CN112368611B - Resin composition, light-shielding film, method for producing light-shielding film, and substrate with partition - Google Patents

Resin composition, light-shielding film, method for producing light-shielding film, and substrate with partition Download PDF

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Publication number
CN112368611B
CN112368611B CN201980041920.9A CN201980041920A CN112368611B CN 112368611 B CN112368611 B CN 112368611B CN 201980041920 A CN201980041920 A CN 201980041920A CN 112368611 B CN112368611 B CN 112368611B
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resin composition
light
partition
film
partition wall
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CN112368611A (en
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饭冢英祐
诹访充史
小林秀行
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Toray Industries Inc
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Toray Industries Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations
    • H10K59/8731—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/875—Arrangements for extracting light from the devices
    • H10K59/879—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H10K59/8792—Arrangements for improving contrast, e.g. preventing reflection of ambient light comprising light absorbing layers, e.g. black layers

Abstract

A resin composition comprising: a resin; and an organometallic compound containing at least 1 metal selected from the group consisting of silver, gold, platinum and palladium; and a photopolymerization initiator or a quinonediazide compound; and a solvent. Provided is a resin composition which can form a partition wall having both high reflectance and high light-shielding property even under a heating condition of 250 ℃.

Description

Resin composition, light-shielding film, method for producing light-shielding film, and substrate with partition
Technical Field
The present invention relates to a resin composition, a light-shielding film formed from the resin composition, a method for producing the light-shielding film, and a substrate with barrier ribs having barrier ribs after patterning.
Background
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 passes red, green, and blue. However, the color display using such a color filter has a problem in that the light utilization efficiency is poor and the color reproducibility is poor.
For this reason, as a color display device having improved light use efficiency, a color display device including a wavelength conversion section including a phosphor for wavelength conversion, a polarization separation unit, and a polarization conversion unit has been proposed (for example, see patent document 1). For example, a color display device has been proposed which includes a blue light source, a liquid crystal element, and a wavelength conversion section having a phosphor excited by blue light to emit red fluorescence, a phosphor excited by blue light to emit green fluorescence, and a light scattering layer for scattering the blue light (see, for example, patent document 2).
However, in the color filters including the color conversion phosphors as described in patent documents 1 and 2, since fluorescence is generated in all directions, the light extraction efficiency is low, and the luminance is insufficient. In particular, in high-definition display devices called 4K and 8K, the problem of luminance is remarkable because the pixel size is reduced, and higher luminance is required.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2000-131683
Patent document 2: japanese laid-open patent publication No. 2009-244383
Patent document 3: japanese patent laid-open No. 2000-347394
Patent document 4: japanese patent laid-open publication No. 2006-259421
Disclosure of Invention
Problems to be solved by the invention
In order to improve the luminance of the display device, it is effective to improve the reflectance of the partition walls partitioning the color conversion phosphors. In addition, in order to prevent color mixing of light between adjacent pixels, it is necessary to improve light-shielding properties of the barrier ribs. In view of the above, a partition material having both high reflectance and high light-shielding property is required.
In order to form a partition wall having both high reflectance and high light-shielding property, the inventors of the present application first studied using a material obtained by adding a black pigment to a white partition wall material having high reflectance. However, this method has the following problems: light is absorbed by the white pigment and the black pigment 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 documents 3 and 4, the following techniques are proposed: by adding a specific metal compound, blackening is achieved by firing after patterning. However, these blackening techniques have the following problems: firing at 400 ℃ or higher is required, and the light-shielding property does not improve when heated at 250 ℃ or lower.
Accordingly, an object of the present invention is to provide a resin composition capable of forming a partition wall having both high reflectance and high light-shielding property even under a heating condition of 250 ℃.
Means for solving the problems
The present invention is a resin composition containing:
a resin; and
an organometallic compound containing at least 1 metal selected from the group consisting of silver, gold, platinum and palladium; and
a photopolymerization initiator or a quinonediazide compound; and
a solvent.
Effects of the invention
The resin composition of the present invention allows light to pass through during the pattern exposure step after film formation, and the light-shielding property is improved by heating the exposed film at a temperature of 120 ℃ or higher and 250 ℃ or lower, so that a fine and thick barrier rib pattern having high reflectance and high light-shielding property can be formed even under heating conditions of 250 ℃ or lower.
Drawings
Fig. 1 is a sectional view showing one embodiment of the partition-equipped substrate of the present invention having partition walls after patterning.
Fig. 2 is a sectional view showing one embodiment of the partition-equipped substrate of the present invention having partition walls after pattern formation and pixels containing a color-converting light-emitting material.
Fig. 3 is a cross-sectional view showing one embodiment of the substrate with partition walls of the present invention having a low refractive index layer.
FIG. 4 is a cross-sectional view showing one embodiment of the partition-equipped substrate of the present invention having a low refractive index layer and an inorganic protective layer I.
Fig. 5 is a cross-sectional view showing one embodiment of the partition-equipped substrate of the present invention having a low refractive index layer and an inorganic protective layer II.
Fig. 6 is a cross-sectional view showing one embodiment of the substrate with partition walls of the present invention having a color filter.
Fig. 7 is a sectional view showing one embodiment of the partition-equipped substrate of the present invention having a color filter and an inorganic protective layer III and/or a yellow organic protective layer.
Fig. 8 is a sectional view showing one embodiment of the partition-equipped substrate of the present invention having a color filter and an inorganic protective layer IV and/or a yellow organic protective layer.
FIG. 9 is a sectional view showing one embodiment of the partition-equipped substrate of the present invention having light-shielding partitions.
Fig. 10 is a sectional view showing the configuration of a display device used for color mixture evaluation in the example.
Detailed Description
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 described below in detail, but the present invention is not limited to the following embodiments and can be carried out with various modifications according to the purpose and application.
The resin composition of the present invention can be preferably used as a material for forming partition walls for partitioning color conversion phosphors. The resin composition of the present invention preferably contains: a resin; and an organometallic compound containing at least 1 metal selected from the group consisting of silver, gold, platinum and palladium (hereinafter, sometimes referred to as "organometallic compound"); and a photopolymerization initiator or a quinonediazide compound; and a solvent.
The resin has a function of improving the 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, and more preferably 20% by weight or more, from the viewpoint of improving the crack resistance of the partition wall in the heat treatment. On the other hand, the content of the resin in the solid content of the resin composition is preferably 60% by weight or less, and more preferably 50% by weight or less, from the viewpoint of improving the light resistance. Here, the solid content means all components contained in the resin composition except volatile components such as a solvent. The amount of the solid content can be determined by calculating the remaining amount of the resin composition after heating to evaporate the volatile component.
Examples of the resin include polysiloxane, polyimide precursor, polybenzoxazole precursor, and (meth) acrylic polymers. The (meth) acrylic polymer herein refers to a polymer of methacrylic acid ester and/or acrylic acid ester. More than 2 of these polymers may be contained. Among them, polysiloxanes are preferred in view of excellent transparency, heat resistance and light resistance.
Polysiloxanes are hydrolysis/dehydration condensates of organosilanes. 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). Other repeating units may also be included. By including the repeating unit 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 wall can be improved. The polysiloxane preferably contains 10 to 80 mol% of the repeating unit represented by the general formula (2) in all repeating units. The crack resistance can be further improved by containing 10mol% or more of the repeating unit represented by the general formula (2). The content of the repeating unit represented by the general formula (2) is more preferably 15mol% or more, and still more preferably 20mol% or more. On the other hand, by containing 80 mol% or less of the repeating unit represented by the general formula (2), the molecular weight of the polysiloxane can be sufficiently increased at the time of polymerization, and the coatability can be improved. The content of the repeating unit represented by the general formula (2) is more preferably 70 mol% or less.
[ chemical formula 1]
Figure BDA0002850644660000051
In the above general formula (2), R 1 And R 2 Each of which may be the same or different and represents a 1-valent organic group having 1 to 20 carbon atoms. R is from the viewpoint of easy adjustment of the molecular weight of polysiloxane at the time of polymerization 1 And R 2 Preferably a group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms. However, at least a part of the hydrogen atoms of the alkyl group and the aryl group may be substituted by a radical polymerizable group. In this case, the radical polymerizable group can be radical polymerized in the cured product of the negative photosensitive resin composition.
When the resin composition of the present invention has negative photosensitivity, the polysiloxane preferably further contains a repeating unit selected from a repeating unit represented by the following general formula (3) and a repeating unit represented by the following general formula (4). By including the repeating unit derived from the fluorine-containing alkoxysilane compound represented by the general formula (3) or the general formula (4), the refractive index of the polysiloxane can be reduced, and when the white pigment described later is contained, the difference in refractive index between the polysiloxane and the white pigment can be increased, the interface reflection can be further improved, and the reflectance can be further improved. More preferably, the polysiloxane contains 20 to 80 mol% in total of a repeating unit selected from the group consisting of a repeating unit represented by the general formula (3) and a repeating unit represented by the general formula (4). By including the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4) in a total amount of 20mol% or more, when the white pigment described later is contained, the interface reflection between the polysiloxane and the white pigment can be further improved, and the reflectance can be further improved. The total content of the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4) is more preferably 40 mol% or more. On the other hand, by including the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4) in a total amount of 80 mol% or less, excessive hydrophobization of the polysiloxane can be suppressed, and the compatibility with other components in the composition can be improved to improve the resolution. The total content of the repeating unit represented by the general formula (3) and the repeating unit represented by the general formula (4) is more preferably 70 mol% or less. Other repeating units may also be included.
[ chemical formula 2]
Figure BDA0002850644660000061
In the above general formulae (3) and (4), R 3 Represents an alkyl group, an alkenyl group, an aryl group or an arylalkyl group having 1 to 10 carbon atoms, wherein all or a part of hydrogen atoms are replaced by fluorine. R 4 Represents a single bond, -O-, -CH 2 -CO-, -CO-or-O-CO-. R is 5 Represents a 1-valent organic group having 1 to 20 carbon atoms. From the viewpoint of further lowering the refractive index of polysiloxane, R 3 An alkyl group having 1 to 6 carbon atoms in which all or a part of hydrogen atoms is substituted by fluorine is preferable. In the photocurable material of the negative photosensitive resin composition, the alkenyl group may be radical-polymerized.
The repeating units represented by the above general formulae (2) to (4) are derived from alkoxysilane compounds represented by the following general formulae (5) to (7), respectively. Specifically, the polysiloxane containing the repeating units represented by the general formulae (2) to (4) can be obtained by hydrolyzing and polycondensing an alkoxysilane compound containing an alkoxysilane compound represented by the following general formulae (5) to (7). Other alkoxysilane compounds may also be used.
[ chemical formula 3]
Figure BDA0002850644660000071
In the above general formulae (5) to (7), R 1 ～R 5 Respectively represent the same as R in general formulas (2) to (4) 1 ～R 5 The same group. R is 6 The same or different, and represents a 1-valent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.
As the alkoxysilane compound represented by the general formula (5), examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, ethylmethyldimethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane, gamma-acryloxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3-dimethylethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxysilylpropylpropionic acid, 3-dimethylethyloxysilylpropylpropionic acid, 3-dimethylmethoxycyclohexylsilylpropyldicarboxylic anhydride, 3-dimethylethoxysilylpropyldicarboxylic anhydride, 3-dimethylmethoxydicarboxylic anhydride, 3-dimethylmethoxysilane, 3-dimethylethoxysilylpropyldicarboxylic anhydride, 3-dimethylmethoxyanhydride, and the like, 5-dimethylmethoxysilylpentanoic acid, 5-dimethylethoxysilylpentanoic acid, 3-dimethylmethoxysilylpropylphthalic anhydride, 3-dimethylethoxysilylpropylphthalic anhydride, 4-dimethylmethoxysilylbutyric acid, 4-dimethylethoxysilylbutyric acid, and the like. More than 2 of these compounds may also be used.
Examples of the alkoxysilane compound represented by the general formula (6) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctylpropoxysilane, tridecafluorooctyltripropoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane. More than 2 of these compounds may also be used.
Examples of the alkoxysilane compound represented by the general formula (7) include bis (trifluoromethyl) dimethoxysilane, bis (trifluoropropyl) diethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, and the like. More than 2 of these compounds may also be used.
Examples of other alkoxysilane compounds include: trifunctional alkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane; tetrafunctional alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, and silicate 51 (tetraethoxysilane oligomer); monofunctional alkoxysilane compounds such as trimethylmethoxysilane and triphenylmethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 3-ethyl-3- { [3- (trimethoxysilyl) propoxy ] methyl } oxetane, 3-ethyl-3- { [3- (triethoxysilyl) propoxy ] methyl } oxetane and other epoxy or oxetane group-containing alkoxysilane compounds: alkoxysilane compounds having an aromatic ring such as phenyltrimethoxysilane, phenyltriethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, 1-phenylethyltrimethoxysilane, 1-phenylethyltriethoxysilane, 2-phenylethyltrimethoxysilane, 2-phenylethyltriethoxysilane, 3-trimethoxysilylpropylphthalic anhydride and 3-triethoxysilylpropylphthalic anhydride; alkoxysilane compounds containing a radical polymerizable group such as styryltrimethoxysilane, styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, gamma-acryloylpropyltrimethoxysilane, gamma-acryloylpropyltriethoxysilane, gamma-methacryloylpropyltrimethoxysilane, and gamma-methacryloylpropyltriethoxysilane; and alkoxysilane compounds having a carboxyl group such as 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilylbutyric acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylpentanoic acid, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-triethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, and 3-triethoxysilylpropylphthalic anhydride.
From the viewpoint of setting the content of the repeating unit represented by the general formula (2) in all the repeating units of the polysiloxane to the above range, the content of the alkoxysilane compound represented by the general formula (5) in the alkoxysilane compound serving as a raw material of the polysiloxane is preferably 10mol% or more, more preferably 15mol% or more, and further preferably 20mol% or more. On the other hand, from the same viewpoint, the content of the alkoxysilane compound represented by the general formula (5) is preferably 80 mol% or less, and more preferably 70 mol% or less. The total content of the alkoxysilane compounds represented by the general formulae (6) and (7) is preferably 20mol% or more, and more preferably 40 mol% or more, from the viewpoint of setting the total content of the repeating units represented by the general formulae (3) and (4) to the above range. On the other hand, from the same viewpoint, the total content of the alkoxysilane compounds represented by the general formulae (6) and (7) is preferably 80 mol% or less, and more preferably 70 mol% or less.
From the viewpoint of coatability, the weight average molecular weight (Mw) of the polysiloxane is preferably 1,000 or more, more preferably 2,000 or more. On the other hand, from the viewpoint of developability, the Mw of the polysiloxane is preferably 50,000 or less, and more preferably 20,000 or less. Here, mw of the polysiloxane in the present invention refers to a polystyrene equivalent value measured by Gel Permeation Chromatography (GPC).
