ⁶ in general formulas (5) to (7). m represents 1 or 2; 4-m R ⁶ and m R ⁷ may be the same or different.

Examples of fluorine-containing alkoxysilane compounds represented by general formula (10) include trifluoroethyltrimethoxysilane, trifluoroethyltriethoxysilane, trifluoroethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, trifluoro Propyltriethoxysilane, trifluoropropyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, heptadecafluorodecyltriisopropoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyl trimethoxysilane, tridecafluorooctyltriisopropoxysilane, trifluoroethylmethyldimethoxysilane, trifluoroethylmethyldiethoxysilane, trifluoroethylmethyldiisopropoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane Silane, trifluoropropylmethyldiisopropoxysilane, heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecylmethyldiethoxysilane, heptadecafluorodecylmethyldiisopropoxysilane, tridecafluorooctylmethyldimethoxysilane, tridecafluorooctyl methyldiethoxysilane, tridecafluorooctylmethyldiisopropoxysilane, trifluoroethylethyldimethoxysilane, trifluoroethylethyldiethoxysilane, trifluoroethylethyldiisopropoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyl Diethoxysilane, trifluoropropylethyldiisopropoxysilane, heptadecafluorodecylethyldimethoxysilane, heptadecafluorodecylethyldiethoxysilane, heptadecafluorodecylethyldiisopropoxysilane, tridecafluorooctylethyldiethoxysilane, tri decafluorooctylethyldimethoxysilane, tridecafluorooctylethyldiisopropoxysilane, and the like. You may use 2 or more types of these.

The content of polysiloxane in the low refractive index layer (C) is preferably 4% by weight or more from the viewpoint of suppressing cracks. On the other hand, the content of polysiloxane is 32% by weight or less from the viewpoint of ensuring thixotropic properties due to the network between silica particles, maintaining an appropriate air layer in the low refractive index layer (C), and further reducing the refractive index. is preferred.

Silica particles having no hollow structure in the low refractive index layer (C) include, for example, "Snowtex" (registered trademark) manufactured by Nissan Chemical Industries, Ltd. and "Organo Silica Sol" (registered trademark) series (isopropyl alcohol dispersion , ethylene glycol dispersion, methyl ethyl ketone dispersion, dimethylacetamide dispersion, methyl isobutyl ketone dispersion, propylene glycol monomethyl acetate dispersion, propylene glycol monomethyl ether dispersion, methanol dispersion, ethyl acetate dispersion, butyl acetate dispersion, xylene -n-butanol dispersion, toluene dispersion, etc. Product numbers PGM-ST, PMA-ST, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, etc.). You may contain 2 or more types of these.

The content of silica particles that do not have a hollow structure in the low refractive index layer (C) ensures thixotropy due to the network between silica particles, maintains an appropriate air layer in the low refractive index layer (C), and refraction From the viewpoint of further reducing the rate, 68% by weight or more is preferable. On the other hand, the content of silica particles having no hollow structure is preferably 96% by weight or less from the viewpoint of suppressing cracks.

The thickness of the low refractive index layer (C) is preferably 0.1 μm or more, more preferably 0.5 μm or more, from the viewpoint of covering the steps of the pixels (B) and suppressing the occurrence of defects. On the other hand, the thickness of the low refractive index layer (C) is preferably 20 μm or less, more preferably 10 μm or less, from the viewpoint of reducing stress that causes cracks in the low refractive index layer (C).

As a method for forming the low refractive index layer (C), a coating method is preferable because the forming method is easy. For example, the low refractive index layer (C) can be formed by applying a low refractive index resin composition containing polysiloxane and silica particles onto the pixels (B), drying, and then heating.

The substrate with partition walls of the present invention preferably further has an inorganic protective layer I having a thickness of 50 to 1,000 nm on the low refractive index layer (C). Since the presence of the inorganic protective layer I makes it difficult for moisture in the atmosphere to reach the low refractive index layer (C), it is possible to suppress fluctuations in the refractive index of the low refractive index layer (C) and suppress luminance degradation. can.

FIG. 4 shows a cross-sectional view of one embodiment of the substrate with partition walls of the present invention having a low refractive index layer and an inorganic protective layer I. As shown in FIG. It has patterned partition walls 2 and pixels 3 on an underlying substrate 1, and further has a low refractive index layer 4 and an inorganic protective layer I5 thereon.

Further, the substrate with partition walls of the present invention preferably further has an inorganic protective layer II having a thickness of 50 to 1,000 nm between the pixel (B) and the low refractive index layer (C). By having the inorganic protective layer II, it becomes difficult for the raw material forming the pixel (B) to move from the pixel (B) to the low refractive index layer, so that the refractive index fluctuation of the low refractive index layer (C) is suppressed. , luminance deterioration can be suppressed.

FIG. 5 shows a cross-sectional view of one embodiment of the substrate with partition walls of the present invention having a low refractive index layer and an inorganic protective layer II. It has patterned partition walls 2 and pixels 3 on a base substrate 1 , and further has an inorganic protective layer II 6 and a low refractive index layer 4 thereon.

In addition, the substrate with partition walls of the present invention preferably further has a color filter (hereinafter sometimes referred to as “color filter”) having a thickness of 1 to 5 μm between the base substrate and the pixels (B). . A color filter has a function of transmitting visible light in a specific wavelength range to give a desired hue to the transmitted light. By including the color filter, the color purity of the display device can be improved. Color purity can be further improved by setting the thickness of the color filter to 1 μm or more. On the other hand, by setting the thickness of the color filter to 5 μm or less, the luminance can be further improved.

FIG. 6 shows a cross-sectional view of one mode of the substrate with partition walls of the present invention having a color filter. It has patterned partition walls 2 and color filters 7 on a base substrate 1 , and pixels 3 on the color filters 7 .

Examples of the color filter include a color filter using a pigment-dispersed material in which a pigment is dispersed in a photoresist, which is used for flat panel displays such as liquid crystal displays. 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, a yellow color filter that selectively transmits a wavelength of 500 nm or more, A red color filter that selectively transmits wavelengths of 600 nm or more may be used. Moreover, the color filter may be laminated separately from the pixel (B) containing the color-converting luminescent material, or may be integrally laminated.

Further, the substrate with partition walls of the present invention preferably further has an inorganic protective layer III and/or a yellow organic protective layer having a thickness of 50 to 1,000 nm between the color filter and the pixel (B). By having the inorganic protective layer III, it becomes difficult for the raw materials for forming the color filter to reach the pixels (B) containing the color conversion light-emitting material from the color filter. Luminance degradation can be suppressed. In addition, by having the yellow organic protective layer, it is possible to cut blue leakage light that has not been completely converted by the pixels (B) containing the color-converting light-emitting material, thereby improving color reproducibility.

FIG. 7 shows a cross-sectional view of one embodiment of the substrate with partition walls of the present invention having a color filter and an inorganic protective layer III and/or a yellow organic protective layer. It has patterned barrier ribs 2 and color filters 7 on a base substrate 1 , and has an inorganic protective layer III and/or a yellow organic protective layer 8 thereon, and an inorganic protective layer III and/or a yellow organic protective layer 8 . It has pixels 3 arranged separated by partition walls 2 covered with a protective layer 8 .

Further, the substrate with partition walls of the present invention preferably further has an inorganic protective layer IV and/or a yellow organic protective layer having a thickness of 50 to 1,000 nm on the underlying substrate. The inorganic protective layer IV and/or the yellow organic protective layer act as a refractive index adjusting layer, extracting light emitted from the pixel (B) more efficiently, and can further improve the luminance of the display device. In addition, the yellow organic protective layer cuts the blue leakage light that has not been completely converted by the pixels (B) containing the color-converting light-emitting material, and can improve color reproducibility. The inorganic protective layer IV and/or the yellow organic protective layer are more preferably provided between the underlying substrate and the partition walls (A) and the pixels (B).

FIG. 8 shows a cross-sectional view of one embodiment of the substrate with partition walls of the present invention having an inorganic protective layer IV and/or a yellow organic protective layer. It has an inorganic protective layer IV and/or a yellow organic protective layer 9 on a base substrate 1, and has patterned barrier ribs 2 and color filters 7 thereon, and patterned barrier ribs thereon. 2 and pixels 3.

Examples of materials constituting the inorganic protective layers I to 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. . You may contain 2 or more types of these. Among these, silicon nitride or silicon oxide is more preferable because of its low water vapor permeability and high permeability.