The 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 in consideration of the reaction scale, the size, shape, and the like of the reaction vessel according to physical properties suitable for the intended use. Examples of the various conditions include acid concentration, reaction temperature, and reaction time.
For the hydrolysis reaction, an acid catalyst such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acid and/or anhydride thereof, ion exchange resin, or the like can be used. Among them, an acidic aqueous solution containing an acid selected from formic acid, acetic acid and phosphoric acid is preferable.
In the case where an acid catalyst is used in the hydrolysis reaction, the amount of the acid catalyst to be added is preferably 0.05 parts by weight or more, and more preferably 0.1 parts by weight or more, based on 100 parts by weight of the total alkoxysilane compound used in the hydrolysis reaction, from the viewpoint of accelerating the hydrolysis. 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, and more preferably 10 parts by weight or less, based on 100 parts by weight of the entire alkoxysilane compound. The total amount of the alkoxysilane compound is an amount including all of the alkoxysilane compound, a hydrolysate thereof, and a condensate thereof. The same applies below.
The hydrolysis reaction can be carried out in a solvent. The solvent can be appropriately selected in consideration of stability, wettability, volatility, and the like of the resin composition.
In the case where a solvent is generated by the hydrolysis reaction, the hydrolysis can be carried out without a solvent. In the case of using in the resin composition, it is also preferable to adjust the resin composition to an appropriate concentration by further adding a solvent after the completion of the hydrolysis reaction. After hydrolysis, the whole amount or a part of the produced alcohol may be distilled off by heating and/or under reduced pressure, and then an appropriate solvent may be added.
In the case of using a solvent in the hydrolysis reaction, the amount of the solvent added is preferably 50 parts by weight or more, and more preferably 80 parts by weight or more, based on 100 parts by weight of the entire alkoxysilane compound, from the viewpoint of suppressing the formation of gel. 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, based on 100 parts by weight of the total alkoxysilane compound, from the viewpoint of accelerating the hydrolysis.
The water used in the hydrolysis reaction is preferably ion-exchanged water. The amount of water can be arbitrarily set, but is preferably 1.0 to 4.0 moles per 1 mole of the entire alkoxysilane compound.
Examples of the dehydration condensation reaction include a method in which a silanol compound solution obtained by hydrolysis of an organosilane compound is directly heated. The heating temperature is preferably 50 ℃ 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 an alkali catalyst may be performed in order to increase the polymerization degree of polysiloxane. Further, depending on the purpose, an appropriate amount of the product alcohol or the like may be distilled off under heating and/or reduced pressure after the dehydration condensation reaction, and then an appropriate 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 catalyst removal method, water washing, treatment with an ion exchange resin, and the like are preferable from the viewpoints of ease of operation and removability. The water washing means the following method: the polysiloxane solution is diluted with an appropriate hydrophobic solvent, washed several times with water, and the resulting organic layer is concentrated using an evaporator or the like. By treatment based on an ion exchange resin is meant a method of contacting a polysiloxane solution with a suitable ion exchange resin.
The organometallic compound has the following functions: when the partition wall (A-1) is patterned, the partition wall is decomposed and aggregated in the exposure step and/or the heating step to form black particles or yellow particles, thereby increasing the OD value of the partition wall (A-1). Since the OD value is low before exposure and increases after patterning, the exposed light can be sufficiently transmitted to the bottom in the exposure step to be photocured or photodecomposed. For example, in the case of a resin composition having negative photosensitivity, if a resin composition containing a large amount of black pigment is used in advance to form the partition (a-1) having a high OD value and pattern formation is performed, photocuring of the bottom portion tends to be insufficient. As a result, the shape of the obtained partition wall (A-1) tends to be inverted. When the resin composition of the present invention containing the organometallic compound is used for patterning, the resin composition can be sufficiently photocured to the bottom, and thus the taper angle can be easily set to a preferable range described later.
Examples of the organometallic compound include: silver-containing organic metal compounds such as silver neodecanoate, silver octanoate and silver salicylate; gold-containing organic metal compounds such as gold chloro (triphenylphosphine) and tetrachloroauric acid tetrahydrate; platinum-containing organic metal compounds such as bis (acetylacetonato) platinum, dichlorobis (triphenylphosphine) platinum, and dichlorobis (benzonitrile) platinum; palladium-containing organic metal compounds such as bis (acetylacetonato) palladium, dichlorobis (triphenylphosphine) palladium, dichlorobis (benzonitrile) palladium, tetrakis (triphenylphosphine) palladium, and dibenzylideneacetone palladium. These compounds may be contained in 2 or more kinds.
Among them, when an organometallic compound containing silver such as silver neodecanoate, silver octoate, or silver salicylate is contained, it decomposes and aggregates in the exposure step to turn black, and further decomposes and aggregates in the subsequent heating step to turn yellow.
On the other hand, when the catalyst contains a platinum-containing organic metal compound such as bis (acetylacetonato) platinum, dichlorobis (triphenylphosphine) platinum, dichlorobis (benzonitrile) platinum, or the like; palladium-containing organic metal compounds selected from bis (acetylacetonato) palladium, dichlorobis (triphenylphosphine) palladium, dichlorobis (benzonitrile) palladium, tetrakis (triphenylphosphine) palladium, dibenzylideneacetone palladium and the like are decomposed and aggregated in the exposure step and/or the heating step to become black.
Among them, from the viewpoint of further improving the OD value, an organic metal compound selected from bis (acetylacetonato) palladium, dichlorobis (triphenylphosphine) palladium, dichlorobis (benzonitrile) palladium and tetrakis (triphenylphosphine) palladium is preferable.
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 wt% or more, the OD value of the partition wall obtained can be further improved. The content of the organometallic compound is more preferably 1.5% by weight or more. On the other hand, the reflectance can be further improved by setting the content of the organometallic compound to 5% by weight or less.
When the resin composition of the present invention is used for patterning the partition wall (a-1) described later, it preferably has negative or positive photosensitivity. When negative photosensitivity is given, it is preferable to contain a photopolymerization initiator, so that partition walls having a high-definition pattern shape can be formed. The negative photosensitive resin composition preferably further contains a photopolymerizable compound. On the other hand, in the case of imparting positive photosensitivity, it is preferable to contain a quinone diazide compound.
The photopolymerization initiator may be any photopolymerization initiator as long as it is a photopolymerization initiator that decomposes and/or reacts by irradiation with light (including ultraviolet rays and electron beams) to generate radicals. Examples thereof include: α -aminoalkylphenone compounds such as 2-methyl- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and the like; acylphosphine oxide compounds such as 2,4, 6-trimethylbenzoylphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) - (2, 4-trimethylpentyl) -phosphine oxide and the like; oxime ester compounds such as 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1, 2-octanedione-1- [4- (phenylthio) -2- (O-benzoyl oxime) ], 1-phenyl-1, 2-butanedione-2- (O-methoxycarbonyl) oxime, 1, 3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, and ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyl oxime); benzil ketal compounds such as benzil dimethyl ketal; α -hydroxyketone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and 1-hydroxycyclohexyl phenyl ketone; benzophenone compounds such as benzophenone, 4-bis (dimethylamino) benzophenone, 4-bis (diethylamino) benzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4 ' -methyl-diphenylsulfide, alkylated benzophenone, and 3,3', 4' -tetrakis (t-butylperoxycarbonyl) benzophenone; acetophenone compounds such as 2, 2-diethoxyacetophenone, 2, 3-diethoxyacetophenone, 4-tert-butyldichloroacetophenone, benzylideneacetophenone and 4-azidobenzylideneacetophenone; aromatic ketone ester compounds such as methyl 2-phenyl-2-oxoacetate; and benzoate compounds such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, and methyl 2-benzoylbenzoate. These compounds may be contained in 2 or more kinds.
The content of the photopolymerization initiator in the resin composition of the present invention is preferably 0.01% by weight or more, and more preferably 1% by weight or more in the solid content, from the viewpoint of efficiently performing radical curing. On the other hand, the content of the photopolymerization initiator in the solid content is preferably 20% by weight or less, and more preferably 10% by weight or less, from the viewpoint of suppressing elution of the residual photopolymerization initiator and the like and further improving yellowing.
The photopolymerizable compound in the present invention means a compound having 2 or more ethylenically unsaturated double bonds in the molecule. In view of ease of radical polymerization, the photopolymerizable compound preferably has a (meth) acryloyl group.
Examples of the photopolymerizable compound include: diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1, 3-butanediol diacrylate, 1, 3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 9-nonanediol dimethacrylate, 1, 10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, pentapentaerythritol undecalacrylate, tripentaerythritol dodecamethacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol heptapentapentaerythritol decamethacrylate, pentapentaerythritol undecamrylate, and the like. These compounds may be contained in 2 or more kinds.
The content of the photopolymerizable compound in the resin composition of the invention is preferably 1% by weight or more in solid content from the viewpoint of efficiently performing radical curing. On the other hand, from the viewpoint of suppressing an excessive reaction of radicals and improving resolution, the content of the photopolymerizable compound is preferably 40 wt% or less in the solid content.
The quinone diazide compound is preferably a compound in which a sulfonic acid of naphthoquinone diazide is bonded to a compound having a phenolic hydroxyl group in the form of an ester. As the compound having a phenolic hydroxyl group used herein, for example, there may be mentioned: BIS-Z, tekP-4HBPA (tetra P-DO-BPA), trIsP-HAP, trIsP-PA, BISRS-2P, BISRS-3P (trade name, manufactured by NIPPON CHEMICAL INDUSTRY Co., ltd.); BIR-PC, BIR-PTBP, BIR-BIPC-F (trade name, manufactured by Asahi organic materials industries Co., ltd.), 4' -sulfonyldiphenol, BPFL (trade name, manufactured by JFE Chemicals Co., ltd.), and the like. The quinone diazide compound is preferably a compound obtained by introducing naphthoquinone diazide-4-sulfonate or naphthoquinone diazide-5-sulfonate to the compound having a phenolic hydroxyl group through an ester bond, and examples thereof include THP-17, TDF-517 (product name, manufactured by Toyo Synthesis industries, ltd.), SBF-525 (product name, manufactured by AZ Electronic Materials, ltd.), and the like.
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 in terms of solid content, from the viewpoint of improving sensitivity. On the other hand, the content of the quinonediazide compound in the solid content is preferably 25% by weight or less, and more preferably 20% by weight or less, from the viewpoint of improving the resolution.
The solvent has a function of adjusting the viscosity of the resin composition to a range suitable for application and improving the uniformity of the partition wall. The solvent is preferably a combination of a solvent having a boiling point of more than 150 ℃ and 250 ℃ or lower under atmospheric pressure and a solvent having a boiling point of 150 ℃ or lower under atmospheric pressure.
Examples of the solvent include: alcohols such as ethanol, propanol, isopropanol, diacetone alcohol and the like; glycols such as ethylene glycol and propylene glycol; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl 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; amides such as dimethylformamide and dimethylacetamide; acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; gamma-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and the like. These solvents may be contained in 2 or more kinds. Among them, from the viewpoint of coatability, it is preferable to combine diacetone alcohol as a solvent having a boiling point of more than 150 ℃ and not more than 250 ℃ under atmospheric pressure and propylene glycol monomethyl ether as a solvent having a boiling point of not more than 150 ℃ under atmospheric pressure.
The content of the solvent may be arbitrarily set according to the coating method and the like. For example, when the film is formed by spin coating, the content of the solvent is usually 50 wt% or more and 95 wt% or less in the resin composition.
The resin composition of the present invention preferably further contains a complex compound having a phosphorus atom (hereinafter, sometimes referred to as "complex compound"). The complex compound can coordinate with the organometallic compound in the resin composition, and the solubility of the organometallic compound in the solvent is improved to promote the decomposition of the organometallic compound, and the OD value of the obtained partition wall is further improved. Examples of the complexing compound include triphenylphosphine, tri-tert-butylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine tetrafluoroborate, tris (2-furyl) phosphine, tris (1-adamantyl) phosphine, tris (diethylamino) phosphine, tris (4-methoxyphenyl) phosphine, and tris (o-tolyl) phosphine. These compounds may be contained in 2 or more kinds. The content of the complex 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 present invention preferably further contains a white pigment and/or a black pigment. The white pigment has a function of further improving the reflectance of the partition walls. The black pigment has a function of adjusting an OD value.
Examples of the white pigment include titanium dioxide, zirconium oxide, zinc oxide, barium sulfate, and a composite compound thereof. More than 2 of these pigments may be contained. Among them, titanium dioxide, which has a high reflectance and is easily industrially used, is preferable.
The crystal structure of titanium dioxide is classified into anatase type, rutile type and brookite type. Among them, rutile type titanium oxide is preferable in view of low photocatalytic activity.
The white pigment may be subjected to surface treatment. Preferably, the barrier ribs formed by surface treatment with a metal selected from Al, si and Zr can have improved light resistance and heat resistance.
The median particle diameter of the white pigment is preferably 100 to 500nm from the viewpoint of further improving the reflectance of the partition walls. The median particle diameter of the white pigment can be calculated from a particle size distribution obtained by measurement by a laser diffraction method using a particle size distribution measuring apparatus (N4-PLUS; manufactured by Beckman-Coulter Co., ltd.) or the like.
As titanium dioxide pigments which are preferably used as white pigments, there may be mentioned, for example: r960 (rutile, siO) from Dupont 2 /Al 2 O 3 Treatment, the average primary particle size is 210 nm); CR-97 (rutile type, al) from Shigao industries 2 O 3 /ZrO 2 Treatment, the average primary particle size is 250 nm); JR-301 (rutile type, al) manufactured by tayca 2 O 3 Treatment, wherein the average primary particle size is 300 nm); JR-405 (rutile type, al) manufactured by Tayca corporation 2 O 3 The treatment is carried out on the raw materials,average primary particle diameter of 210 nm); JR-600A, tayca (strain) (rutile type, al) 2 O 3 Treatment, the average primary particle size is 250 nm); JR-603, tayca (strain) (rutile type, al) 2 O 3 /ZrO 2 Treatment, average primary particle diameter of 280 nm), and the like. More than 2 of these pigments may also be used.
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, and more preferably 30% by weight or more, in the solid content. On the other hand, the content of the white pigment is preferably 60% by weight or less, more preferably 55% by weight or less in the solid content, from the viewpoint of improving the surface smoothness of the partition wall.
Examples of the black pigment include a black organic pigment, a mixed color organic pigment, and a black inorganic pigment.
Examples of the black organic pigment include carbon black, perylene black, aniline black, and benzofuranone-based pigments. These pigments may also be coated with a resin.
Examples of the mixed color organic pigment include pseudo-black pigments obtained by mixing 2 or more pigments selected from red, blue, green, violet, yellow, magenta, cyan (cyan), and the like. Among them, a mixed pigment of a red pigment and a blue pigment is preferable from the viewpoint of having a high OD value and high pattern processability appropriately. The weight ratio of the red pigment to 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 by Color Index (CI), and the following examples are given. Examples of the red pigment include pigment red (hereinafter abbreviated as PR) 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, PR220, PR223, PR224, PR226, PR227, PR228, PR240, and PR 254. More than 2 of these pigments may be contained. Examples of the blue pigment include pigment blue (hereinafter abbreviated as PB) 15 and PB15: 3. PB15: 4. PB15: 6. PB22, PB60, PB64, and the like. More than 2 of these pigments may also be contained.
Examples of the black inorganic pigment include: graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, gold, platinum, and palladium; a metal oxide; a metal composite oxide; a metal sulfide; a metal nitride; a metal oxynitride; metal carbides, and the like. More than 2 of these pigments may also be contained.
Among the above black pigments, preferred are pigments selected from titanium nitride, zirconium nitride, carbon black, and mixed pigments having a weight ratio of red pigment to blue pigment of 20/80 to 80/20, from the viewpoint of having high light-shielding properties. Further, from the viewpoint of easily adjusting the taper angle of the partition wall (A-1) to a preferable range described later, a pigment selected from titanium nitride, zirconium nitride, and a mixed pigment in which the weight ratio of the red pigment to the blue pigment is 20/80 to 80/20 is more preferable.
From the viewpoint of further suppressing the light mixing in the adjacent pixels by adjusting the reflectance and OD to the above ranges, the content of the black pigment in the resin composition is preferably 0.01 wt% or more, more preferably 0.05 wt% or more, of the solid content. On the other hand, from the viewpoint of adjusting the reflectance and OD to the above ranges, the content of the black pigment is preferably 5% by weight or less, more preferably 3% by weight or less in the solid content.
The resin composition of the present invention preferably further contains a photobase generator. Since the photobase generator is contained, a base is generated in the exposure step to promote decomposition and aggregation of the organometallic compound in the resin composition, the organometallic compound can be converted into black particles or yellow particles more efficiently, and the OD value of the obtained partition wall can be further improved.
The photobase generator may be any photobase generator as long as it is a substance that decomposes and/or reacts by irradiation with light (including ultraviolet rays and electron rays) to generate a base. Examples thereof include guanidine such as 1,5, 7-triazacyclo [4, 0] dec-5-ene 2- (9-oxoxanthen-2-yl) propionate, 1- (anthraquinone-2-yl) ethyl N-cyclohexylcarbamate, 9-anthrylmethyl N, N-diethylcarbamate, 9-anthrylmethyl N-cyclohexylcarbamate, 9-anthrylmethyl piperidine-1-carboxylate, 9-anthrylmethyl N, N-dicyclohexylcarbamate, 1- (anthraquinone-2-yl) ethyl N, N-dicyclohexylcarbamate, cyclohexylammonium 2- (3-benzoylphenyl) propionate, 1, 2-dicyclohexyl-4, 5-tetramethylbiguanide butyltriphenylborate, 1, 2-diisopropyl-3- [ bis (dimethylamino) methylene ] guanidine 2- (3-benzoylphenyl) propionate, 2-nitrophenyl-methyl 4-hydroxypiperidine-1-carboxylate, and 2- (3-benzoylphenyl) propionate. More than 2 of these compounds may also be used.
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 of 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 the resolution.
The resin composition of the present invention may contain a liquid repellent compound. The liquid repellent compound is a compound that imparts a property of repelling water and organic solvents (liquid repellency) to the resin composition. The compound having such properties is not particularly limited, and specifically, a compound having a fluoroalkyl group is preferably used. By containing the liquid-repellent compound, the liquid-repellent property can be imparted to the top of the partition wall after the partition wall (a-1) is formed. Thus, for example, when forming a pixel (B) containing a color-converting luminescent material described later, it is possible to easily coat the color-converting luminescent material having a different composition for each pixel.
As a liquid-repellent compound, there may be mentioned, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethyleneglycol bis (1,1,2,2-tetrafluorobutyl) ether, hexaethyleneglycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropyleneglycol bis (1,1,2,2-tetrafluorobutyl) ether, hexapropyleneglycol bis (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- (perfluorooctanesulfonamide) propyl ] -N, and compounds having a fluoroalkyl group or a fluoroalkylene group at a terminal, a main chain and/or a side chain, such as N' -dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkyl sulfonamide propyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonyl glycinate, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl phosphate), and monoperfluoroalkylethyl phosphate. Further, as commercially available liquid repellent compounds, there are exemplified: "Megafac" (registered trademark) F142D, F172, F173, F183, F444, F477 (manufactured by Dainippon ink chemical Co., ltd.); FTOP EF301, 303 and 352 (manufactured by New autumn field chemical Co., ltd.); fluoradFC-430, FC-431 (manufactured by Sumitomo 3M)); "ASAHIGATE" (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 and BM-1100 (manufactured by Yu merck Co., ltd.); NBX-15, FTX-218, DFX-18 (manufactured by Neos, inc.), and the like. These compounds may be contained in 2 or more kinds. Among them, a liquid repellent compound having a photopolymerizable group is more preferable in terms of high reactivity and capability of forming a strong bond with the resin. Examples of the liquid repellent compound having a fluorine atom and a photopolymerizable group include "Megafac" (registered trade name) "RS-76-E, RS-56, RS-72-k, RS-75, RS-76-E, RS-76-NS, RS-76, and RS-90 (trade name, manufactured by DIC corporation). In this case, the photopolymerizable group can be photopolymerized in the partition wall (a-1) formed of a photocurable material of the negative photosensitive resin composition.
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, in terms of solid content, from the viewpoint of improving the liquid repellency of the partition walls and improving the ink jet coatability. On the other hand, the content of the liquid repellent compound is preferably 10% by weight or less, more preferably 5% by weight or less, in the solid content, from the viewpoint of improving the compatibility with the resin and the white pigment.
The resin composition of the present invention may contain an ultraviolet absorber, a polymerization inhibitor, a surfactant, an adhesion improver, and the like as necessary.
By including an ultraviolet absorber in the resin composition of the present invention, light resistance can be improved and resolution can be further improved. As the ultraviolet absorber, from the viewpoint of transparency and non-coloring property, preferably used are: benzotriazole-based compounds such as 2- (2H-benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4, 6-tert-amylphenol, 2- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, and 2- (2 '-hydroxy-5' -methacryloyloxyethylphenyl) -2H-benzotriazole; benzophenone-based compounds such as 2-hydroxy-4-methoxybenzophenone; and triazine compounds such as 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ (hexyl) oxy ] -phenol.
The resin composition of the present invention contains a polymerization inhibitor, whereby the resolution can be further improved. Examples of the polymerization inhibitor include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1, 4-benzoquinone, and t-butylcatechol. Examples of commercially available polymerization inhibitors include "IRGANOX" (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, 295 (the above products are trade names, manufactured by BASF JAPAN). These polymerization inhibitors may be contained in 2 or more kinds.
By adding a surfactant to the resin composition of the present invention, the fluidity at the time of coating can be improved. Examples of the surfactant include: "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (trade name, manufactured by japan ink chemical industry co.); fluorine-based surfactants such as NBX-15 and FTX-218 (trade name, manufactured by Neos, inc.); silicone surfactants such as "BYK" (registered trademark) -333, 301, 331, 345 and 307 (trade name, BYK-CHEMIE JAPAN, inc.); a polyalkylene oxide surfactant; poly (meth) acrylate surfactants, and the like. These surfactants may be contained in an amount of 2 or more.
By adding the adhesion improver to the resin composition of the present invention, a partition wall having improved adhesion to the base substrate and high reliability can be obtained. Examples of the adhesion improver include alicyclic epoxy compounds and silane coupling agents. Among these, the alicyclic epoxy compound has high heat resistance, and thus can further suppress color change after heating.
Examples of the alicyclic epoxy compound include: 3',4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, 1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol, epsilon-caprolactone-modified 3',4' -epoxycyclohexylmethyl 3',4' -epoxycyclohexanecarboxylate, 1, 2-epoxy-4-vinylcyclohexane, butane tetracarboxylic acid tetra (3, 4-epoxycyclohexylmethyl) modified epsilon-caprolactone, 3, 4-epoxycyclohexylmethyl methacrylate, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, hydrogenated bisphenol A bis (propylene glycol glycidyl ether) ether, hydrogenated bisphenol A bis (ethylene glycol glycidyl ether) ether, 1, 4-cyclohexanedicarboxylic acid diglycidyl ester, 1, 4-cyclohexanedimethanol diglycidyl ether, and the like. These compounds may be contained in 2 or more kinds.
From the viewpoint of further improving the adhesion to the base substrate, the content of the adhesion improver in the resin composition of the present invention is preferably 0.1% by weight or more, more preferably 1% by weight or more, of the solid content. On the other hand, the content of the adhesion improver is preferably 20% by weight or less, more preferably 10% by weight or less of the solid content, from the viewpoint of further suppressing the color change due to heating.
The resin composition of the present invention can be produced by, for example, mixing the above-described resin, organometallic compound, photopolymerization initiator or quinonediazide compound, solvent, and other components as necessary.
Next, the light-shielding film of the present invention will be described. The light-shielding film of the present invention is obtained by curing the resin composition of the present invention. 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 substrate, in addition to the partition (a-1) described later. The film thickness of the light-shielding film is preferably 10 μm or more.
Next, a method for manufacturing a light-shielding film of the present invention will be described. The method for producing a light-shielding film of the present invention preferably comprises the steps of: a film-forming step of coating the resin composition of the present invention on a base substrate and drying the coating to obtain a dried film; an exposure step of pattern-exposing the obtained dried film; a developing step of dissolving and removing a part soluble in a developing solution in the exposed dry film; and a heating step of heating the developed dry film to cure the film.
The method for producing a light-shielding film according to the present invention is characterized in that in the heating step, the OD value at a film thickness of 10 μm is increased by 0.3 or more by heating the developed film at a temperature of 120 ℃ to 250 ℃. From the viewpoint of further improving the OD value, the heating temperature in the heating step is preferably 150 ℃ or higher, and more preferably 180 ℃ or higher. The heating temperature in the heating step is preferably 250 ℃ or lower, and more preferably 240 ℃ or lower, from the viewpoint of suppressing the occurrence of cracks in the heated film. The heating time is preferably 15 minutes to 2 hours. Since the film formed from the resin composition of the present invention has a low OD value during exposure and an increased OD value after patterning, it can be sufficiently photocured up to the bottom in the exposure step to obtain a partition wall having a preferable taper angle described later. Further, since the OD value after patterning is high, a partition wall having both high reflectance and high light-shielding property can be obtained.
Examples of the method for 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 temperature is preferably 80 to 120 ℃ and the drying time is preferably 1 to 15 minutes.
The exposure step is a step of photocuring a desired portion of the dried film or photolyzing an unnecessary portion of the dried film by exposure to make an arbitrary portion of the dried film soluble in a 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 or the like without using a photomask.
As the exposure apparatus, for example, a proximity exposure apparatus can be cited. Examples of the actinic light to be irradiated in the exposure step include near infrared light, visible light, and ultraviolet light is preferable. Examples of the light source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, and a germicidal lamp, and an ultrahigh-pressure mercury lamp is preferable.
The exposure conditions can be appropriately selected depending on the thickness of the dried film to be exposed. In general, it is preferable to use 1 to 100mW/cm 2 The output of the ultra-high pressure mercury lamp is controlled to be 1 to 10,000mJ/cm 2 The exposure is performed with the exposure amount of (1).
The developing step is a step of: the developer-soluble portion of the exposed dry film is dissolved and removed by a developer to obtain a dry film patterned into an arbitrary pattern shape (hereinafter, referred to as a pattern before heating) in which only a portion insoluble in the developer remains. Examples of the pattern shape include a lattice shape and a stripe shape.
Examples of the developing method include a dipping method, a spraying method, and a brushing method.
As the developing solution, a solvent capable of dissolving an unnecessary portion in the dried 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, an aqueous alkali solution is preferable as the developer. Examples of the aqueous alkali solution include: aqueous solutions of inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and calcium hydroxide; and aqueous solutions of organic bases such as tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, and diethanolamine. Among them, from the viewpoint of improving the resolution, a potassium hydroxide aqueous solution or a tetramethylammonium hydroxide aqueous solution is preferable. The concentration of the aqueous alkali solution is preferably 0.05 wt% or more, and more preferably 0.1 wt% or more, from the viewpoint of improving developability. On the other hand, the concentration of the aqueous alkali solution is preferably 5 wt% or less, and more preferably 1 wt% or less, from the viewpoint of suppressing the peeling and corrosion of the pattern before heating. The developing temperature is preferably 20 to 50 ℃ for easy process control.
The heating step is a step of heating and curing the pre-heating pattern formed in the developing step. Examples of the heating device include a hot plate and an oven. Preferred heating temperatures and heating times are as described above.
Next, the partition-equipped substrate of the present invention will be described. The substrate with a partition wall of the present invention has a partition wall (hereinafter, sometimes referred to as "partition wall (a-1)") after pattern formation (a-1) on a base substrate. The base substrate functions as a support in the substrate with the partition wall. In the case of a pixel including a color conversion light-emitting material described later, the partition wall has a function of suppressing light mixture between adjacent pixels.
In the substrate with a partition wall of the present invention, the partition wall (A-1) has a reflectance of 20 to 60% at a wavelength of 550nm at a thickness of 10 μm and an OD value of 1.0 to 3.0 at a thickness of 10 μm. By setting the reflectance to 20% or more and the OD value to 3.0 or less, the luminance of the display device can be improved by the reflection on the side surfaces of the (a-1) partition walls. On the other hand, by setting the reflectance to 60% or less and the OD value to 1.0 or more, light transmitted through the partition wall (a-1) can be suppressed, and light mixture between adjacent pixels can be suppressed.
Fig. 1 is a sectional view showing one embodiment of the partition-equipped substrate of the present invention having partition walls after pattern formation. The base substrate 1 has partition walls 2 after patterning.
< base substrate >
Examples of the base substrate include a glass plate, a resin plate, and a resin film. The glass plate is preferably made of alkali-free glass. As materials of the resin plate and the resin film, polyester, (meth) acrylic acid polymer, transparent polyimide, polyether sulfone, and the like are preferable. The thickness of the glass plate and the resin plate is preferably 1mm or less, and more preferably 0.8mm or less. The thickness of the resin film is preferably 100 μm or less.
< bulkhead (A-1) >)
The partition wall (A-1) has a reflectance of 20 to 60% and an OD value of 1.0 to 3.0 when the thickness is 10 μm at a wavelength of 550nm. The thickness of the partition (A-1) is the length of the partition (A-1) in the direction perpendicular to the base substrate (height direction). In the case of the substrate with partition walls shown in fig. 1, the thickness of the partition walls 2 is denoted by reference character H. The length of the partition wall (A-1) in the direction horizontal to the base 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 denoted by symbol L.