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

The thicknesses of the inorganic protective layers I to IV are determined by exposing a cross section perpendicular to the base substrate using a polishing apparatus such as a cross section polisher, and then observing the cross section at an enlarged scale using a scanning electron microscope or a transmission electron microscope. can be measured by

Examples of the method for forming the inorganic protective layers I to IV include a sputtering method. The inorganic protective layer is preferably colorless and transparent or yellow and transparent.

The yellow organic protective layer is obtained, for example, by patterning the resin composition of the present invention containing an organometallic compound containing silver as an organometallic compound. As described above, the organometallic compound containing silver has the function of yellowing the protective layer by decomposing and aggregating in the heating process during pattern formation to form yellow particles. Examples of organometallic compounds containing silver include silver neodecanoate, silver octylate, and silver salicylate. Among these, silver neodecanoate is preferable from the viewpoint of yellowing. In the yellow organic protective layer resin composition, the content of the organometallic compound containing silver is preferably 0.2 to 5% by weight based on the solid content. By setting the content of the organometallic compound containing silver to 0.2% by weight or more, the yellowing can be further enhanced. The content of the organometallic compound containing silver is more preferably 1.5% by weight or more in the solid content. On the other hand, by setting the content of the organometallic compound containing silver to 5% by weight or less in the solid content, the transmittance can be further improved.

The resin composition forming the yellow organic protective layer may contain a yellow pigment. Examples of yellow pigments include pigment yellow (hereinafter abbreviated as PY) PY12, PY13, PY17, PY20, PY24, PY83, PY86, PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY138, PY139, PY147 , PY148, PY150, PY153, PY154, PY166, PY168, PY185 and the like. Among them, a yellow pigment selected from PY139, PY147, PY148 and PY150 is preferable from the viewpoint of selectively shielding blue light.
As a method of patterning the yellow organic protective layer, a method of forming a pattern by a photosensitive paste method is preferable, as in the case of the barrier ribs (A-1) described above.

When the yellow organic protective layer 8 is formed on the color filter 7 as shown in FIG. 7, the yellow organic protective layer 8 may serve as an overcoat layer for flattening each pixel of the color filter.

The thickness of the yellow organic protective layer is preferably 100 nm or more, more preferably 500 nm or more, from the viewpoint of sufficiently shielding blue leakage light. On the other hand, the thickness of the yellow organic protective layer is preferably 3000 nm or less, more preferably 2000 nm or less, from the viewpoint of suppressing a decrease in light extraction efficiency.

Next, the display device of the present invention will be described. A display device of the present invention includes the substrate with partition walls and a light emitting source. As the light emission source, a light emission source selected from a liquid crystal cell, an organic EL cell, a mini LED cell and a micro LED cell is preferable. An organic EL cell is more preferable as the light source because of its excellent light emission characteristics. Here, a mini-LED cell refers to a cell in which a large number of LEDs each having a length and width of about 100 μm to 10 mm are arranged. A micro LED cell refers to a cell in which a large number of LEDs each having a length and width of less than 100 μm are arranged.

A method for manufacturing a display device of the present invention will be described by taking an example of a display device having a substrate with partition walls and an organic EL cell of the present invention. A photosensitive polyimide resin is applied on a glass substrate, and an insulating film having an opening is formed by photolithography. After aluminum is sputtered thereon, the aluminum is patterned by photolithography to form a back electrode layer made of aluminum in the openings where there is no insulating film. Subsequently, tris(8-quinolinolato)aluminum (hereinafter abbreviated as Alq3) was formed thereon as an electron transport layer by vacuum vapor deposition, and then Alq3 as a light-emitting layer was formed with dicyanomethylenepyran, quinacridone and 4,4′. forming a white light-emitting layer doped with bis(2,2-diphenylvinyl)biphenyl; Next, N,N'-diphenyl-N,N'-bis(α-naphthyl)-1,1'-biphenyl-4,4'-diamine is deposited as a hole transport layer by vacuum deposition. Finally, ITO is deposited as a transparent electrode by sputtering to fabricate an organic EL cell having a white light-emitting layer. A display device can be produced by bonding the aforementioned substrate with partition walls to the organic EL cell obtained in this manner so as to face each other with a sealant.

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited to these scopes. The names of the compounds using abbreviations among the compounds used are shown below.
PGMEA: propylene glycol monomethyl ether acetate DAA: diacetone alcohol BHT: dibutylhydroxytoluene.

The solid content concentrations of the polysiloxane solutions in Synthesis Examples 1 to 4 were obtained by the following method. 1.5 g of the polysiloxane solution was put into an aluminum cup and heated at 250° C. for 30 minutes using a hot plate to evaporate the liquid. The weight of the solid content remaining in the aluminum cup after heating was weighed, and the solid content concentration of the polysiloxane solution was obtained from the ratio to the weight before heating.

The weight average molecular weight of polysiloxane in Synthesis Examples 1 to 4 was obtained by the following method. Using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation), using tetrahydrofuran as a mobile phase, perform GPC analysis based on "JIS K7252-3 (enacted date = 2008/03/20)", A polystyrene equivalent weight average molecular weight was measured.

The content ratio of each repeating unit in polysiloxane in Synthesis Examples 1 to 4 was obtained by the following method. A polysiloxane solution is injected into a “Teflon” (registered trademark) NMR sample tube with a diameter of 10 mm and ²⁹ Si-NMR measurement is performed, and the Si derived from a specific organosilane is compared with the integrated value of the entire Si derived from the organosilane. The content ratio of each repeating unit was calculated from the ratio of the integrated value of. ²⁹ Si-NMR measurement conditions are shown below.
Apparatus: Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.)
Measurement method: Gated decoupling method Measurement nucleus frequency: 53.6693 MHz ( ²⁹ Si nucleus)
Spectrum width: 20000Hz
Pulse width: 12 μs (45° pulse)
Pulse repetition time: 30.0 seconds Solvent: Acetone-d6
Reference substance: Tetramethylsilane Measurement temperature: 23°C
Sample rotation speed: 0.0 Hz.

Synthesis Example 1 Polysiloxane (PSL-1) solution In a 1000 ml three-necked flask, 147.32 g (0.675 mol) of trifluoropropyltrimethoxysilane and 40.66 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane were added. , 26.23 g (0.10 mol) of 3-trimethoxysilylpropyl succinic anhydride, 12.32 g (0.05 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and 0.808 g of BHT. , and 171.62 g of PGMEA were charged, and an aqueous phosphoric acid solution prepared by dissolving 2.265 g of phosphoric acid (1.0% by weight relative to the charged monomers) in 52.65 g of water was added over 30 minutes while stirring at room temperature. After that, 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. over 30 minutes. After 1 hour from the start of heating, the temperature of the solution (internal temperature) reached 100° C., and the solution was heated and stirred for 2 hours (internal temperature: 100 to 110° C.) to obtain a polysiloxane solution. A mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liter/min during the temperature rise and heating and stirring. A total of 131.35 g of methanol and water, which are by-products, were distilled during the reaction. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (PSL-1) solution. The weight average molecular weight of the obtained polysiloxane (PSL-1) was 4,000. Also, trifluoropropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, and 3-(3,4-epoxycyclohexyl)propyl in polysiloxane (PSL-1) The molar ratio of each repeating unit derived from trimethoxysilane was 67.5 mol %, 17.5 mol %, 10 mol % and 5 mol %, respectively.

Synthesis Example 2 Polysiloxane (PSL-2) solution In a 1000 ml three-necked flask, 116.07 g (0.475 mol) of diphenyldimethoxysilane, 0.20 mol of dimethyldimethoxysilane, and 43 g of 3-methacryloxypropyltrimethoxysilane were added. 46 g (0.175 mol), 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 12.32 g (0.05 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane , 0.843 g of BHT, and 176.26 g of PGMEA were charged, and 30% of an aqueous phosphoric acid solution prepared by dissolving 2.221 g of phosphoric acid in 43.65 g of water (1.0% by weight based on the charged monomers) was stirred at room temperature. added over a period of minutes. Thereafter, in the same manner as in Synthesis Example 1, a polysiloxane solution was obtained. A total of 136.90 g of methanol and water, which are by-products, were distilled during the reaction. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (PSL-2) solution. The weight average molecular weight of the obtained polysiloxane (PSL-2) was 2,800. Also, diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride and 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane in polysiloxane (PSL-2) The molar ratio of each repeating unit derived was 47.5 mol %, 20 mol %, 17.5 mol %, 10 mol % and 5 mol %, respectively.