In the present invention, it is considered that: the reflectance on the side surfaces of the partition walls contributes to improvement of the luminance of the display device, and the light-shielding property of the partition walls contributes to suppression of color mixing. On the other hand, since the reflectance and the OD value per unit thickness are considered to be the same regardless of the thickness direction and the width direction, the present invention focuses on the reflectance and the OD value per unit thickness of the partition wall. 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 wall (A-1), and the reflectance and OD value when the thickness is 10 μm are noted.
If the reflectance at a thickness of 10 μm is less than 20%, the reflectance on the side surfaces of the partition walls becomes small, and the luminance of the display device becomes insufficient. The reflectance at a thickness of 10 μm is preferably 30% or more, and more preferably 35% or more. Although the higher the reflectance, the greater the reflection on the partition wall side surface, and hence the luminance of the display device can be improved, if the reflectance is higher than 60%, color mixture occurs between adjacent pixels. The reflectance at a thickness of 10 μm is more preferably 44% or less.
When the OD value at a thickness of 10 μm is less than 1.0, color mixture occurs between adjacent pixels. The OD value at a thickness of 10 μm is preferably 1.5 or more, more preferably 2.0 or more. On the other hand, if the OD value at a thickness of 10 μm is larger than 3.0, reflection on the side surfaces of the partition walls becomes small, and the luminance of the display device becomes insufficient. The OD value at a thickness of 10 μm is more preferably 2.5 or less.
The reflectance of the partition wall (A-1) at a wavelength of 550nm with a thickness of 10 μm can be measured in SCI mode using a spectrophotometer (for example, CM-2600d manufactured by Konica Minolta) from the upper surface of the partition wall (A-1) with a thickness of 10 μm. However, when a sufficient area for measurement cannot be secured or when a measurement sample having a thickness of 10 μm cannot be collected, a solid film (solid film) having the same composition as the partition wall (A-1) and a thickness of 10 μm is prepared when the composition of the partition wall (A-1) is known, and the reflectance at the thickness of 10 μm can be determined by measuring the reflectance in the same manner for the solid film instead of the partition wall (A-1). For example, the material on which the partition walls (A-1) are formed can be used to form a solid film with a thickness of 10 μm, the solid film can be produced under the same processing conditions as those for the formation of the partition walls (A-1) except that no pattern is formed, and the reflectance can be measured from the upper surface of the obtained solid film in the same manner.
The OD value of the partition wall (A-1) having a thickness of 10 μm can be calculated from the following formula (1) by measuring the intensity of incident light and transmitted light from the upper surface of the partition wall (A-1) having a thickness of 10 μm using an optical densitometer (e.g., 361T (visual) manufactured by X-rite). However, when a sufficient area for measurement cannot be secured or when a measurement sample having a thickness of 10 μm cannot be collected, a solid film having the same composition as the partition wall (A-1) and a thickness of 10 μm can be prepared in the same manner as the measurement of reflectance when the composition of the partition wall (A-1) is known, and the OD value at the thickness of 10 μm can be determined by measuring the OD value in the same manner for the solid film instead of the partition wall (A-1).
OD value = log10 (I) 0 /I)···(1)
I 0 : intensity of incident light
I: the intensity of the transmitted light.
As means for adjusting the reflectance and the OD value to the above ranges, for example, the partition wall (a-1) may have a preferable composition as described later.
The taper angle of the partition wall (A-1) is preferably 45 to 110 degrees. The taper angle of the partition (A-1) is an angle formed by the side edge and the bottom edge of the cross section of the partition. In the case of the substrate with the partition wall shown in fig. 1, the taper angle of the partition wall 2 is represented by a symbol θ. By setting the taper angle to 45 DEG or more, the difference between the widths of the upper part and the bottom part of the partition wall (A-1) is reduced, and the width of the partition wall (A-1) can be easily set to a preferable range described later. The taper angle is more preferably 70 ° or more. On the other hand, when a pixel (B) containing a color conversion light-emitting material, which will be described later, is formed by ink jet coating, the ink collapse can be suppressed and the ink jet coatability can be improved by setting the taper angle to 110 ° or less. Here, the collapse of the ink means a phenomenon in which the ink crosses over the partition wall and mixes into the adjacent pixel portion. The taper angle is more preferably 95 ° or less. The taper angle of the partition wall (A-1) can be determined by: an arbitrary cross section of the partition wall (A-1) was observed under the conditions of an acceleration voltage of 3.0kV and a magnification of 2,500 times using an optical microscope (FE-SEM (for example, S-4800 manufactured by Hitachi Ltd.), and an angle formed by a side edge and a bottom edge of the cross section of the partition wall (A-1) was measured.
The means for setting the taper angle of the partition wall (A-1) to the above range includes, for example, forming the partition wall (A-1) into a preferable composition described later and using the resin composition of the present invention described above.
In the case where the substrate with the partition has a pixel (B) containing a color conversion luminescent material described later, the thickness of the partition (a-1) is preferably larger than the thickness of the pixel. 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 efficiently extracting light emission from the bottom of the pixel. The width of the partition wall (a-1) is preferably a width sufficient for further improving the luminance by light reflection on the side surfaces of the partition wall and further suppressing light mixing of adjacent pixels due to light leakage. Specifically, the width of the partition wall is preferably 5 μm or more, and more preferably 15 μm or more. On the other hand, the width of the partition wall (A-1) is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of securing a large number of pixel light-emitting regions and further improving the luminance.
The partition wall (A-1) has a repeating pattern of 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 in the lateral direction and 2000 in the longitudinal direction. The number of pixels affects the resolution (fineness) of the displayed image. Therefore, it is necessary to form pixels in a number corresponding to the required resolution of the image and the screen size of the image display device, and it is preferable to determine the partition wall pattern formation size in accordance with the number.
The partition wall (a-1) preferably contains a resin, a white pigment, and particles formed of at least 1 metal oxide or metal selected from the group consisting of palladium oxide, platinum oxide, gold oxide, silver oxide, palladium, platinum, gold, and silver (hereinafter sometimes referred to as "metal oxide particles or metal particles"). The resin has a function of improving the crack resistance and light resistance of the partition wall. The white pigment has a function of further improving the reflectance of the partition wall. The metal oxide particles or the metal particles have a function of adjusting an OD value and suppressing light mixing of adjacent pixels.
The resin and the white pigment are as described previously as the materials constituting the resin composition. The content of the resin in the partition (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 in the heat treatment. On the other hand, the content of the resin in the partition wall (a-1) is preferably 60% by weight or less, more preferably 50% by weight or less, from the viewpoint of improving the light resistance.
From the viewpoint of further improving the reflectance, the content of the white pigment in the partition wall (a-1) is preferably 20% by weight or more, and more preferably 30% by weight or more. On the other hand, the content of the white pigment in the partition wall (a-1) is preferably 60% by weight or less, more preferably 55% by weight or less, from the viewpoint of improving the surface smoothness of the partition wall.
The metal oxide particles or the metal particles are black particles or yellow particles generated by decomposition and aggregation of the organometallic compound in the resin composition in the exposure step and/or the heating step. From the viewpoint of further suppressing the color mixture of light in adjacent pixels by adjusting the reflectance and OD to the ranges described above, the content of the metal oxide particles or the metal particles in the partition (a-1) is preferably 0.2 wt% or more, and more preferably 0.5 wt% or more. On the other hand, from the viewpoint of adjusting the reflectance and OD to the above ranges, the content of the metal oxide particles or the metal particles in the partition wall (a-1) is preferably 5 wt% or less, and more preferably 3 wt% or less.
The partition wall (A-1) preferably further contains a liquid repellent compound. By containing the liquid-repellent compound, the partition wall (a-1) can be imparted with a liquid-repellent property, and for example, when (B) a pixel containing a color-converting light-emitting material described later is formed, color-converting light-emitting materials having different compositions can be easily applied to the respective pixels. The liquid repellent compound is as described above as a material constituting the resin composition.
The content of the liquid-repellent compound in the partition (a-1) is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, from the viewpoint of improving the liquid-repellent property of the partition and improving the ink jet coatability. On the other hand, 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, from the viewpoint of improving compatibility with the resin or the white pigment.
From the viewpoint of improving the ink-jet coatability and facilitating the color conversion luminescent material to be coated, the contact angle of the partition wall (a-1) with respect to the surface of the propylene glycol monomethyl ether acetate is preferably 10 ° or more, more preferably 20 ° or more, and still more preferably 40 ° or more. On the other hand, from the viewpoint of improving the adhesion between the partition wall and the base substrate, the surface contact angle of the partition wall (a-1) is preferably 70 ° or less, and more preferably 60 ° or less. Here, the surface contact angle of the partition wall (A-1) can be measured with respect to the upper part of the partition wall by the wettability test method of the substrate glass surface prescribed in JIS R3257 (1999/04/20 in the established year and month). The method of making the contact angle of the surface of the partition wall (a-1) within the above range includes, for example, a method of using the above-described liquid repellent compound.
As the method of patterning the partition wall (A-1) on the base substrate, a photosensitive paste method is preferable in view of easy adjustment of the pattern shape. As a method for patterning the partition walls by the photosensitive paste method, for example, a method having the following steps is preferable: a coating step of coating the resin composition on a base substrate and drying the resin composition to obtain a dried film; an exposure step of pattern-exposing the obtained dried film in accordance with a desired pattern shape; a developing step of dissolving and removing a developer-soluble portion of the exposed dry film; and a heating step of curing the developed partition walls. The resin composition preferably has positive or negative photosensitivity. The pattern exposure may be performed through a photomask having a predetermined opening, or an arbitrary pattern may be directly drawn using a laser or the like without using a photomask. When the light-shielding partition (A-2) described later is provided on the partition-equipped substrate, the partition (A-1) can be patterned on the light-shielding partition (A-2) in the same manner. The respective steps are as described above as a method for manufacturing a light-shielding film.
< light-shielding partition wall (A-2) >
The substrate with partition walls of the present invention preferably further has (A-2) partition walls (hereinafter, sometimes referred to as "light-shielding partition walls (A-2)") after patterning, which have an OD value of 0.5 or more when the thickness is 1.0 μm, between the base substrate and the partition walls after patterning (A-1). By providing the light-shielding partition (A-2), light-shielding properties are improved, light leakage from the backlight in the display device is suppressed, and a high-contrast and clear image can be obtained.
Fig. 6 is a sectional view showing one embodiment of the partition-equipped substrate of the present invention having light-shielding partitions. The base substrate 1 has barrier ribs 2 and light-shielding barrier ribs 7 after patterning, and pixels 3 are arranged in regions partitioned by the barrier ribs 2 and the light-shielding barrier ribs 7.
The OD value of the light-shielding partition (A-2) is 0.5 or more when the thickness is 1.0 [ mu ] m. As will be described later, the thickness of the light-shielding partition (A-2) is preferably 0.5 to 10 μm. For this reason, in the present invention, 1.0 μm was selected as a representative value of the thickness of the partition wall (A-2), and the OD value at the thickness of 1.0 μm was noted. By setting the OD value at 1.0 μm or more to 0.5, the light-shielding property can be further improved, and a clear image with higher contrast can be obtained. The OD value at a thickness of 1.0 μm is more preferably 1.0 or more. On the other hand, the OD value at a thickness of 1.0 μm is preferably 4.0 or less, and the patterning property can be improved. The OD value at a thickness of 1.0 μm is more preferably 3.0 or less. The OD value of the light-shielding partition (A-2) can be measured in the same manner as the OD value of the partition (A-1). As a means for setting the OD value to the above range, for example, a preferable composition described later can be given to the light-shielding partition (a-2).
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, the thickness of the light-shielding partition (A-2) is preferably 10 μm or less, more preferably 5 μm or less, from the viewpoint of improving flatness. The width of the light-shielding partition (A-2) is preferably about the same as that of the partition (A-1).
The light-shielding partition (A-2) preferably contains a resin and a black pigment. The resin has a function of improving the 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 the resin include epoxy resins, (meth) acrylic polymers, polyurethanes, polyesters, polyimides, polyolefins, and polysiloxanes. These resins may be contained in 2 or more kinds. Among them, polyimide is preferable in terms of excellent heat resistance and solvent resistance.
Examples of the black pigment include pigments exemplified as the black pigment in the resin composition, palladium oxide, platinum oxide, gold oxide, and silver oxide. From the viewpoint of having high light-shielding properties, a black pigment selected from titanium nitride, zirconium nitride, carbon black, palladium oxide, platinum oxide, gold oxide, and silver oxide is preferable.
As a method for patterning the light-shielding partition (a-2) on the base substrate, for example, the following method is preferable: a method of forming a pattern by using the photosensitive material described in jp 2015-1654 a in the same manner as in the partition wall (a-1) described above by a photosensitive paste method.
The partition-equipped substrate of the present invention preferably further includes (B) pixels containing a color conversion luminescent material (hereinafter sometimes referred to as "pixels (B)") arranged to be spaced apart by the partition (a-1). The pixel (B) has the following functions: color display can be realized by converting at least a part of the wavelength region of incident light and emitting emitted light in a wavelength region different from that of the incident light.
A cross-sectional view of one embodiment of the partition-equipped substrate of the present invention having partition walls (a-1) after pattern formation and pixels (B) containing a color-converting light-emitting material is shown in fig. 2. Partition walls 2 after patterning are provided on a base substrate 1, and pixels 3 are arranged in regions partitioned by the partition walls 2.
The color conversion material preferably contains a phosphor selected from inorganic phosphors and organic phosphors.
The partition-equipped substrate of the present invention can be used as a display device by combining a backlight that emits blue light, liquid crystal formed on a TFT, and a pixel (B), for example. In this case, it is preferable that a red phosphor which emits red fluorescence when excited by blue excitation light is contained in a region corresponding to a red pixel. Similarly, it is preferable that a green phosphor which emits green fluorescence when excited by blue excitation light be contained in a region corresponding to a green pixel. The region corresponding to the blue pixel preferably does not contain a phosphor.
The partition-equipped substrate of the present invention can be used also in a display device of a system using blue micro LEDs (a large number of blue LEDs corresponding to each pixel separated by white partitions are arranged on a substrate) as a backlight. ON/OFF of each pixel can be realized by ON/OFF of the blue micro LED, and liquid crystal is not required. The substrate with a partition of the present invention can be used for any of partitions for separating pixels and partitions for separating blue micro LEDs in a backlight.
The inorganic phosphor is preferably an inorganic phosphor that emits light of various colors such as green and red by excitation light of blue, that is, an inorganic phosphor that has an emission spectrum having a peak in a region of 500 to 700nm when excited by excitation light of a wavelength of 400 to 500nm. Examples of the inorganic phosphor include YAG-based phosphors, TAG-based phosphors, sialon-based phosphors, and Mn 4+ Activated fluoride complex phosphors, inorganic semiconductors called quantum dots, and the like. 2 or more kinds of these inorganic phosphors may also be used. Among them, quantum dots are preferable. Since the quantum dots have a smaller average particle size than other phosphors, the surface of the (B) pixel can be smoothed to suppress light scattering on the surface, and thus the light extraction efficiency can be further improved, and the luminance can be further improved.
Examples of the quantum dots include particles made of group II-IV, group III-V, group IV-VI, group IV semiconductors, and the like. Examples of the inorganic semiconductor include Si, ge, sn, se, te, B, C (including diamond), P, BN, BP, and,BAs、AlN、AlP、AlAs、AlSb、GaN、GaP、GaAs、GaSb、InN、InP、InAs、InSb、ZnO、ZnS、ZnSe、ZnTe、CdS、CdSe、CdSeZn、CdTe、HgS、HgSe、HgTe、BeS、BeSe、BeTe、MgS、MgSe、GeS、GeSe、GeTe、SnS、SnSe、SnTe、PbO、PbS、PbSe、PbTe、CuF、CuCl、CuBr、CuI、Si 3 N 4 、Ge 3 N 4 、Al 2 O 3 And the like. 2 or more kinds of the above inorganic semiconductors may also be used.
The quantum dots may contain a p-type dopant or an n-type dopant. In addition, the quantum dot may have a core-shell structure. In the core-shell structure, any suitable functional layer (single layer or multiple layers) may be formed around the shell according to the purpose, and the surface of the shell may be subjected to surface treatment and/or chemical modification.
Examples of the shape of the quantum dot include a spherical shape, a columnar shape, a scaly shape, a plate shape, and an amorphous shape. The average particle diameter of the quantum dot can be arbitrarily selected depending on the desired emission wavelength, and is preferably 1 to 30nm. When the average particle diameter of the quantum dot is 1 to 10nm, the peak in the emission spectrum can be made sharper in each of blue, green and red colors. The average particle diameter of the quantum dot is preferably 2nm or more, and preferably 8nm or less. For example, when the average particle diameter of the quantum dot is about 2nm, blue light is emitted, when the average particle diameter of the quantum dot is about 3nm, green light is emitted, and when the average particle diameter of the quantum dot is about 6nm, red light is emitted. The average particle diameter of the quantum dots can be measured by a dynamic light scattering method. Examples of a measuring apparatus for the average particle diameter include a dynamic light scattering photometer DLS-8000 (manufactured by Otsuka Denshi Co., ltd.).
The organic phosphor is preferably an organic phosphor that emits light of various colors such as green and red by using excitation light of blue. Examples of the phosphor emitting red fluorescence include a methylene pyrrole derivative having a basic skeleton represented by the following structural formula (8), and examples of the phosphor emitting green fluorescence include a methylene pyrrole derivative having a basic skeleton represented by the following structural formula (9). In addition, perylene derivatives, porphyrin derivatives, oxazine derivatives, pyrazine derivatives, and the like, which emit red or green fluorescence by selection of substituents, can be cited. These organic phosphors may be contained in 2 or more kinds. Among them, a methylene pyrrole derivative is preferable in view of high quantum yield. The methylene pyrrole derivative can be obtained by, for example, the method described in japanese patent application laid-open No. 2011-241160.
[ chemical formula 4]
Figure BDA0002850644660000331
The organic phosphor is soluble in a solvent, and thus can easily form a pixel (B) of a desired thickness.
The thickness of the pixel (B) is preferably 0.5 μm or more, more preferably 1 μm or more, from the viewpoint of improving the color characteristics. 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 and curved surface workability of the display device.
The size of each pixel (B) is usually about 20 to 200. Mu.m.
The pixels (B) are preferably arranged with a partition (A-1) therebetween. By providing the partition wall between the pixels, diffusion and color mixing of emitted light can be further suppressed.
As a method for forming the pixel (B), for example, a method of filling a coating liquid containing a color conversion luminescent material (hereinafter, referred to as a color conversion luminescent material coating liquid) in a space partitioned by the partition wall (a-1) can be cited. The color conversion luminescent material coating liquid may further contain a resin and a solvent.
The method of filling the color conversion luminescent material coating liquid is preferably an inkjet coating method or the like from the viewpoint of facilitating the application of different kinds of color conversion luminescent materials to respective pixels.
The resultant coating film may be dried under reduced pressure and/or dried by heating. In the case of reduced pressure drying, the reduced pressure drying temperature is preferably 80 ℃ or lower in order to prevent recondensation of the drying solvent on the inner wall of the reduced pressure chamber. The pressure for drying under reduced pressure is preferably not more than the vapor pressure of the solvent contained in the coating film, and is preferably 1 to 1000Pa. The drying time under reduced pressure is preferably 10 to 600 seconds. In the case of heat drying, examples of the heat drying device include an oven and a hot plate. The heating and drying temperature is preferably 60 to 200 ℃. The heating and drying time is preferably 1 to 60 minutes.
The substrate with partition walls of the present invention preferably further has (C) a low refractive index layer (hereinafter sometimes referred to as "low refractive index layer (C)") having a refractive index of 1.20 to 1.35 at a wavelength of 550nm, on the pixel (B). 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.
A cross-sectional view of one embodiment of the substrate with partition walls of the present invention having a low refractive index layer is shown in fig. 3. The base substrate 1 has the partition walls 2 and the pixels 3 after patterning, 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, and more preferably 1.23 or more, from the viewpoint of appropriately suppressing reflection of light from the backlight and allowing light to be efficiently incident on the pixel (B). On the other hand, the refractive index of the low refractive index layer (C) is preferably 1.35 or less, more preferably 1.30 or less, from the viewpoint of improving the luminance. Here, the refractive index of the low refractive index layer (C) can be measured by irradiating light having a wavelength of 550nm from a direction perpendicular to the surface of the cured film under the condition of 20 ℃ under atmospheric pressure using a prism coupler.
The low refractive index layer (C) preferably contains polysiloxane and silica particles having no hollow structure. The polysiloxane functions as a binder having high compatibility with inorganic particles such as silica particles and capable of forming a transparent layer. In addition, by containing the silica particles, fine voids can be efficiently formed in the low refractive index layer (C) to lower the refractive index, and the refractive index can be easily adjusted to the above range. Further, by using silica particles having no hollow structure, there is no hollow structure in which cracks are likely to occur during curing shrinkage, and therefore cracks can be suppressed. In the low refractive index layer (C), the polysiloxane and the silica particles having no hollow structure may be contained independently from each other, or the polysiloxane and the silica particles having no hollow structure may be contained in a state in which the polysiloxane and the silica particles having no hollow structure are bonded to each other. 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 in which the polysiloxane is bonded to the silica particles having no hollow structure.
The 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. The fluorine-containing polysiloxane can be obtained by hydrolyzing and polycondensing a plurality of alkoxysilane compounds containing at least a fluorine-containing alkoxysilane compound represented by the following general formula (10). Other alkoxysilane compounds may be further used.
[ chemical formula 5]
R 7 m Si(OR 6 ) 4-m (10)
In the above general formula (10), R 7 Represents a fluoroalkyl group having a fluorine number of 3 to 17. R is 6 Represents R in the general formulae (5) to (7) 6 The same group. m represents 1 or 2.4-m R 6 And m R 7 May be the same or different, respectively.
As the fluorine-containing alkoxysilane compound represented by the general formula (10), examples thereof include trifluoroethyl trimethoxysilane, trifluoroethyl triethoxysilane, trifluoroethyl triisopropoxysilane, trifluoropropyl trimethoxysilane, trifluoropropyl triethoxysilane, trifluoropropyl triisopropoxysilane, heptadecafluorodecyl trimethoxysilane, heptadecafluorodecyl triethoxysilane, heptadecafluorodecyl triisopropoxysilane, tridecafluorooctyl triethoxysilane, tridecafluorooctyl trimethoxysilane, tridecafluorooctyl triisopropoxysilane, trifluoroethyl methyldimethoxysilane, trifluoroethyl methyldiethoxysilane, trifluoroethyl methyldiisopropoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylmethyldiisopropoxysilane, heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecylmethyldiethoxysilane, heptadecafluorodecylmethyldiisopropoxysilane, tridecafluorooctylmethyldimethoxysilane, tridecafluorooctylmethyldiisopropoxysilane, trifluoroethylethyl dimethoxysilane, trifluoroethylethyl diethoxysilane, trifluoroethylethyl diisopropoxysilane, trifluoropropylethyl dimethoxysilane, trifluoropropylethyldiethoxysilane, trifluoropropylethylethylethyldiethoxysilane, trifluoropropylethylethyldiethoxysilane, heptadecafluoroethylmethyldiethoxysilane, heptadecafluoroethyldimethoxysilane, heptadecafluoroethyldiethoxysilane, heptadecafluoroethylethyldiethoxysilane, heptadecafluoroethyldiethoxysilane, and the like. More than 2 of these compounds may also be used.
The content of the polysiloxane in the low refractive index layer (C) is preferably 4 wt% or more from the viewpoint of suppressing cracking. On the other hand, the content of the polysiloxane is preferably 32 wt% or less from the viewpoint of ensuring thixotropy by the network between silica particles, appropriately maintaining the air layer in the low refractive index layer (C), and further reducing the refractive index.
Examples of the silica particles having no hollow structure in the low refractive index layer (C) include "Snowtex" (registered trademark) manufactured by nippon chemical industry, and "organic 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, and other types of PGM-ST, PMA-ST, IPA-ST-L, IPA-ST-UP, and the like). These silica particles may be contained in 2 or more kinds.
From the viewpoint of ensuring thixotropy by the network between silica particles, appropriately maintaining an air layer in the low refractive index layer (C), and further lowering the refractive index, the content of silica particles having no hollow structure in the low refractive index layer (C) is preferably 68% by weight or more. On the other hand, the content of the silica particles having no hollow structure is preferably 96% by weight or less from the viewpoint of suppressing cracking.
The thickness of the low refractive index layer (C) is preferably 0.1 μm or more, and more preferably 0.5 μm or more, from the viewpoint of suppressing the occurrence of defects by covering the step of the pixel (B). On the other hand, the thickness of the low refractive index layer (C) is preferably 20 μm or less, and more preferably 10 μm or less, from the viewpoint of reducing stress that causes cracking of the low refractive index layer (C).
The method for forming the low refractive index layer (C) is preferably a coating method in view of ease of the forming method. For example, the low refractive index layer (C) can be formed by applying a low refractive index resin composition containing polysiloxane and silica particles to the pixel (B), drying the applied composition, and heating the dried composition.
In addition, the substrate with a partition wall of the present invention preferably further has an inorganic protective layer I having a thickness of 50 to 1,000nm on the low refractive index layer (C). By having the inorganic protective layer I, moisture in the atmosphere hardly reaches the low refractive index layer (C), and therefore, variation in refractive index of the low refractive index layer (C) can be suppressed, and deterioration in luminance can be suppressed.
Fig. 4 is a cross-sectional view showing one embodiment of the partition-equipped substrate of the present invention having a low refractive index layer and an inorganic protective layer I. The base substrate 1 has patterned partition walls 2 and pixels 3, and further has a low refractive index layer 4 and an inorganic protective layer I5 thereon.
In the substrate with a partition wall of the present invention, it is preferable that an inorganic protective layer II having a thickness of 50 to 1,000nm is further provided between the pixel (B) and the low refractive index layer (C). By having the inorganic protective layer II, the raw material for forming the pixel (B) is less likely to move from the pixel (B) to the low refractive index layer, and thus variation in the refractive index of the low refractive index layer (C) can be suppressed, and luminance degradation can be suppressed.
Fig. 5 is a cross-sectional view showing one embodiment of the partition-equipped substrate of the present invention having a low refractive index layer and an inorganic protective layer II. The base substrate 1 has the partition walls 2 and the pixels 3 after patterning, and further has an inorganic protective layer II6 and a low refractive index layer 4 on them.
The partition-equipped substrate of the present invention preferably further includes a color filter (hereinafter sometimes referred to as "color filter") having a thickness of 1 to 5 μm between the base substrate and the pixel (B). The color filter has a function of transmitting visible light in a specific wavelength region and changing the transmitted light into a desired color tone. By providing the color filter, the color purity of the display device can be improved. The color purity can be further improved by setting the thickness of the color filter to 1 μm or more. On the other hand, the luminance can be further improved by setting the thickness of the color filter to 5 μm or less.
A cross-sectional view of one embodiment of the substrate with partition walls of the present invention having a color filter is shown in fig. 6. The partition walls 2 and the color filter 7 after patterning are provided on the base substrate 1, and the pixels 3 are provided on the color filter 7.
Examples of the color filter include a color filter using a pigment dispersion type material in which a pigment is dispersed in a photoresist, which is used for a flat panel display such as a liquid crystal display. More specifically, examples thereof include a blue color filter which selectively transmits wavelengths of 400nm to 550nm, a green color filter which selectively transmits wavelengths of 500nm to 600nm, a yellow color filter which selectively transmits wavelengths of 500nm or more, and a red color filter which selectively transmits wavelengths of 600nm or more. The color filter may be stacked separately from the pixel (B) containing the color conversion luminescent material, or may be stacked integrally.
In addition, 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 1,000nm between the color filter and the pixel (B). By having the inorganic protective layer III, the raw material for forming the color filter is less likely to reach the pixel (B) containing the color conversion luminescent material from the color filter, and thus the luminance degradation of the pixel (B) containing the color conversion luminescent material can be suppressed. Further, by providing the yellow organic protective layer, blue leakage light which is not completely converted by the pixel (B) containing the color conversion light emitting material can be cut off, and color reproducibility can be improved.
Fig. 7 is a cross-sectional view showing one embodiment of the partition-equipped substrate of the present invention having a color filter and an inorganic protective layer III and/or a yellow organic protective layer. The partition walls 2 and the color filters 7 after patterning are provided on the base substrate 1, the inorganic protective layer III and/or the yellow organic protective layer 8 are provided on the partition walls, and the pixels 3 arranged with the partition walls 2 (the partition walls 2 are covered with the inorganic protective layer III and/or the yellow organic protective layer 8) spaced apart are provided.
In addition, the substrate with a partition wall of the present invention preferably further comprises an inorganic protective layer IV and/or a yellow organic protective layer having a thickness of 50 to 1,000nm on the base substrate. The inorganic protective layer IV and/or the yellow organic protective layer can function as a refractive index adjusting layer, and can more efficiently extract light emitted from the pixel (B), thereby further improving the luminance of the display device. In addition, the yellow organic protective layer can cut off blue leakage light that is not converted by the pixel (B) containing the color conversion light emitting material, and can improve color reproducibility. The inorganic protective layer IV and/or the yellow organic protective layer are preferably provided between the base substrate and the partition (a) and the pixel (B).