Synthesis Example 3 Polysiloxane (PSL-3) solution In a 1000 ml three-necked flask, 147.32 g (0.675 mol) of trifluoropropyltrimethoxysilane and 43.46 g (0.175 mol) of 3-methacryloxypropyltrimethoxysilane were added. ), 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 12.32 g (0.05 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and 0.05 mol of BHT. 810 g of PGMEA and 172.59 g of PGMEA were charged, and an aqueous phosphoric acid solution prepared by dissolving 2.293 g of phosphoric acid (1.0% by weight relative to the charged monomers) in 54.45 g of water was added over 30 minutes while stirring at room temperature. . Thereafter, in the same manner as in Synthesis Example 1, a polysiloxane solution was obtained. A total of 140.05 g of methanol and water, which are by-products, were distilled during the reaction. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (PSL-3) solution. The weight average molecular weight of the obtained polysiloxane (PSL-3) was 4,100. Also, trifluoropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride and 3-(3,4-epoxycyclohexyl)propyltrisilane in polysiloxane (PSL-3). The molar ratio of each repeating unit derived from methoxysilane was 67.5 mol %, 17.5 mol %, 10 mol % and 5 mol %, respectively.

Synthesis Example 4 Polysiloxane (PSL-4) solution In a 1000 ml three-necked flask, 34.05 g (0.250 mol) of methyltrimethoxysilane, 99.15 g (0.500 mol) of phenyltrimethoxysilane, and 31 g of tetraethoxysilane were added. .25 g (0.150 mol), 24.64 g (0.100 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, and 174.95 g of PGMEA were charged and added to 56.70 g of water with stirring at room temperature. A phosphoric acid aqueous solution in which 0.945 g of phosphoric acid (0.50% by weight based on the charged monomer) was dissolved was added over 30 minutes. Thereafter, in the same manner as in Synthesis Example 1, a polysiloxane solution was obtained. A total of 129.15 g of methanol and water, which are by-products, were distilled during the reaction. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane (PSL-4) solution. The weight average molecular weight of the obtained polysiloxane (PSL-4) was 4,200. Further, the molar ratio of each repeating unit derived from methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, and 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane in polysiloxane (PSL-4) is , 25 mol %, 50 mol %, 15 mol % and 10 mol %, respectively.

The compositions of Synthesis Examples 1 to 4 are summarized in Table 1.

Synthesis Example 5 Green organic phosphor 3,5-dibromobenzaldehyde (3.0 g), 4-t-butylphenylboronic acid (5.3 g), tetrakis(triphenylphosphine) palladium (0) (0.4 g), and Potassium carbonate (2.0 g) was placed in the flask and the flask was purged with nitrogen. Degassed toluene (30 mL) and degassed water (10 mL) were added thereto and refluxed for 4 hours. After cooling the reaction solution to room temperature and liquid-separating, the organic layer was wash|cleaned by the saturated salt solution. The organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. The resulting reaction product was purified by silica gel column chromatography to give 3,5-bis(4-t-butylphenyl)benzaldehyde (3.5 g) as a white solid. Next, 3,5-bis(4-t-butylphenyl)benzaldehyde (1.5 g) and 2,4-dimethylpyrrole (0.7 g) were placed in a flask, followed by anhydrous dichloromethane (200 mL) and trifluoroacetic acid (1 drop) was added and stirred for 4 hours under a nitrogen atmosphere. A dehydrated dichloromethane solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.85 g) was added to the reaction mixture, and the mixture was further stirred for 1 hour. After completion of the reaction, boron trifluoride diethyl ether complex (7.0 mL) and diisopropylethylamine (7.0 mL) were added and stirred for 4 hours, then water (100 mL) was added and stirred to separate the organic layer. bottom. The organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. The resulting reaction product was purified by silica gel column chromatography to obtain 0.4 g of green powder (yield 17%). The ¹ H-NMR analysis results of the obtained green powder are as follows, and it was confirmed that the green powder obtained above was [G-1] represented by the following structural formula.
¹ H-NMR (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).

Synthesis Example 6 Red organic phosphor A mixed solution of 300 mg of 4-(4-t-butylphenyl)-2-(4-methoxyphenyl)pyrrole, 201 mg of 2-methoxybenzoyl chloride and 10 ml of toluene was heated at 120° C. under a nitrogen stream. Heated for 6 hours. After cooling to room temperature, the solvent was evaporated. The obtained residue was washed with 20 ml of ethanol and vacuum dried to obtain 260 mg of 2-(2-methoxybenzoyl)-3-(4-t-butylphenyl)-5-(4-methoxyphenyl)pyrrole. rice field. Next, 2-(2-methoxybenzoyl)-3-(4-t-butylphenyl)-5-(4-methoxyphenyl)pyrrole 260 mg, 4-(4-t-butylphenyl)-2-(4- A mixed solution of 180 mg of methoxyphenyl)pyrrole, 206 mg of methanesulfonic anhydride and 10 ml of degassed toluene was heated at 125° C. for 7 hours under a nitrogen stream. After cooling the reaction mixture to room temperature, 20 ml of water was added and extracted with 30 ml of dichloromethane. After the organic layer was washed twice with 20 ml of water, it was evaporated and dried in a vacuum to obtain a pyrromethene compound as a residue. Next, 305 mg of diisopropylethylamine and 670 mg of boron trifluoride diethyl ether complex were added to a mixed solution of the obtained pyrromethene derivative and 10 ml of toluene under a nitrogen stream, and the mixture was stirred at room temperature for 3 hours. 20 ml of water was poured into the reaction mixture and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, dried over magnesium sulfate, and evaporated. After purification by silica gel column chromatography and vacuum drying, 0.27 g of reddish purple powder was obtained (yield 70%). The results of ¹ H-NMR analysis of the obtained reddish purple powder are as follows, and it was confirmed that the reddish purple powder obtained above was [R-1] represented by the following structural formula.
¹ H-NMR (CDCl ₃ (d=ppm)): 1.19 (s, 18H), 3.42 (s, 3H), 3.85 (s, 6H), 5.72 (d, 1H), 6.20 (t, 1H), 6.42-6.97 (m, 16H), 7.89 (d, 4H).

Synthesis Example 7 Silica Particle-Containing Polysiloxane Solution (LS-1)
0.05 g (0.4 mmol) of methyltrimethoxysilane, 0.66 g (3.0 mmol) of trifluoropropyltrimethoxysilane, and 0.10 g (0.0 mmol) of trimethoxysilylpropylsuccinic anhydride are placed in a 500 ml three-necked flask. .4 mmol), 7.97 g (34 mmol) of γ-acryloxypropyltrimethoxysilane, and 15.6% by weight of an isopropyl alcohol dispersion of silica particles (IPA-ST-UP: manufactured by Nissan Chemical Industries, Ltd.). 224.37 g was added, and 163.93 g of ethylene glycol mono-t-butyl ether was added. An aqueous phosphoric acid solution prepared by dissolving 0.088 g of phosphoric acid in 4.09 g of water was added over 3 minutes while stirring at room temperature. After that, 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. After 1 hour from the start of heating, the internal temperature of the solution reached 100° C., and by further heating and stirring for 2 hours (the internal temperature was 100 to 110° C.), a silica particle-containing polysiloxane solution (LS-1) was obtained. rice field. During the temperature rise and heating and stirring, 0.05 l (liter) of nitrogen was flowed per minute. A total of 194.01 g of methanol and water, which are by-products, were distilled during the reaction. The obtained silica particle-containing polysiloxane solution (LS-1) had a solid content concentration of 24.3% by weight, and the content of polysiloxane and silica particles in the solid content was 15% by weight and 85% by weight, respectively. . Polysiloxanes methyltrimethoxysilane, trifluoropropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, and γ-acryloxypropyltrimethoxysilane in the obtained silica particle-containing polysiloxane (LS-1) The molar ratio of each repeating unit derived from was 1.0 mol%, 8.0 mol%, 1.0 mol% and 90.0 mol%, respectively.

Example 1 Partition wall resin composition (P-1)
As a white pigment, titanium dioxide pigment (R-960; manufactured by BASF Japan Co., Ltd. (hereinafter "R-960")) 5.00 g, and as a resin, the polysiloxane (PSL-1) solution obtained in Synthesis Example 1 5.00 g was mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-1). Further, 1.00 g of bis(acetylacetonato)palladium as an organometallic compound and 0.861 g of triphenylphosphine as a coordinating compound having a phosphorus atom (equimolar amount relative to the organometallic compound) were added to DAA8. .139 g to obtain an organometallic compound solution (OM-1).