Fig. 8 is a sectional view showing one embodiment of the partition-equipped substrate of the present invention having an inorganic protective layer IV and/or a yellow organic protective layer. An inorganic protective layer IV and/or a yellow organic protective layer 9 are provided on the base substrate 1, and the partition walls 2 and the color filters 7 after patterning are provided thereon, and the partition walls 2 and the pixels 3 after patterning are provided thereon.
Examples of the material constituting the inorganic protective layers I to IV include: metal oxides such as silicon oxide, indium tin oxide, gallium zinc oxide, and the like; metal nitrides such as silicon nitride; and fluorides such as magnesium fluoride. More than 2 of these materials may be contained. Among these, silicon nitride and silicon oxide are more preferable in terms of low water vapor permeability and high permeability.
The thickness of the inorganic protective layers I to IV is preferably 50nm or more, and more preferably 100nm or more, from the viewpoint of sufficiently suppressing the permeation of substances such as water vapor. On the other hand, the thickness of the inorganic protective layers I to IV is preferably 800nm or less, and more preferably 500nm or less, from the viewpoint of suppressing the decrease in transmittance.
The thickness of the inorganic protective layers I to IV can be measured by: a cross section perpendicular to the base substrate is exposed by using a polishing device such as a cross section polisher, and the cross section is observed under magnification by using a scanning electron microscope or a transmission electron microscope.
Examples of the method for forming the inorganic protective layers I to IV include a sputtering method. The inorganic protective layer is preferably colorless transparent or yellow 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 the organometallic compound. As described above, the silver-containing organic metal compound has a function of turning a protective layer into yellow particles by decomposition and aggregation in a heating step at the time of pattern formation. Examples of the silver-containing organometallic compound include silver neodecanoate, silver octanoate, and silver salicylate. Among them, silver neodecanoate is preferable from the viewpoint of further enabling yellowing. In the resin composition for a yellow organic protective layer, the content of the silver-containing organic metal compound is preferably 0.2 to 5% by weight in the solid content. By setting the content of the silver-containing organometallic compound to 0.2% by weight or more, further yellowing can be achieved. The content of the silver-containing organometallic compound is more preferably 1.5% by weight or more in the solid content. On the other hand, the transmittance can be further improved by setting the content of the silver-containing organometallic compound to 5% by weight or less in the solid content.
The resin composition forming the yellow organic protective layer may contain a yellow pigment. Examples of the yellow pigment 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, and PY 185. Among them, a yellow pigment selected from PY139, PY147, PY148, and PY150 is preferable from the viewpoint of selectively blocking blue light.
As a method for patterning the yellow organic protective layer, a method of patterning by a photosensitive paste method is preferable, similarly to the partition wall (a-1) described above.
As shown in fig. 7, in the case where the yellow organic protective layer 8 is formed on the color filter 7, the yellow organic protective layer 8 may function as an overcoat layer for planarizing each pixel of the color filter.
The thickness of the yellow organic protective layer is preferably 100nm or more, and more preferably 500nm or more, from the viewpoint of sufficiently shielding the blue leakage light. On the other hand, the thickness of the yellow organic protective layer is preferably 3000nm or less, more preferably 2000nm or less, from the viewpoint of suppressing the decrease in light extraction efficiency.
Next, the display device of the present invention will be explained. The display device of the present invention has the substrate with a partition and a light-emitting source. The light-emitting source is preferably a light-emitting source selected from a liquid crystal cell, an organic EL cell, a mini LED cell, and a micro LED cell. From the viewpoint of excellent light emission characteristics, an organic EL unit is more preferable as the light emission source. Here, the mini LED unit is a unit in which a large number of LEDs having a longitudinal and lateral length of about 100 μm to 10mm are arranged. The micro LED unit is a unit in which a large number of LEDs having a length of less than 100 μm in the longitudinal and lateral directions are arranged.
The method for manufacturing a display device of the present invention is described by taking an example of a display device including the partition-equipped substrate and the organic EL unit of the present invention. A photosensitive polyimide resin was applied on a glass substrate, and an insulating film having an opening was formed by photolithography. After sputtering aluminum thereon, aluminum was patterned by photolithography, and a back electrode layer made of aluminum was formed in the opening portion without the insulating film. Next, tris (8-quinolinolato) aluminum (hereinafter abbreviated as Alq 3) was formed thereon as an electron transporting layer by a vacuum deposition method, and then a white light emitting layer in which dicyanomethylenepyran, quinacridone, and 4,4' -bis (2, 2-diphenylvinyl) biphenyl were doped in Alq3 was formed as a light emitting layer. Next, N '-diphenyl-N, N' -bis (α -naphthyl) -1,1 '-biphenyl-4, 4' -diamine was formed as a hole transporting layer by a vacuum evaporation method. Finally, ITO was formed as a transparent electrode by sputtering, and an organic EL cell having a white light-emitting layer was produced. The partition-equipped substrate and the organic EL cell thus obtained are opposed to each other and bonded to each other with a sealant, whereby a display device can be manufactured.
Examples
The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to these ranges. Among the compounds used, the abbreviated compounds are named as follows.
PGMEA: propylene glycol monomethyl ether acetate
DAA: diacetone alcohol
BHT: dibutylhydroxytoluene.
The solid content concentration of the polysiloxane solutions in synthesis examples 1 to 4 was determined by the following method. 1.5g of the polysiloxane solution was weighed into an aluminum cup and heated at 250 ℃ for 30 minutes using a hot plate to evaporate the liquid components. 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 determined from the ratio to the weight before heating.
The weight average molecular weight of the polysiloxanes in synthesis examples 1 to 4 was determined by the following method. GPC analysis was performed in accordance with JIS K7252-3 (2008/03/20 in manufactured year and month) using a GPC analyzer (HLC-8220; manufactured by Tosoh Co., ltd.) and tetrahydrofuran as a mobile phase, and the weight average molecular weight in terms of polystyrene was measured.
The content ratio of each repeating unit in the polysiloxanes of synthesis examples 1 to 4 was determined by the following method. The polysiloxane solution was injected into a NMR sample tube made of "Teflon" (registered trade name) having a diameter of 10mm, and the mixture was subjected to 29 In the Si-NMR measurement, the content ratio of each repeating unit was calculated from the ratio of the integral value of Si derived from a specific organosilane to the integral value of all Si derived from the organosilane. 29 The Si-NMR measurement conditions are shown below.
The device comprises the following steps: nuclear magnetic resonance apparatus (JNM-GX 270; manufactured by Nippon electronics Co., ltd.)
The determination method comprises the following steps: gated decoupling method
Measurement of nuclear frequency: 53.6693MHz ( 29 Si nucleus)
Spectral width: 20000Hz
Pulse width: 12 mu s (45 degree pulse)
Pulse repetition time: 30.0 seconds
Solvent: acetone-d 6
Reference substance: tetramethylsilane
Measuring temperature: 23 deg.C
Sample rotation speed: 0.0Hz.
Synthesis example 1 polysiloxane (PSL-1) solution
A1000 ml three-necked flask was charged with 147.32g (0.675 mol) of trifluoropropyltrimethoxysilane, 40.66g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, 26.23g (0.10 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 12.32g (0.05 mol) of 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane, 0.808g of BHT0.62 g and 171.62g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 2.265g (1.0% by weight based on the charged monomer) of phosphoric acid in 52.65g of water was added thereto with stirring at room temperature for 30 minutes. Then, the flask was immersed in an oil bath at 70 ℃ and stirred for 90 minutes, after which the oil bath was heated to 115 ℃ over 30 minutes. 1 hour after the start of the temperature rise, the solution temperature (internal temperature) reached 100 ℃ and then the mixture was heated and stirred for 2 hours (internal temperature 100 to 110 ℃ C.) to obtain a polysiloxane solution. During the temperature rise and the heating and stirring, a mixed gas of 95 vol% nitrogen and 5 vol% oxygen was flowed at a rate of 0.05 l/min. Methanol as a by-product was distilled off during the reaction, and 131.35g of hydrate was obtained. To the polysiloxane solution thus obtained, PGMEA was added so that the solid content concentration became 40 wt%, to obtain a polysiloxane (PSL-1) solution. The weight average molecular weight of the polysiloxane (PSL-1) thus obtained was 4,000. The molar ratios of the respective repeating units derived from trifluoropropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride and 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane in the polysiloxane (PSL-1) were 67.5mol%, 17.5mol%, 10mol% and 5mol%, respectively.
Synthesis example 2 polysiloxane (PSL-2) solution
Into a 1000ml three-necked flask, 116.07g (0.475 mol) of diphenyldimethoxysilane, 0.20mol of dimethyldimethoxysilane, 43.46g (0.175 mol) of 3-methacryloxypropyltrimethoxysilane, 26.23g (0.10 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 12.32g (0.05 mol) of 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane, 0.843g of BHT, and 176.26g of PGMEA were charged, and an aqueous phosphoric acid solution prepared by dissolving 2.221g (1.0% by weight based on the charged monomers) of phosphoric acid in 43.65g of water was added with stirring at room temperature for 30 minutes. Then, a polysiloxane solution was obtained in the same manner as in Synthesis example 1. Methanol was distilled off as a by-product in the reaction, and the hydration amounted to 136.90g. To the polysiloxane solution thus obtained, PGMEA was added so that the solid content concentration became 40 wt%, to obtain a polysiloxane (PSL-2) solution. The weight average molecular weight of the polysiloxane (PSL-2) obtained was 2,800. The molar ratios of the respective repeating units derived from diphenyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride and 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane in the polysiloxane (PSL-2) were 47.5mol%, 20mol%, 17.5mol%, 10mol% and 5mol%, respectively.
Synthesis example 3 polysiloxane (PSL-3) solution
147.32g (0.675 mol) of trifluoropropyltrimethoxysilane, 43.46g (0.175 mol) of 3-methacryloxypropyltrimethoxysilane, 26.23g (0.10 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 12.32g (0.05 mol) of 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane, 0.810g of BHT0, and 172.59g of PGMEA were put into a 1000ml three-necked flask, and an aqueous phosphoric acid solution prepared by dissolving 2.293g (1.0 wt% with respect to the charged monomers) of phosphoric acid in 54.45g of water was added thereto over 30 minutes with stirring at room temperature. Then, a polysiloxane solution was obtained in the same manner as in Synthesis example 1. Methanol as a by-product was distilled off during the reaction and 140.05g of hydrate was obtained. To the polysiloxane solution thus obtained, PGMEA was added so that the solid content concentration became 40 wt%, to obtain a polysiloxane (PSL-3) solution. The weight average molecular weight of the polysiloxane (PSL-3) thus obtained was 4,100. The molar ratios of the respective repeating units derived from trifluoropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride and 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane in the polysiloxane (PSL-3) were 67.5mol%, 17.5mol%, 10mol% and 5mol%, respectively.
Synthesis example 4 polysiloxane (PSL-4) solution
A1000 ml three-necked flask was charged with 34.05g (0.250 mol) of methyltrimethoxysilane, 99.15g (0.500 mol) of phenyltrimethoxysilane, 31.25g (0.150 mol) of tetraethoxysilane, 24.64g (0.100 mol) of 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane and 174.95g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 0.945g (0.50 wt% based on the charged monomer) of phosphoric acid in 56.70g of water was added thereto over 30 minutes with stirring at room temperature. Then, a polysiloxane solution was obtained in the same manner as in Synthesis example 1. Methanol as a by-product was distilled off during the reaction and the hydration amounted to 129.15g. To the polysiloxane solution thus obtained, PGMEA was added so that the solid content concentration became 40 wt%, to obtain a polysiloxane (PSL-4) solution. The weight average molecular weight of the polysiloxane (PSL-4) thus obtained was 4,200. The molar ratios of the respective repeating units derived from methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane and 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane in the polysiloxane (PSL-4) were 25mol%, 50mol%, 15mol% and 10mol%, respectively.
The compositions of synthesis examples 1 to 4 are summarized in Table 1.
[ Table 1]
Figure BDA0002850644660000451
Synthesis example 5 Green organic phosphor
3, 5-dibromobenzaldehyde (3.0 g), 4-tert-butylphenyl boronic acid (5.3 g), and tetrakis (triphenylphosphine) are added) Palladium (0) (0.4 g) and potassium carbonate (2.0 g) were put in a flask and replaced with nitrogen. Degassed toluene (30 mL) and degassed water (10 mL) were added thereto, and the mixture was refluxed for 4 hours. The reaction solution was cooled to room temperature, liquid separation was performed, and then the organic layer was washed with saturated brine. The organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. The obtained reaction product was purified by means of a silica gel column chromatography to give 3, 5-bis (4-tert-butylphenyl) benzaldehyde (3.5 g) as a white solid. Subsequently, 3, 5-bis (4-tert-butylphenyl) benzaldehyde (1.5 g) and 2, 4-dimethylpyrrole (0.7 g) were placed in a flask, dehydrated dichloromethane (200 mL) and trifluoroacetic acid (1 drop) were added, and the mixture was stirred under a nitrogen atmosphere for 4 hours. To the reaction mixture was added a solution of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (0.85 g) in dehydrated dichloromethane, and the mixture was 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 after stirring for 4 hours, water (100 mL) was further added, and the mixture was stirred to separate the organic layer. The organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. The obtained reaction product was purified by silica gel column chromatography to obtain 0.4g of green powder (yield: 17%). Of the resulting green powder 1 The results of H-NMR analysis are shown below, 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)。
[ chemical formula 6]
Figure BDA0002850644660000471
Synthesis example 6 Red organic phosphor
A mixed solution of 300mg of 4- (4-tert-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 201mg of 2-methoxybenzoyl chloride and 10ml of toluene was heated at 120 ℃ for 6 hours under a nitrogen stream. After cooling to room temperature, the solvent was evaporated. Washing the obtained residue with 20ml of ethanolVacuum drying was carried out, whereby 260mg of 2- (2-methoxybenzoyl) -3- (4-tert-butylphenyl) -5- (4-methoxyphenyl) pyrrole was obtained. Subsequently, a mixed solution of 260mg of 2- (2-methoxybenzoyl) -3- (4-tert-butylphenyl) -5- (4-methoxyphenyl) pyrrole, 180mg of 4- (4-tert-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 206mg of methanesulfonic anhydride and 10ml of degassed toluene was heated at 125 ℃ for 7 hours under a nitrogen stream. After the reaction mixture was cooled to room temperature, 20ml of water was poured into the reaction mixture, and the mixture was extracted with 30ml of dichloromethane. The organic layer was washed 2 times with 20ml of water, evaporated, and vacuum-dried to obtain a residue of a methylenepyrrole. Then, to a mixed solution of the obtained methylene-pyrrole and 10ml of toluene, 305mg of diisopropylethylamine and 670mg of boron trifluoride diethyl ether complex were added under a nitrogen stream, and the mixture was stirred at room temperature for 3 hours. To the reaction mixture was added 20ml of water, followed by extraction with 30ml of dichloromethane. The organic layer was washed with 20ml of water 2 times, dried over magnesium sulfate, and evaporated. Purification was performed by silica gel column chromatography, and after vacuum drying, 0.27g of a purple powder was obtained (yield: 70%). Of the resulting reddish-purple powder 1 The results of H-NMR analysis are shown below, and it was confirmed that the magenta 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)。
[ chemical formula 7]
Figure BDA0002850644660000481
Synthesis example 7 Silicone solution containing silica particles (LS-1)
A500 ml three-necked flask was charged with 224.37g of an isopropyl alcohol dispersion (IPA-ST-UP: manufactured by Nissan chemical industries, ltd.) of methyltrimethoxysilane 0.05g (0.4 mmol), trifluoropropyltrimethoxysilane 0.66g (3.0 mmol), trimethoxysilylpropylsuccinic anhydride 0.10g (0.4 mmol), gamma-acryloyloxypropyltrimethoxysilane 7.97g (34 mmol) and 15.6 wt% of silica particles, and 163.93g of ethylene glycol mono-t-butyl ether was further added. An aqueous phosphoric acid solution prepared by dissolving 0.088g of phosphoric acid in 4.09g of water was added thereto over 3 minutes while stirring at room temperature. Then, the flask was immersed in an oil bath at 40 ℃ and stirred for 60 minutes, after which the oil bath was heated to 115 ℃ over 30 minutes. 1 hour after the start of the temperature rise, the internal temperature of the solution reached 100 ℃ and then the mixture was heated and stirred for 2 hours (internal temperature 100 to 110 ℃) to obtain a polysiloxane solution (LS-1) containing silica particles. During the temperature rise and the heating and stirring, nitrogen gas was passed through the mixture at a rate of 0.05l (liter)/min. As a by-product, 194.01g of methanol and water were distilled off during the reaction. The solid content concentration of the obtained polysiloxane solution containing silica particles (LS-1) was 24.3 wt%, and the contents of polysiloxane and silica particles in the solid content were 15 wt% and 85 wt%, respectively. The molar ratios of the respective repeating units derived from methyltrimethoxysilane, trifluoropropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride and γ -acryloxypropyltrimethoxysilane of the polysiloxane in the obtained silica particle-containing polysiloxane (LS-1) were 1.0mol%, 8.0mol%, 1.0mol% and 90.0mol%, respectively.