Next, 9.98 g of the pigment dispersion (MW-1), 1.86 g of the organometallic compound solution (OM-1), 0.98 g of polysiloxane (PSL-1) solution, and ethanone as a photopolymerization initiator. 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (“Irgacure” (registered trademark) OXE-02, BASF Japan Ltd. ) (hereinafter “OXE-02”)) 0.050 g, bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide (“Irgacure” 819, manufactured by BASF Japan Co., Ltd. (hereinafter “IC-819”) )) 0.400 g, as a photobase generator, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium 2-(3-benzoylphenyl)propionate (WPBG-266 (trade name), Fujifilm Wako Pure Chemical Industries, Ltd. (hereinafter “WPBG-266”)) 0.100 g, and as a photopolymerizable compound, dipentaerythritol hexaacrylate (“KAYARAD” (registered trademark) DPHA, Shin Nihon Yakugyo Co., Ltd. ( hereinafter “DPHA”))) 1.20 g, a photopolymerizable fluorine-containing compound (“Megafac” (registered trademark) RS-76-E, manufactured by DIC Corporation (hereinafter “RS-76-E”) as a liquid-repellent compound )), 1.00 g of a 40% by weight PGMEA diluted solution of 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (“Celoxide” (registered trademark) 2021P, manufactured by Daicel Corporation (hereinafter “Celoxide ® 2021P”))) 0.100 g, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl) propionate] (“Irganox” ® 1010, BASF Japan Co., Ltd. (hereinafter “IRGANOX (registered trademark) 1010”)) 0.030 g, and acrylic surfactant (“BYK” (registered trademark) 352, BYK Chemie Japan Co., Ltd. (hereinafter “BYK- 352")) was dissolved in 4.20 g of solvent PGMEA and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a partition wall resin composition (P-1).

Examples 2 to 3 Partition wall resin compositions (P-2) to (P-3)
A partition wall resin composition (P-2 ) and (P-3) were obtained.

Example 4 Resin composition for partition walls (P-4)
Instead of the 40% by weight PGMEA diluted solution of RS-76-E, "Megafac" (registered trademark) F477 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) 40% by weight PGMEA diluted solution was used. A partition wall resin composition (P-4) was obtained in the same manner as in Example 1.

Example 5 Partition wall resin composition (P-5)
5.00 g of R-960 as a white pigment and 5.00 g of a polysiloxane (PSL-4) solution as a resin are mixed and dispersed using a mill-type dispersing machine filled with zirconia beads to obtain a pigment dispersion (MW -4) was obtained. 9.98 g of the pigment dispersion (MW-4), 1.86 g of the organometallic compound solution (OM-1), 1.16 g of the polysiloxane (PSL-4) solution, and WPBG-as a photobase generator. 0.10 g of 266, 1.00 g of a 40% by weight PGMEA diluted solution of F477 as a liquid-repellent compound, 0.100 g of Celoxide (registered trademark) 2021P, and THP-17 (trade name, Toyo Gosei Co., Ltd.) as a quinonediazide compound. ), 0.100 g of a 10% by weight PGMEA diluted solution of surfactant BYK-352, and 4.10 g of PGMEA were mixed and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a partition wall resin composition (P-5).

Example 6 Partition wall resin composition (P-6)
An organometallic compound solution (OM-2) was prepared in the same manner as the organometallic compound solution (OM-1) except that silver neodecanoate was used instead of bis(acetylacetonato)palladium as the organometallic compound. bottom. A partition wall resin composition (P-6) was obtained in the same manner as in Example 1, except that the organometallic compound solution (OM-2) was used instead of the organometallic compound solution (OM-1).

Example 7 Partition wall resin composition (P-7)
An organometallic compound solution (OM-3) was prepared in the same manner as the organometallic compound solution (OM-1) except that chlorotriphenylphosphine gold was used instead of bis(acetylacetonato)palladium as the organometallic compound. was prepared. A partition wall resin composition (P-7) was obtained in the same manner as in Example 1, except that the organometallic compound solution (OM-3) was used instead of the organometallic compound solution (OM-1).

Example 8 Partition wall resin composition (P-8)
An organometallic compound solution (OM- 4) was prepared. A partition wall resin composition (P-8) was obtained in the same manner as in Example 1, except that the organometallic compound solution (OM-4) was used instead of the organometallic compound solution (OM-1).

Example 9 Partition wall resin composition (P-9)
The addition amount of the organometallic compound solution (OM-1) was changed to 0.929 g, the addition amount of the polysiloxane (PSL-1) solution was changed to 1.41 g, and PGMEA 4.20 g was changed to PGMEA 4.70 g as the solvent. A partition wall resin composition (P-9) was obtained in the same manner as in Example 1.

Example 10 Partition wall resin composition (P-10)
The addition amount of the organometallic compound solution (OM-1) was changed to 0.400 g, the addition amount of the polysiloxane (PSL-1) solution was changed to 1.940 g, and PGMEA 4.20 g was changed to PGMEA 6.27 g as a solvent. A resin composition for partition walls (P-10) was obtained in the same manner as in Example 1.

Example 11 Partition wall resin composition (P-11)
The addition amount of the organometallic compound solution (OM-1) was changed to 4.595 g, the addition amount of the polysiloxane (PSL-1) solution was changed to 0.010 g, and PGMEA 4.20 g was changed to PGMEA 2.92 g as a solvent. A resin composition for partition walls (P-11) was obtained in the same manner as in Example 1.

Example 12 Partition wall resin composition (P-12)
5.00 g of R-960 as a white pigment, 5.00 g of polysiloxane (PSL-1) solution as a resin, and 0.01 g of titanium nitride as a black pigment are mixed, and a mill-type disperser filled with zirconia beads is used. to obtain a pigment dispersion (MW-2). Instead of pigment dispersion (MW-1), 9.99 g of pigment dispersion (MW-2) was added, the amount of polysiloxane (PSL-1) solution added was changed to 1.38 g, and PGMEA4. A partition wall resin composition (P-12) was obtained in the same manner as in Example 9, except that 72 g was used.

Example 13 Partition wall resin composition (P-13)
10.0 g of polysiloxane (PSL-1) solution as a resin and 0.15 g of titanium nitride as a black pigment are mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW- 3) was obtained. Instead of the pigment dispersion (MW-1), add 9.99 g of the pigment dispersion (MW-3), change the amount of polysiloxane (PSL-1) solution added to 15.16 g, and add the amount of PGMEA A resin composition for partition walls (P-13) was obtained in the same manner as in Example 1, except that the weight was changed from 4.20 g to 0.11 g.

Example 14 Partition wall resin composition (P-14)
Instead of the organometallic compound solution (OM-1), 1.85 g of a 10% DAA solution of bis(acetylacetonato)palladium was used as the organometallic compound, and the amount of polysiloxane (PSL-1) solution added was 1. A resin composition for partition walls (P-14) was obtained in the same manner as in Example 1, except that the solvent was changed from 4.20 g to 3.85 g PGMEA.

Example 15 Partition wall resin composition (P-15)
Example 1 except that the photobase generator WPBG-266 was not added, the amount of polysiloxane (PSL-1) solution added was changed to 1.21 g, and PGMEA 4.20 g was changed to PGMEA 4.07 g as a solvent. A partition wall resin composition (P-15) was obtained in the same manner.