Example 1 resin composition for partition wall (P-1)
5.00g of a polysiloxane (PSL-1) solution obtained in Synthesis example 1 as a resin was mixed with 5.00g of a titanium dioxide pigment (R-960, manufactured by BASF JAPAN, ltd. (hereinafter referred to as "R-960")) as a white pigment, and dispersed by using a mill-type dispersing machine packed with zirconia beads to obtain a pigment dispersion (MW-1). In addition, 1.00g of bis (acetylacetonato) palladium as an organometallic compound and 0.861g (equimolar amount to the organometallic compound) of triphenylphosphine as a coordinating compound having a phosphorus atom were dissolved in 8.139g of DAA to obtain an organometallic compound solution (OM-1).
Next, 9.98g of the pigment dispersion (MW-1), 1.86g of the organic metal compound solution (OM-1), 0.98g of the polysiloxane (PSL-1) solution, 0.050g of 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime) ("Irgacure" (registered trademark) OXE-02, manufactured by BASF JAPAN (trademark) (hereinafter, referred to as "OXE-02")) as a photopolymerization initiator, 0.050g of bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide ("Irgacure" 819, ") (manufactured by PAN) (hereinafter, referred to as" IC-819 ")), 0.400g of 2- (3-benzoylphenyl) propionic acid 1, 2-diisopropyl-3- [ bis (dimethylamino) methylene ] guanidine (WPBG-266) (manufactured by Fuji corporation and Photonic acid film (BG) manufactured by Wako corporation (trademark), 266 g of the photopolymerization initiator (" BG-76 g of the photopolymerization initiator "), 0.76 g of the photopolymerization initiator (" PAD-100 g of the photopolymerization initiator ("PAD"), 100g of the photopolymerization initiator ("PAD") as a new photopolymerization initiator, 100g of the photopolymerization initiator ("PAD-HA-20 g of the photopolymerization initiator (" PAD "(registered trademark), and the photopolymerization initiator) (hereinafter, 100g of the photopolymerization initiator) (hereinafter, 100% of the photopolymerization initiator) and the photopolymerization initiator) (hereinafter, the photopolymerization initiator) are referred to be referred to as" PDHA-60 g of the photopolymerization initiator, 0.100g (corresponding to a concentration of 500 ppm) of PGMEA10 wt% diluted solution of 3',4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate ("Celloxide" (registered trademark) 2021P), ("Irganox" (registered trademark) 1010 "manufactured by DAICEL (registered trademark) and" IRGANOX "(registered trademark) 1010" manufactured by BASF JAPAN (registered trademark) was 0.100g, and 0.030g (corresponding to a concentration of 500 ppm) of acrylic surfactant ("BYK" (registered trademark) 352 and PGMEA10 wt% diluted solution of BYK-CHEMIE (BYK-CHEMIE) (hereinafter, referred to as "BYK-352") were dissolved in PGMEA4.20g solvent, followed by stirring. The resulting mixture was filtered through a 5.0 μm filter to obtain a resin composition (P-1) for partition walls.
Examples 2 to 3 resin compositions (P-2) to (P-3) for partition walls
Resin compositions (P-2) and (P-3) for partition walls were obtained in the same manner as in example 1, except that the polysiloxane (PSL-2) or (PSL-3) solution was used in place of the polysiloxane (PSL-1) solution.
Example 4 resin composition for partition wall (P-4)
A resin composition for partition walls (P-4) was obtained in the same manner as in example 1, except that a 40 wt% PGMEA diluted solution "Megafac" (registered trademark) F477 (manufactured by Dainippon ink chemical industries, ltd.) was used in place of the 40 wt% PGMEA diluted solution of RS-76-E.
Example 5 resin composition for partition wall (P-5)
5.00g of R-960 as a white pigment and 5.00g of a polysiloxane (PSL-4) solution as a resin were mixed and dispersed using a mill type disperser filled with zirconia beads to obtain a pigment dispersion (MW-4). 9.98g of the pigment dispersion (MW-4), 1.86g of the organometallic compound solution (OM-1), 1.16g of the polysiloxane (PSL-4) solution, 0.10g of WPBG-266 as a photobase generator, 1.00g of a 40 wt% PGMEA diluted solution of F477 as a liquid repellent compound, 0.100g of Celloxide (registered trademark) 2021P, 1.60g of THP-17 (trade name, manufactured by Toyo Synthesis industries, ltd.) as a quinonediazide compound, 0.100g of a PGMEA10 wt% diluted solution of a surfactant BYK-352, and 4.10g of PGMEA were mixed and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a resin composition (P-5) for partition walls.
Example 6 resin composition for partition wall (P-6)
An organometallic compound solution (OM-2) was prepared in the same manner as in the organometallic compound solution (OM-1) except that silver neodecanoate was used as the organometallic compound instead of palladium bis (acetylacetonate). A resin composition (P-6) for partition walls was obtained in the same manner as in example 1, except that the organometallic compound solution (OM-2) was used in place of the organometallic compound solution (OM-1).
Example 7 resin composition for partition wall (P-7)
The organometallic compound solution (OM-3) is prepared in the same manner as the organometallic compound solution (OM-1) except that triphenylphosphine gold chloride is used as the organometallic compound instead of bis (acetylacetonato) palladium. A resin composition (P-7) for partition walls was obtained in the same manner as in example 1, except that the organometallic compound solution (OM-3) was used in place of the organometallic compound solution (OM-1).
Example 8 resin composition for partition wall (P-8)
An organometallic compound solution (OM-4) is prepared in the same manner as in the organometallic compound solution (OM-1) except that bis (acetylacetonate) platinum is used as the organometallic compound instead of bis (acetylacetonate) palladium. A resin composition (P-8) for partition walls was obtained in the same manner as in example 1, except that the organometallic compound solution (OM-4) was used in place of the organometallic compound solution (OM-1).
Example 9 resin composition for partition wall (P-9)
A resin composition for partition walls (P-9) was obtained in the same manner as in example 1 except that the amount of the organometallic compound solution (OM-1) added was changed to 0.929g, the amount of the polysiloxane (PSL-1) solution added was changed to 1.41g, and PGMEA4.20g as a solvent was changed to PGMEA 4.70g.
Example 10 resin composition for partition wall (P-10)
A resin composition (P-10) for partition walls was obtained in the same manner as in example 1 except that the amount of the organometallic compound solution (OM-1) added was changed to 0.400g, the amount of the polysiloxane (PSL-1) solution added was changed to 1.940g, and the amount of the solvent PGMEA4.20g was changed to PGMEA 6.27g.
Example 11 resin composition for partition wall (P-11)
A resin composition (P-11) for partition walls was obtained in the same manner as in example 1 except that the amount of the organometallic compound solution (OM-1) added was changed to 4.595g, the amount of the polysiloxane (PSL-1) solution added was changed to 0.010g, and the amount of the solvent PGMEA4.20g was changed to PGMEA 2.92g.
Example 12 resin composition for partition wall (P-12)
5.00g of R-960 as a white pigment, 5.00g of a polysiloxane (PSL-1) solution as a resin, and 0.01g of titanium nitride as a black pigment were mixed and dispersed by a mill-type dispersing machine filled with zirconia beads to obtain a pigment dispersion (MW-2). A resin composition for partition walls (P-12) was obtained in the same manner as in example 9 except that 9.99g of the pigment dispersion (MW-2) was added in place of the pigment dispersion (MW-1), the amount of the polysiloxane (PSL-1) solution added was changed to 1.38g, and 4.72g of PGMEA was used as a solvent.
Example 13 resin composition for partition wall (P-13)
10.0g of polysiloxane (PSL-1) solution as a resin and 0.15g of titanium nitride as a black pigment were mixed and dispersed using a mill-type dispersing machine filled with zirconia beads to obtain a pigment dispersion (MW-3). A resin composition for partition walls (P-13) was obtained in the same manner as in example 1, except that 9.99g of the pigment dispersion (MW-3) was added in place of the pigment dispersion (MW-1), the amount of the polysiloxane (PSL-1) solution added was changed to 15.16g, and the amount of PGMEA added was changed from 4.20g to 0.11 g.
Example 14 resin composition for partition wall (P-14)
A resin composition for partition walls (P-14) was obtained in the same manner as in example 1, except that 1.85g of a DAA solution containing 10% of bis (acetylacetonato) palladium as an organometallic compound was used in place of the organometallic compound solution (OM-1), the amount of the polysiloxane (PSL-1) solution added was changed to 1.34g, and the amount of PGMEA4.20g as a solvent was changed to PGMEA 3.85g.
Example 15 resin composition for partition wall (P-15)
A resin composition for partition walls (P-15) was obtained in the same manner as in example 1, except that the amount of the photobase generator WPBG-266 added was changed to 1.21g and the amount of the polysiloxane (PSL-1) solution added was changed to PGMEA4.20g and the amount of the solvent PGMEA4.07g.
Example 16 resin composition for partition wall (P-16)
A resin composition for partition walls (P-16) was obtained in the same manner as in example 1, except that a 40 wt% PGMEA diluted solution of the liquid repellent compound RS-76-E was not added, the amount of the polysiloxane (PSL-1) solution added was changed to 2.01g, and PGMEA4.20g was changed to PGMEA4.17g as the solvent.
Comparative example 1 resin composition for partition wall (P-17)
A resin composition for partition walls (P-17) was obtained in the same manner as in example 1 except that 0.867g of an organometallic compound solution (OM-5) prepared by using 1.861g of triphenylphosphine and 8.139g of DAA8 as a complexing compound having a phosphorus atom was added instead of the organometallic compound solution (OM-1), the amount of the polysiloxane (PSL-1) solution was changed to 1.41g, and the amount of PGMEA was changed to 4.76g from 4.20 g.
Comparative example 2 resin composition for partition wall (P-18)
5.00g of R-960 as a white pigment, 5.00g of a polysiloxane (PSL-1) solution as a resin, and 0.10g of titanium nitride as a black pigment were mixed and dispersed using a mill-type dispersing machine packed with zirconia beads to obtain a pigment dispersion (MW-4). Next, 10.02g of the pigment dispersion (MW-4), 1.73g of the polysiloxane (PSL-1) solution, 0.050g of OXE-02 as a photopolymerization initiator, 0.400g of IC-819, 0.10g of WPBG-266 as a photobase generator, 1.20g of DPHA as a photopolymerizable compound, 1.00g of a 40 wt% PGMEA diluted solution of RS-76-E as a liquid repellent compound, 0.100g of Celloxide (registered trademark) 2021P, 0.030g of IRGANOX (registered trademark) 1010, 0.100g of a PGMEA10 wt% diluted solution of BYK-352 as a surfactant, and 5.31g of PGMEA5 as a solvent were mixed and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a resin composition (P-18) for partition walls.
Comparative example 3 resin composition for partition wall (P-19)
5.00g of R-960 as a white pigment, 5.00g of a polysiloxane (PSL-1) solution as a resin, and 0.10g of zirconium nitride as a black pigment were mixed and dispersed using a mill-type dispersing machine packed with zirconia beads to obtain a pigment dispersion (MW-5). A resin composition (P-19) for partition walls was obtained in the same manner as in comparative example 2, except that pigment dispersion (MW-5) was used in place of pigment dispersion (MW-4).
Comparative example 4 resin composition for partition wall (P-20)
5.00g of R-960 as a white pigment, 5.00g of a polysiloxane (PSL-1) solution as a resin, and 0.05g of a mixed pigment of PR254 and PB64 as a black pigment in a weight ratio of 60/40 were mixed and dispersed using a mill-type dispersing machine filled with zirconia beads to obtain a pigment dispersion (MW-6). A resin composition (P-20) for partition walls was obtained in the same manner as in comparative example 2, except that a pigment dispersion (MW-6) was used in place of the pigment dispersion (MW-4).
Comparative example 5 resin composition for partition wall (P-21)
An organometallic compound solution (OM-5) was prepared in the same manner as the organometallic compound solution (OM-1) except that tris (acetylacetonato) iron was used as the organometallic compound instead of bis (acetylacetonato) palladium. A resin composition (P-21) for partition walls was obtained in the same manner as in example 1, except that the organometallic compound solution (OM-5) was used in place of the organometallic compound solution (OM-1).
Comparative example 6 resin composition for partition walls (P-22)
An organometallic compound solution (OM-5) is prepared in the same manner as the organometallic compound solution (OM-1) except that bis (acetylacetonato) nickel is used as the organometallic compound instead of bis (acetylacetonato) palladium. A resin composition (P-22) for partition walls was obtained in the same manner as in example 1, except that the organometallic compound solution (OM-6) was used in place of the organometallic compound solution (OM-1).