Example 16 Partition wall resin composition (P-16)
A 40% by weight PGMEA diluted solution of the liquid repellent compound RS-76-E was not added, the amount of polysiloxane (PSL-1) solution added was changed to 2.01 g, and PGMEA 4.20 g was changed to PGMEA 4.17 g as a solvent. A partition wall resin composition (P-16) was obtained in the same manner as in Example 1, except that

Comparative Example 1 Partition wall resin composition (P-17)
Organometallic compound solution (OM-5) obtained by using 1.861 g of triphenylphosphine and 8.139 g of DAA as a coordinating compound having a phosphorus atom instead of organometallic compound solution (OM-1). Partition walls were formed in the same manner as in Example 1, except that .867 g was added, the amount of polysiloxane (PSL-1) solution added was changed to 1.41 g, and the amount of PGMEA added was changed from 4.20 g to 4.76 g. to obtain a resin composition (P-17) for

Comparative Example 2 Partition wall resin composition (P-18)
5.00 g of R-960 as a white pigment, 5.00 g of polysiloxane (PSL-1) solution as a resin, and 0.10 g of titanium nitride as a black pigment were mixed, and a mill-type disperser filled with zirconia beads. to obtain a pigment dispersion (MW-4). Next, 10.02 g of the pigment dispersion (MW-4), 1.73 g of the polysiloxane (PSL-1) solution, 0.050 g of OXE-02 as a photopolymerization initiator, and 0.05 g of IC-819 were mixed. 400 g, 0.10 g of WPBG-266 as a photobase generator, 1.20 g of DPHA as a photopolymerizable compound, 1.00 g of a 40% by weight PGMEA diluted solution of RS-76-E as a liquid-repellent compound, celoxide (registered 0.100 g of 2021P (trademark), 0.030 g of IRGANOX (registered trademark) 1010, 0.100 g of a 10% by weight PGMEA diluted solution of BYK-352 as a surfactant, and 5.31 g of PGMEA as a solvent were mixed and stirred. . The resulting mixture was filtered through a 5.0 μm filter to obtain a partition wall resin composition (P-18).

Comparative Example 3 Partition wall resin composition (P-19)
5.00 g of R-960 as a white pigment, 5.00 g of polysiloxane (PSL-1) solution as a resin, and 0.10 g of zirconium nitride as a black pigment were mixed, and a mill-type disperser filled with zirconia beads. to obtain a pigment dispersion (MW-5). A partition wall resin composition (P-19) was obtained in the same manner as in Comparative Example 2, except that the pigment dispersion (MW-5) was used instead of the pigment dispersion (MW-4).

Comparative Example 4 Partition wall resin composition (P-20)
5.00 g of R-960 as a white pigment, 5.00 g of a polysiloxane (PSL-1) solution as a resin, and a mixed pigment of a 60/40 weight ratio of red pigment PR254 and blue pigment PB64 as a black pigment. 0.05 g was mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain a pigment dispersion (MW-6). A partition wall resin composition (P-20) was obtained in the same manner as in Comparative Example 2, except that the pigment dispersion (MW-6) was used instead of the pigment dispersion (MW-4).

Comparative Example 5 Partition wall resin composition (P-21)
An organometallic compound solution (OM- 5) was prepared. A partition wall resin composition (P-21) was obtained in the same manner as in Example 1, except that the organometallic compound solution (OM-5) was used instead of the organometallic compound solution (OM-1).

Comparative Example 6 Partition wall resin composition (P-22)
An organometallic compound solution (OM- 5) was prepared. A partition wall resin composition (P-22) was obtained in the same manner as in Example 1, except that the organometallic compound solution (OM-6) was used instead of the organometallic compound solution (OM-1).

The compositions of Examples 1-16 and Comparative Examples 1-6 are summarized in Tables 2-3.

Preparation Example 1 Color Conversion Luminescent Material Composition (CL-1)
Green quantum dot material (Lumidot 640 CdSe / ZnS, average particle size 6.3 nm: manufactured by Aldrich) 0.5 wt% toluene solution 20 parts by weight, DPHA 45 parts by weight, "Irgacure" (registered trademark) 907 ( 5 parts by weight of BASF Japan Co., Ltd.), 166 parts by weight of 30% by weight PGMEA solution of acrylic resin (SPCR-18 (trade name), Showa Denko Co., Ltd.) and 97 parts by weight of toluene are mixed and stirred. and dissolved uniformly. The resulting mixture was filtered through a 0.45 μm syringe filter to prepare a color-converting luminescent material composition (CL-1) Preparation Example 2 Color-converting luminescent material composition (CL-2)
Color in the same manner as in Preparation Example 1, except that 0.4 parts by weight of the green phosphor G-1 obtained in Synthesis Example 5 was used instead of the green quantum dot material, and the amount of toluene added was changed to 117 parts by weight. Conversion luminescent material composition (CL-2) was prepared Preparation Example 3 Color conversion luminescent material composition (CL-3)
Color in the same manner as in Preparation Example 1, except that 0.4 parts by weight of the red phosphor R-1 obtained in Synthesis Example 6 was used instead of the green quantum dot material, and the amount of toluene was changed to 117 parts by weight. Preparation Example 4 Color Filter Forming Material (CF-1) to Prepare Conversion Luminescent Material Composition (CL-3)
C. I. Pigment Green 59, 90 g, C.I. I. 60 g of Pigment Yellow 150, 75 g of a polymer dispersant (“BYK” (registered trademark)-6919 (trade name) manufactured by BYK Chemie (hereinafter “BYK-6919”)), a binder resin (“Adeka Arkles” (registered trademark) ) 100 g of WR301 (trade name, manufactured by ADEKA Corporation) and 675 g of PGMEA were mixed to prepare a slurry. A beaker containing the slurry was connected to a Dyno mill and a tube, and zirconia beads with a diameter of 0.5 mm were used as media to perform dispersion treatment at a peripheral speed of 14 m/s for 8 hours to obtain Pigment Green 59 dispersion (GD-1). was made.

Pigment Green 59 dispersion (GD-1) 56.54 g, acrylic resin (“Cyclomer” (registered trademark) P (ACA) Z250 (trade name) manufactured by Daicel Allnex Co., Ltd. (hereinafter “P (ACA) Z250” )) 3.14 g, DPHA 2.64 g, a photopolymerization initiator (“OPTOMER” (registered trademark) NCI-831 (trade name) manufactured by ADEKA Corporation (hereinafter “NCI-831”)) 0.330 g, 0.04 g of a surfactant (BYK” (registered trademark)-333 (trade name) manufactured by BYK-Chemie (hereinafter “BYK-333”)), 0.01 g of BHT as a polymerization inhibitor, and 37 g of PGMEA as a solvent. 30 g were mixed to prepare a color filter forming material (CF-1).

Preparation Example 5 Resin composition for light-shielding barrier ribs 150 g of carbon black (MA100 (trade name) manufactured by Mitsubishi Chemical Corporation), 75 g of polymer dispersant BYK-6919, 100 g of P(ACA)Z250, and 675 g of PGMEA were mixed. to prepare a slurry. A beaker containing the slurry was connected to a Dyno mill and a tube, and zirconia beads with a diameter of 0.5 mm were used as media to perform dispersion treatment at a peripheral speed of 14 m/s for 8 hours to prepare a pigment dispersion liquid (MB-1). bottom.

Pigment dispersion (MB-1) 56.54 g, P (ACA) Z250 3.14 g, DPHA 2.64 g, NCI-831 0.330 g, BYK-333 0.04 g, tertiary polymerization inhibitor 0.01 g of butylcatechol and 37.30 g of PGMEA were mixed to prepare a resin composition for light-shielding partition walls.

Preparation Example 6 Low refractive index layer-forming material 5.350 g of the silica particle-containing polysiloxane solution (LS-1) obtained in Synthesis Example 6, 1.170 g of ethylene glycol mono-t-butyl ether, and 3.48 g of DAA After mixing, the mixture was filtered through a 0.45 μm syringe filter to prepare a low refractive index layer-forming material.
Preparation Example 7 Yellow organic protective layer-forming material (YL-1)
C. I. 150 g of Pigment Yellow 150, 75 g of polymer dispersant (“BYK” (registered trademark)-6919 (trade name) manufactured by BYK-Chemie Co., Ltd. (hereinafter “BYK-6919”)), a binder resin (“ADEKA Arkles” (registered trademark) ) 100 g of WR301 (trade name, manufactured by ADEKA Corporation) and 675 g of PGMEA were mixed to prepare a slurry. A beaker containing the slurry was connected to a Dyno mill and a tube, and zirconia beads with a diameter of 0.5 mm were used as media to perform dispersion treatment at a peripheral speed of 14 m/s for 8 hours to obtain Pigment Yellow 150 dispersion (YD-1). was made.

Pigment Yellow 150 dispersion liquid (YD-1) 3.09 g, polysiloxane (PSL-1) solution 23.54 g as resin, DPHA 6.02 g as photopolymerizable compound, silver neodecanoate as organometallic compound 6.02 g of the prepared organometallic compound solution (OM-2), 0.20 g of OXE-02 as a photopolymerization initiator, 0.40 g of IC-819, 0.060 g of IRGANOX (registered trademark) 1010, and BYK 0.050 g of a 10% by weight diluted solution of PGMEA of -352 (equivalent to a concentration of 500 ppm) was dissolved in 61.15 g of solvent PGMEA and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a yellow organic protective layer-forming material (YL-1).

(Examples 17-20, Examples 22-28, Examples 38-45, Comparative Examples 7-9)
A 10 cm square non-alkali glass substrate (manufactured by AGC Techno Glass Co., Ltd., thickness 0.7 mm) was used as the base substrate. A partition wall resin composition shown in Tables 4 and 5 was spin-coated thereon, and dried at a temperature of 90° C. for 2 minutes using a hot plate (trade name: SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). , to prepare a dry film. The prepared dried film was exposed through a photomask using a parallel light mask aligner (trade name: PLA-501F, manufactured by Canon Inc.) with an ultra-high pressure mercury lamp as a light source at an exposure amount of 200 mJ/cm ² (i-line). exposed with Then, using an automatic developing device ("AD-2000 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), shower development is performed using a 0.045% by weight potassium hydroxide aqueous solution for 100 seconds, and then water is used for 30 seconds. Rinse for seconds. Furthermore, using an oven (trade name IHPS-222, manufactured by ESPEC Co., Ltd.), it was heated in the air at a temperature of 230 ° C. for 30 minutes, and a partition with a height of 10 µm and a width of 20 µm was formed on the glass substrate with a short side of 30 µm. , were formed in a grid-like pattern with a pitch interval of 150 μm on the long side.

The regions separated by the partition walls of the obtained substrate with partition walls were coated with the color-converting light-emitting material compositions shown in Tables 4 and 5 using an inkjet method in a nitrogen atmosphere, dried at 100° C. for 30 minutes, and the thickness was reduced. Pixels of 5.0 μm were formed to obtain a substrate with partition walls having the structure shown in FIG.

(Example 21)
A 10 cm square non-alkali glass substrate (manufactured by AGC Techno Glass Co., Ltd., thickness 0.7 mm) was used as the base substrate. A partition wall resin composition shown in Table 4 was spin-coated thereon, and dried at a temperature of 90° C. for 2 minutes using a hot plate (trade name: SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). A membrane was prepared. The prepared dried film was exposed through a photomask using a parallel light mask aligner (trade name: PLA-501F, manufactured by Canon Inc.) with an ultra-high pressure mercury lamp as a light source at an exposure amount of 200 mJ/cm ² (i-line). exposed with Then, using an automatic developing device ("AD-2000 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), shower development is performed with a 2.38% by weight tetramethylammonium hydroxide aqueous solution for 90 seconds, and then rinsed with water for 30 seconds. bottom. Thereafter, similarly to the above, bleaching was performed by exposing with an exposure amount of 500 mJ/cm ² (i-line) without a photomask. Furthermore, using an oven (trade name IHPS-222, manufactured by ESPEC Co., Ltd.), it was heated in the air at a temperature of 230 ° C. for 30 minutes, and a partition with a height of 10 µm and a width of 20 µm was formed on the glass substrate with a short side of 30 µm. , were formed in a grid-like pattern with a pitch interval of 150 μm on the long side.

The regions separated by the partition walls of the obtained substrate with partition walls were coated with the color-converting light-emitting material compositions shown in Tables 4 and 5 using an inkjet method in a nitrogen atmosphere, dried at 100° C. for 30 minutes, and the thickness was reduced. Pixels of 5.0 μm were formed to obtain a substrate with partition walls having the structure shown in FIG.

(Example 29)
A low refractive index layer-forming material was spin-coated on the partition-attached substrate after forming pixels by the same method as in Example 18, and a hot plate (trade name: SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. and dried at a temperature of 90° C. for 2 minutes to prepare a dry film. Furthermore, using an oven (trade name: IHPS-222, manufactured by ESPEC Co., Ltd.), the substrate was heated in air at a temperature of 90° C. for 30 minutes to form a low refractive index layer, thereby obtaining a substrate with partition walls having the configuration shown in FIG. Obtained.

(Example 30)
An inorganic protective layer with a thickness of 50 to 1,000 nm was formed on the low refractive index layer of the substrate with partition walls having the low refractive index layer obtained in Example 29 using a plasma CVD apparatus (PD-220NL, manufactured by Samco). A silicon nitride film having a thickness of 300 nm corresponding to I was formed to obtain a substrate with partition walls having the structure shown in FIG.

(Example 31)
Silicon nitride with a thickness of 300 nm, which corresponds to an inorganic protective layer II with a thickness of 50 to 1,000 nm, was formed on the substrate with partition walls obtained in Example 18 using a plasma CVD apparatus (PD-220NL, manufactured by Samco). A membrane was formed on the pixel top layer. Thereafter, a low refractive index layer having a thickness of 1.0 μm was formed on the inorganic protective layer II in the same manner as in Example 29 using the low index layer-forming material obtained in Preparation Example 6. The thickness is shown in FIG. A substrate with partition walls having the structure was obtained.

(Example 32)
The colorant obtained in Preparation Example 4 was applied to the regions separated by the partition walls of the substrate with partition walls before pixel formation, which was obtained by the same method as in Example 17, so that the film thickness after curing was 2.5 μm. A filter-forming material (CF-1) was applied and vacuum dried. Exposure was performed at an exposure dose of 40 mJ/cm ² (i-line) through a photomask designed to expose the area of the opening of the substrate with partition walls. After developing with a 0.3% by weight tetramethylammonium aqueous solution for 50 seconds, heat curing was performed at 230° C. for 30 minutes to form a color filter with a thickness of 2.5 μm and a width of 50 μm in the region separated by the partition wall. Thereafter, the color-converting light-emitting material composition (CL-2) obtained in Preparation Example 2 was applied onto the color filter in a nitrogen atmosphere using an inkjet method and dried at 100° C. for 30 minutes to obtain a thickness of 5.5. Pixels of 0 μm were formed to obtain a substrate with partition walls having the configuration shown in FIG. 6 .

(Example 33)
A plasma CVD device (PD-220NL, Samco Co., Ltd.) was placed on the color filter of the substrate with partition walls before pixel formation, on which a color filter having a thickness of 2.5 μm and a width of 50 μm was formed by the same method as in Example 32. was used to form a silicon nitride film with a thickness of 300 nm, which corresponds to the inorganic protective layer III with a thickness of 50 to 1,000 nm. Furthermore, on the inorganic protective layer III, in a nitrogen atmosphere, the color-converting light-emitting material composition (CL-2) obtained in Preparation Example 2 is applied using an inkjet method, dried at 100° C. for 30 minutes, and the thickness is Pixels of 5.0 μm were formed to obtain a substrate with partition walls having the structure shown in FIG.

(Example 34)
A 10 cm square non-alkali glass substrate (manufactured by AGC Techno Glass Co., Ltd., thickness 0.7 mm) was used as the base substrate. A plasma CVD apparatus (PD-220NL, manufactured by Samco) was used to form a silicon nitride film with a thickness of 300 nm thereon, which corresponds to the inorganic protective layer IV with a thickness of 50 to 1,000 nm. A substrate with partition walls having the structure shown in FIG. 8 was obtained in the same manner as in Example 31, except that the above substrate was used instead of the 10 cm square non-alkali glass substrate.
(Example 35)
The yellow organic protective film obtained in Preparation Example 7 was applied onto the color filter of the substrate with partition walls before pixel formation, on which a color filter with a thickness of 2.5 μm and a width of 50 μm was formed by the same method as in Example 32. A layer forming material (YL-1) was applied and vacuum dried. Exposure was performed at an exposure dose of 40 mJ/cm ² (i-line) through a photomask designed to expose the area of the opening of the substrate with partition walls. After developing with a 0.3% by weight tetramethylammonium aqueous solution for 50 seconds, heat curing was performed at 230° C. for 30 minutes to form a yellow organic protective layer having a thickness of 1.0 μm and a width of 50 μm. Furthermore, on the yellow organic protective layer, in a nitrogen atmosphere, using an inkjet method, the color conversion light-emitting material composition (CL-2) obtained in Preparation Example 2 is applied, dried at 100 ° C. for 30 minutes, and the thickness is Pixels of 5.0 μm were formed to obtain a substrate with partition walls having the structure shown in FIG.

(Example 36)
A 10 cm square non-alkali glass substrate (manufactured by AGC Techno Glass Co., Ltd., thickness 0.7 mm) was used as the base substrate. The yellow organic protective layer-forming material (YL-1) obtained in Preparation Example 7 was applied thereon and vacuum dried. After exposing the dry film with an exposure amount of 40 mJ/cm ² (i-line) without passing through a photomask, the film is developed with a 0.3% by weight tetramethylammonium aqueous solution for 50 seconds, and heat-cured at 230° C. for 30 minutes. Thus, a yellow organic protective layer having a thickness of 1.0 μm was formed. A substrate with partition walls having the structure shown in FIG. 8 was obtained in the same manner as in Example 31, except that the above substrate was used instead of the 10 cm square non-alkali glass substrate.

(Example 37)
A 10 cm square non-alkali glass substrate (manufactured by AGC Techno Glass Co., Ltd., thickness 0.7 mm) was used as the base substrate. The material for forming light-shielding barrier ribs obtained in Preparation Example 5 was spin-coated thereon, and dried at a temperature of 90° C. for 2 minutes using a hot plate (trade name: SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.). , to prepare a dry film. The prepared dried film was exposed through a photomask using a parallel light mask aligner (trade name: PLA-501F, manufactured by Canon Inc.) with an ultra-high pressure mercury lamp as the light source, with an exposure amount of 40 mJ/cm ² (i-line). exposed with Thereafter, using an automatic developing device ("AD-2000 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), development is performed with a 0.3% by weight tetramethylammonium aqueous solution for 50 seconds, and then rinsed with water for 30 seconds. bottom. Furthermore, using an oven (trade name: IHPS-222, manufactured by ESPEC Co., Ltd.), it is heated in the air at a temperature of 230 ° C. for 30 minutes, and a glass substrate is coated with 2.0 μm in height, 20 μm in width, and 1.0 μm in thickness. A substrate with light-shielding barrier ribs was obtained in which barrier ribs having an OD value of 2.0 were formed in a lattice pattern with a pitch of 30 μm on the short side and 150 μm on the long side. After that, by the same method as in Example 17, barrier ribs having a height of 10 μm and a width of 20 μm were formed on the light shielding barrier ribs in a lattice pattern similar to that of the light shielding barrier ribs having a pitch of 30 μm on the short side and 150 μm on the long side. obtained a substrate with The color-converting luminescent material composition (CL-2) obtained in Preparation Example 22 was applied to the regions separated by the partition walls of the obtained substrate with partition walls using an inkjet method under a nitrogen atmosphere, and the mixture was heated at 100°C. After drying for 30 minutes, pixels having a thickness of 5.0 μm were formed to obtain a substrate with partition walls having the structure shown in FIG.

Tables 4 and 5 show the configuration of each example and comparative example.

Evaluation methods in each example and comparative example are shown below.

<Refractive index of white pigment>
Regarding the white pigment used in each example and comparative example, the B method (immersion using a microscope) among the plastic refractive index measurement methods specified in JIS K7142-2014 (enacted date = 2014/04/20) method (Becke line method)). The measurement wavelength was 550 nm. However, instead of the immersion liquid used in JIS K7142-2014, "contact liquid" manufactured by Shimadzu Device Manufacturing Co., Ltd. was used, and the measurement was performed under the conditions of immersion liquid temperature: 20°C. A polarizing microscope "Optiphoto" (manufactured by Nikon Corporation) was used as a microscope. Thirty samples of each white pigment were prepared, the refractive index of each sample was measured, and the average value was taken as the refractive index.

<Refractive index of polysiloxane and low refractive index layer>
The polysiloxane, which is the raw material of the partition-forming resin composition used in each of Examples and Comparative Examples, and the low-refractive-index layer-forming material obtained in Preparation Example 26 were each applied onto a silicon wafer with a spinner, followed by hot plate ( It was dried at a temperature of 90° C. for 2 minutes using SCW-636 (trade name, manufactured by Dainippon Screen Mfg. Co., Ltd.). After that, using an oven (IHPS-222; manufactured by ESPEC Co., Ltd.), it was heated in the air at 230° C. for 30 minutes to prepare a cured film. Using a prism coupler (PC-2000 (manufactured by Metricon Co., Ltd.)), the refractive index was measured by irradiating light with a wavelength of 550 nm from the direction perpendicular to the surface of the cured film at 20° C. under atmospheric pressure. , rounded to the second decimal place.

<Resolution>
Using a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), the partition wall resin composition used in each example and comparative example was coated on a 10 cm square non-alkali glass substrate to determine the film thickness after heating. was spin-coated to a thickness of 10 μm, and dried at a temperature of 90° C. for 2 minutes using a hot plate (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) to prepare a dry film with a thickness of 10 μm. .

The prepared dry film was measured using a parallel light mask aligner (trade name: PLA-501F, manufactured by Canon Inc.) with an ultra-high pressure mercury lamp as a light source, and each width of 100 μm, 80 μm, 60 μm, 50 μm, 40 μm, 30 μm and 20 μm. was exposed at an exposure amount of 200 mJ/cm ² (i-line) with a gap of 100 μm through a mask having a line and space pattern of . Then, using an automatic developing device ("AD-2000 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.), shower development is performed using a 0.045% by weight potassium hydroxide aqueous solution for 100 seconds, and then water is used for 30 seconds. Rinse for seconds.

Using a microscope adjusted to a magnification of 100, the pattern after development was enlarged and observed, and the narrowest line width among the patterns in which no residue was observed in the unexposed area was defined as the resolution. However, when there was also a residue in the unexposed area near the pattern with a width of 100 μm, it was defined as “>100 μm”.

<Reflectance>
The partition-forming resin composition used in each example and comparative example was processed under the same conditions as in each example and comparative example, except that the entirety of the resin composition was exposed without using a photomask during exposure. A membrane was prepared. Using the obtained solid film as a model of the partition walls of the substrates with partition walls obtained in each example and comparative example, the glass substrate having the solid film was measured with a spectrophotometer (trade name: CM-2600d, manufactured by Konica Minolta Co., Ltd.). ) was used to measure the reflectance at a wavelength of 550 nm in the SCI mode from the solid film side. However, when cracks occurred in the solid film, the reflectance was not measured because accurate values could not be obtained due to cracks and the like.

<Crack resistance>
The partition wall-forming resin composition used in each example and comparative example was spin-coated so that the film thickness after heating was 5 μm, 10 μm, 15 μm and 20 μm, respectively. For the subsequent steps, except that the whole was exposed without passing through a photomask during exposure, processing was performed under the same conditions as in each example and comparative example, and a solid film was formed on the glass substrate. Using the resulting solid film as a model of the barrier ribs of the substrates with barrier ribs obtained in Examples and Comparative Examples, the glass substrate having the solid film was visually observed to evaluate the presence or absence of cracks in the solid film. If even one crack was confirmed, it was determined that the film had no crack resistance at that film thickness. For example, when there were no cracks at a film thickness of 15 μm and cracks at a film thickness of 20 μm, the crack resistant film thickness was judged to be “≧15 μm”. In addition, the crack-resistant film thickness was determined as “≧20 μm” when there were no cracks even at 20 μm, and the crack-resistant film thickness was determined as “<5 μm” when there were cracks even at 5 μm, and the crack resistance was obtained.

<OD value>
A solid film was formed on a glass substrate as a model of the partition walls of the substrate with partition walls obtained in each example and comparative example in the same manner as in the evaluation of the reflectance. For the glass substrate having the obtained solid film, the intensity of incident light and transmitted light was measured using an optical densitometer (361T (visual); manufactured by X-rite), and the OD value was calculated by the above formula (1). Calculated. As for the OD value, the solid film before the heating process and the OD value after the heating process were measured, and the differences are shown in Tables 6 and 7.

Further, for Example 37, a solid film was similarly formed on a glass substrate as a model of the light shielding partition (A-2). For the obtained glass substrate having a solid film, the intensity of incident light and transmitted light was measured using an optical densitometer (361T (visual); manufactured by X-rite), and the intensity was calculated according to the above formula (1).

<Taper angle>
In each of the examples and comparative examples, an arbitrary cross section of the substrate with partition walls before pixel formation was measured using an optical microscope (FE-SEM (S-4800); manufactured by Hitachi, Ltd.) at an acceleration voltage of 3.0 kV. was observed and the taper angle was measured.

<Surface contact angle>
A solid film was formed on a glass substrate in the same manner as in the evaluation of the reflectance, as a model of the partition walls in the substrates with partition walls obtained in each of the examples and comparative examples. The surface of the obtained solid film was measured at 25 ° C. in the atmosphere using DM-700 manufactured by Kyowa Interface Science Co., Ltd., microsyringe: Teflon (registered trademark) coated needle 22G for contact angle meter manufactured by Kyowa Interface Science Co., Ltd. The surface contact angle was measured in accordance with the substrate glass surface wettability test method defined in JIS R3257 (enacted date = 1999/04/20). However, propylene glycol monomethyl ether acetate was used instead of water, and the contact angle between the surface of the solid film and propylene glycol monomethyl ether acetate was measured.

<Inkjet coatability>
In the substrates with barrier ribs before forming pixels obtained in each example and comparative example, PGMEA was used as an ink for pixel portions surrounded by grid-shaped barrier ribs, and an inkjet coating device (InkjetLabo, cluster technology ( Co., Ltd.) was used for inkjet coating. 160 pL of PGMEA was applied to each grid pattern, and the presence or absence of breakage (a phenomenon in which ink crosses over the partition wall and mixes into the adjacent pixel portion) was observed, and the inkjet applicability was evaluated according to the following criteria. The smaller the breakage, the higher the liquid repellency and the better the inkjet applicability.
A: Ink did not overflow from the pixel.
B: Ink overflowed from the inside of the pixel to the upper surface of the partition in a part.
C: Ink overflowed from the inside of the pixel to the upper surface of the partition on the entire surface.

<Thickness>
For the substrates with partition walls obtained in each example and comparative example, the height of the structure before and after forming the pixel (B) was measured using a Surfcom stylus type film thickness measuring device, and the difference was calculated. , the thickness of the pixel (B) was measured. Further, for Examples 29 and 31, the film thickness of the low refractive index layer (C), for Examples 32 and 36, the film thickness of the color filter, and for Example 37, the thickness (height) of the light-shielding barrier ribs. , respectively, were similarly measured.

Further, for Examples 30 to 31 and 33 to 34, a cross section perpendicular to the base substrate was exposed using a polishing apparatus such as a cross section polisher, and the cross section was enlarged with a scanning electron microscope or a transmission electron microscope. The thicknesses of the inorganic protective layers I to IV were measured by observation.

<Brightness>
A planar light-emitting device equipped with a commercially available LED backlight (peak wavelength 465 nm) was used as a light source, and the substrates with partition walls obtained in each example and comparative example were placed so that the pixel portion was on the light source side. A current of 30 mA is passed through this planar light emitting device to light the LED element, and the luminance (unit: cd/m ² ) based on the CIE1931 standard is measured using a spectral radiance meter (CS-1000, manufactured by Konica Minolta). measured and taken as the initial luminance. However, the evaluation of the brightness was performed using a relative value with the initial brightness of Example 45 being 100 as the standard.

In addition, after lighting the LED element for 48 hours at room temperature (23° C.), the luminance was similarly measured to evaluate the change in luminance over time. However, the evaluation of the brightness was performed using a relative value with the initial brightness of Example 45 being 100 as the standard.

<Color characteristics>
The substrate with partition walls obtained in each example and comparative example was placed on a commercially available white reflector such that the pixels were arranged on the side of the white reflector. Using a spectrophotometer (CM-2600d, manufactured by Konica Minolta, measuring diameter φ8 mm), the substrate with partition walls was irradiated with light from the underlying substrate side, and the spectrum including regular reflection light was measured.

Color standard BT. The color gamut defined by 2020 is defined as the three primary colors red, green and blue on the spectral locus shown in the chromaticity diagram, with the wavelengths of red, green and blue corresponding to 630 nm, 532 nm and 467 nm respectively. From the reflectance (R) at three wavelengths of 470 nm, 530 nm and 630 nm of the obtained reflection spectrum, the emission color of the pixel was evaluated according to the following criteria.
A: _R530 /( _R630 + _R530 + _R470 )≧0.55
B: _R530 /( _R630 + _R530 + _R470 ) < 0.55.

<Display characteristics>
The display characteristics of the display devices produced by combining the substrates with partition walls obtained in each of the examples and the comparative examples and the organic EL elements were evaluated based on the following criteria.
A: The display device has a very vivid green display, and is clear and excellent in contrast.
B: The display device has no problem, although the colors are slightly unnatural.

<Mixed color>
In the substrates with partition walls before forming pixels obtained in each of Examples and Comparative Examples, a color-converting luminescent material composition ( CL-2) was applied and dried at 100° C. for 30 minutes to form pixels with a thickness of 5.0 μm. Then, of the pixel portions surrounded by the grid-like partition walls, the color-converting light-emitting material composition (CL -3) was applied and dried at 100° C. for 30 minutes to form pixels with a thickness of 5.0 μm.

On the other hand, a blue organic EL cell having the same width as the pixel portion surrounded by the grid-like partition walls was prepared, and the substrate with the partition walls and the blue organic EL cell were opposed to each other and bonded with a sealant, as shown in FIG. A display device of the configuration was obtained.

Of the blue organic EL cells 11 in FIG. 10, only the blue organic EL cells bonded immediately below the pixels 3 (CL-2) formed of the color-converting light-emitting material composition (CL-2) are lit. , For the pixel 3 (CL-3) portion formed of the color conversion luminescent material composition (CL-3), using a microscopic spectrophotometer LVmicro-V (manufactured by Lambda Vision Co., Ltd.), the absorption intensity at a wavelength of 630 nm A (630 nm) was measured. A smaller value of the absorption intensity A (630 nm) indicates that color mixture is less likely to occur. Color mixture was determined according to the following criteria.
A: A (630 nm) < 0.01
B: 0.01≦A (630 nm)≦0.5
C: 0.5<A (630 nm).

Tables 6 and 7 show the evaluation results of each example and comparative example.

1: base substrate 2: partition wall 3: pixel 3 (CL-2): pixel 3 (CL-3) formed of color-converting luminescent material composition (CL-2): color-converting luminescent material composition (CL-3 ) Pixel 4 formed by: Low refractive index layer 5: Inorganic protective layer I
6: Inorganic protective layer II
7: Color filter 8: Inorganic protective layer III and/or yellow organic protective layer 9: Inorganic protective layer IV and/or yellow organic protective layer 10: Light blocking partition 11: Blue organic EL cell H: Partition thickness L: Partition width θ: taper angle

Claims (11)

A substrate with barrier ribs having (A-1) patterned barrier ribs on a base substrate, wherein the (A-1) patterned barrier ribs contain a resin, a white pigment, and black or yellow particles. A substrate with partition walls having a reflectance of 20% to 60% per 10 μm thickness at a wavelength of 550 nm and an OD value of 1.0 to 3.0 per 10 μm thickness. The partition wall (A-1) has a resin content of 10% by weight or more and 60% by weight or less, a white pigment content of 20% by weight or more and 60% by weight or less, and a black particle or yellow particle content of 0.5% by weight or more. 2. The substrate with partition walls according to claim 1, wherein the content is 2% by weight or more and 5% by weight or less. The (A-1) patterned partition walls further contain a liquid-repellent compound, and the content of the liquid-repellent compound in the (A-1) patterned partition walls is 0.01% by weight to 10% by weight. 3. The substrate with partition walls according to claim 1 or 2. The substrate with partition walls according to any one of claims 1 to 3, wherein the (A-1) patterned partition walls have a surface contact angle with respect to propylene glycol monomethyl ether acetate of 10° to 70°. The substrate with barrier ribs according to any one of claims 1 to 4, wherein (A-1) the patterned barrier ribs have a taper angle of 45° to 110°. Between the base substrate and (A-1) patterned barrier ribs, there is further provided (A-2) patterned light shielding barrier ribs having an OD value of 0.5 or more per 1.0 μm of thickness. The substrate with partition walls according to any one of claims 1 to 5. The substrate with partition walls according to any one of claims 1 to 6, further comprising (A-1) pixels containing (B) color-converting luminescent material arranged and separated by patterned partition walls. 8. A substrate with partition walls according to claim 7, wherein said color-converting luminescent material contains a phosphor selected from quantum dots and pyrromethene derivatives. 9. The substrate with partition walls according to claim 7, further comprising a color filter having a thickness of 1 to 5 μm between the base substrate and (B) pixels containing the color-converting luminescent material. An inorganic protective layer and/or a yellow organic protective layer with a thickness of 50 to 1,000 nm is further provided on the underlying substrate or between the color filter with a thickness of 1 to 5 μm and the pixel layer containing (B) the color conversion luminescent material. 10. The substrate with partition walls according to claim 9, comprising a layer. 11. A display device comprising the substrate with partition walls according to any one of claims 1 to 10, and a light-emitting light source selected from a liquid crystal cell, an organic EL cell, a mini-LED cell and a micro-LED cell.

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