The compositions of examples 1 to 16 and comparative examples 1 to 6 are summarized in tables 2 to 3.
[ Table 2]
Figure BDA0002850644660000551
[ Table 3]
Figure BDA0002850644660000561
Preparation example 1 color conversion luminescent Material composition (CL-1)
20 parts by weight of a 0.5 wt% toluene solution of a green quantum dot material (Lumidot 640 CdSe/ZnS, average particle diameter 6.3nm, manufactured by Aldrich Co.), 45 parts by weight of DPHA, 5 parts by weight of Irgacure (registered trademark) 907 (manufactured by BASF JAPAN, inc.), 166 parts by weight of a 30 wt% PGMEA solution of an acrylic resin (SPCR-18, manufactured by Showa Denko K.K.), and 97 parts by weight of toluene were mixed and stirred to be uniformly dissolved. The resulting mixture was filtered with a 0.45 μm syringe filter to prepare a color-converting luminescent material composition (CL-1).
Preparation example 2 color conversion luminescent Material composition (CL-2)
A color-converted luminescent material composition (CL-2) was prepared in the same manner as in preparation example 1, except that 0.4 part by weight of the green phosphor G-1 obtained in Synthesis example 5 was used in place of the green quantum dot material and the amount of toluene added was changed to 117 parts by weight.
Preparation example 3 color conversion luminescent Material composition (CL-3)
A color-converted luminescent material composition (CL-3) was prepared in the same manner as in preparation example 1, except that 0.4 part by weight of the red phosphor R-1 obtained in Synthesis example 6 was used in place of the green quantum dot material and the amount of toluene added was changed to 117 parts by weight.
Preparation example 4 color Filter Forming Material (CF-1)
90g of C.I. pigment green 59, 60g of C.I. pigment yellow 150, 75g of a polymer dispersant (BYK (registered trademark) -6919 (trade name) BYK-CHEMIE, inc. (hereinafter, BYK-6919)), 100g of a binder resin (Adeka Arkls (registered trademark) WR301 (trade name) (manufactured by ADEKA Co., ltd.), and 675g of PGMEA were mixed to prepare a slurry. A beaker containing the slurry was connected to a Dynozzie through a tube, and dispersion treatment was performed for 8 hours at a peripheral speed of 14m/s using zirconia beads having a diameter of 0.5mm as a medium to prepare a pigment Green 59 dispersion (GD-1).
56.54g of pigment green 59 dispersion (GD-1), 3.14g of acrylic resin ("Cyclomer" (registered trademark) P (ACA) Z250 (trade name) manufactured by DAICEL ALLNEX corporation (hereinafter, referred to as "P (ACA) Z250"), 2.64g of DPHA, 0.330g of photopolymerization initiator ("Optomer" (registered trademark) NCI-831 (trade name) manufactured by ADEKA corporation (hereinafter, referred to as "NCI-831")), 0.04g of surfactant (BYK "(registered trademark) -333 (trade name) manufactured by BYK-CHEMIE corporation (hereinafter, referred to as" BYK-333 ")), 0.01g of BHT as a polymerization inhibitor, and 37.30g of PGMEA as a solvent were mixed to prepare a color filter forming material (CF-1).
Preparation example 5 resin composition for light-shielding partition wall
150g of carbon black (MA 100 (trade name) manufactured by Mitsubishi chemical corporation), 75g of a polymer dispersant BYK-6919, 100g of P (ACA) Z250, and 675g of PGMEA were mixed to prepare a slurry. The beaker containing the slurry was connected to a Dyno mill through a tube, and dispersion treatment was carried out for 8 hours at a peripheral speed of 14m/s using zirconia beads having a diameter of 0.5mm as a medium to prepare a pigment dispersion (MB-1).
56.54g of pigment dispersion (MB-1), 3.14g of P (ACA) Z250, DPHA2.64g, 0.330g of NCI-831, 0.04g of BYK-333, 0.01g of t-butylcatechol as a polymerization inhibitor, and 37.30g of PGMEA were mixed to prepare a resin composition for a light-shielding partition wall.
Preparation example 6 Low refractive index layer Forming Material
5.350g of the silicone solution containing silica particles (LS-1) obtained in Synthesis example 6, 1.170g of ethylene glycol mono-t-butyl ether, and 3.48g of DAA3 were mixed, and then 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)
150g of C.I. pigment yellow 150, 75g of a polymeric dispersant (BYK (registered trademark) -6919 (trade name) manufactured by BYK-CHEMIE (hereinafter, referred to as "BYK-6919")), 100g of a binder resin (Adeka Arkls (registered trademark) WR301 (trade name) (manufactured by ADEKA) and 675g of PGMEA were mixed to prepare a slurry. The beaker containing the slurry was connected to a Danotmill by a tube, and dispersion treatment was performed for 8 hours at a peripheral speed of 14m/s using zirconia beads having a diameter of 0.5mm as a medium, thereby preparing a pigment yellow 150 dispersion (YD-1).
3.09g of the pigment yellow 150 dispersion (YD-1), 23.54g of a polysiloxane (PSL-1) solution as a resin, 6.02g of DPHA as a photopolymerizable compound, 6.02g of an organic metal compound solution (OM-2) prepared by using silver neodecanoate as an organic metal compound, 0.20g of OXE-02 as a photopolymerization initiator, 0.40g of IC-819, 0.060g of IRGANOX (registered trademark) 1010, and 0.050g (corresponding to a concentration of 500 ppm) of a PGMEA10 wt% diluted solution of BYK-352 were dissolved in 61.15g of a solvent PGMEA and stirred. The resultant mixture was filtered through a 5.0 μm filter to obtain yellow organic protective layer-forming material (YL-1).
(examples 17 to 20, examples 22 to 28, examples 38 to 45, and comparative examples 7 to 9)
A10 cm square alkali-free Glass substrate (0.7 mm thick, manufactured by AGC Techno Glass Co., ltd.) was used as a base substrate. The resin compositions for partition walls shown in tables 4 to 5 were applied by spin coating on the resin composition, and the coating was heated at 90 ℃ using a hot plate (trade name: SCW-636, manufactured by SCREEN, japan Ltd.)Dried for 2 minutes to prepare a dry film. The dry film thus produced was aligned with a parallel photomask exposure machine (product name: PLA-501F, manufactured by Canon corporation) using an ultra-high pressure mercury lamp as a light source, and the exposure amount was 200mJ/cm through a photomask 2 (i-ray) exposure is performed. Then, using an automatic developing apparatus ("AD-2000 (trade name)" manufactured by greenling industry corporation), spray development was performed for 100 seconds using a 0.045 wt% potassium hydroxide aqueous solution, and then rinsing was performed for 30 seconds using water. Then, the glass substrate was heated in an oven (trade name: IHPS-222, manufactured by ESPEC corporation) at 230 ℃ for 30 minutes to form partition walls having a height of 10 μm and a width of 20 μm on the glass substrate in a lattice pattern with a pitch interval of 30 μm on the short side and 150 μm on the long side.
The color-converting phosphor compositions shown in tables 4 to 5 were applied to the regions partitioned by the partition walls of the obtained substrate with partition walls in a nitrogen atmosphere by an ink-jet method, and dried at 100 ℃ for 30 minutes to form pixels having a thickness of 5.0 μm, thereby obtaining a substrate with partition walls having a structure shown in FIG. 2.
(example 21)
As a base substrate, a10 cm square alkali-free Glass substrate (0.7 mm thick, manufactured by AGC Techno Glass Co., ltd.) was used. The resin composition for partition walls shown in Table 4 was applied by spin coating, dried at 90 ℃ for 2 minutes using a hot plate (trade name: SCW-636, manufactured by SCREEN corporation, japan) to prepare a dry film. The dry film thus produced was aligned with a parallel photo-mask exposure machine (trade name: PLA-501F, manufactured by Canon corporation) using an ultra-high pressure mercury lamp as a light source and an exposure of 200mJ/cm through a photomask 2 (i-ray) exposure is performed. Then, using an automatic developing apparatus ("AD-2000 (trade name)" manufactured by greenling industries, ltd.), spray development was performed for 90 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution, followed by rinsing with water for 30 seconds. Then, in the same manner as before, the exposure amount was 500mJ/cm without interposing a photomask 2 The exposure was performed (i-ray) and then rinsing was performed. Further, the glass substrate was heated in an oven (product name: IHPS-222, manufactured by ESPEC) at 230 ℃ for 30 minutes in air, and partition walls having a height of 10 μm and a width of 20 μm were formed on the glass substrate so as to have short sidesAnd partition walls in a lattice pattern having a pitch interval of 30 μm and a long side of 150 μm.
The color-converting phosphor compositions shown in tables 4 to 5 were applied to the regions partitioned by the partition walls of the obtained substrate with partition walls in a nitrogen atmosphere by an ink-jet method, and dried at 100 ℃ for 30 minutes to form pixels having a thickness of 5.0 μm, thereby obtaining a substrate with partition walls having a structure shown in FIG. 2.
(example 29)
A low refractive index layer forming material was spin-coated on a substrate with partition walls on which pixels were formed in the same manner as in example 18, and dried at 90 ℃ for 2 minutes using a hot plate (trade name SCW-636, manufactured by scr corporation, japan) to prepare a dry film. Further, the substrate with the partition wall having the structure shown in FIG. 3 was obtained by heating the substrate in an oven (product name: IHPS-222, manufactured by ESPEC) at 90 ℃ for 30 minutes in air to form a low refractive index layer.
(example 30)
On the low refractive index layer of the substrate with partition walls having the low refractive index layer obtained in example 29, a silicon nitride film having a film thickness of 300nm corresponding to the inorganic protective layer I having a film thickness of 50 to 1,000nm was formed by using a plasma CVD apparatus (PD-220nl, samco), and the substrate with partition walls having the structure shown in fig. 4 was obtained.
(example 31)
On the substrate with partition walls obtained in example 18, a silicon nitride film having a film thickness of 300nm corresponding to the inorganic protective layer II having a thickness of 50 to 1,000nm was formed on the pixel upper layer by using a plasma CVD apparatus (PD-220nl, samco). Then, using the low-refractive-index layer forming material obtained in preparation example 6, 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, thereby obtaining a substrate with partition walls having a structure shown in fig. 5.
(example 32)
The color filter forming material (CF-1) obtained in preparation example 4 was applied to the regions of the substrate with partition walls before pixel formation, which were partitioned by the partition walls and obtained in the same manner as in example 17, so that the cured film thickness was 2.5 μm, and vacuum-dried.Exposing the substrate with the barrier ribs to an exposure dose of 40mJ/cm through a photomask designed to expose the opening region of the substrate with the barrier ribs 2 (i-ray) exposure is performed. After development with a 0.3 wt% aqueous tetramethylammonium solution for 50 seconds, the resultant was cured by heating at 230 ℃ for 30 minutes to form a color filter having a thickness of 2.5 μm and a width of 50 μm in the regions partitioned by the partition walls. Then, the color conversion luminescent material composition (CL-2) obtained in preparation example 2 was applied to a color filter in a nitrogen atmosphere by an ink jet method, and dried at 100 ℃ for 30 minutes to form a pixel having a thickness of 5.0 μm, thereby obtaining a substrate with a partition wall having a structure shown in fig. 6.
(example 33)
A silicon nitride film having a thickness of 300nm corresponding to the inorganic protective layer III having a thickness of 50 to 1,000nm was formed on the color filter of the substrate with partition walls before pixel formation, on which the 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, by using a plasma CVD apparatus (PD-220NL, manufactured by SAMCO Co., ltd.). Further, the color-converting luminescent material composition (CL-2) obtained in preparation example 2 was coated on the inorganic protective layer III in a nitrogen atmosphere by an ink jet method, and dried at 100 ℃ for 30 minutes to form pixels having a thickness of 5.0 μm, thereby obtaining a substrate with partition walls having a structure shown in fig. 7.
(example 34)
As a base substrate, a10 cm square alkali-free Glass substrate (0.7 mm thick, manufactured by AGC Techno Glass Co., ltd.) was used. A silicon nitride film having a thickness of 300nm corresponding to the inorganic protective layer IV having a thickness of 50 to 1,000nm was spin-coated thereon by using a plasma CVD apparatus (PD-220 NL, SAMCO Co.). A substrate with a partition wall having the structure shown in fig. 8 was obtained in the same manner as in example 31, except that the above-described substrate was used instead of the 10cm square alkali-free glass substrate.
(example 35)
The yellow organic protective layer-forming material (YL-1) obtained in preparation example 7 was applied to the color filter of the substrate with partition walls before pixel formation, on which the color filter having a thickness of 2.5 μm and a width of 50 μm was formed, obtained in the same manner as in example 32, and vacuum-dried. A substrate with a partition wallThe exposure amount of the photomask is 40mJ/cm 2 (i-ray) exposure is performed. After development with a 0.3 wt% aqueous tetramethylammonium solution for 50 seconds, the resultant was cured by heating at 230 ℃ for 30 minutes to form a yellow organic resist having a thickness of 1.0 μm and a width of 50 μm. Further, the color conversion luminescent material composition (CL-2) obtained in preparation example 2 was applied to the yellow organic protective layer in a nitrogen atmosphere by an ink jet method, and dried at 100 ℃ for 30 minutes to form pixels having a thickness of 5.0 μm, thereby obtaining a partition-equipped substrate having a structure shown in fig. 7.
(example 36)
As a base substrate, a10 cm square alkali-free Glass substrate (0.7 mm thick, manufactured by AGC Techno Glass Co., ltd.) was used. The yellow organic protective layer-forming material (YL-1) obtained in preparation example 7 was coated thereon, and vacuum-dried. The dried film was exposed to an exposure of 40mJ/cm without interposing a photomask 2 After exposure to light, (i-ray), development was carried out for 50 seconds using a 0.3 wt% aqueous tetramethylammonium solution, and heat curing was carried out at 230 ℃ for 30 minutes, whereby a yellow organic protective layer having a thickness of 1.0 μm was formed. A substrate with a partition wall having the structure shown in fig. 8 was obtained in the same manner as in example 31, except that the above-described substrate was used instead of the 10cm square alkali-free glass substrate.
(example 37)
A10 cm square alkali-free Glass substrate (0.7 mm thick, manufactured by AGC Techno Glass Co., ltd.) was used as a base substrate. The light-shielding partition wall-forming material obtained in preparation example 5 was spin-coated thereon, and dried at 90 ℃ for 2 minutes using a hot plate (trade name: SCW-636, manufactured by SCREEN corporation, japan) to prepare a dry film. The dry film thus produced was aligned with a parallel photo-mask exposure machine (trade name: PLA-501F, manufactured by Canon corporation) using an ultra-high pressure mercury lamp as a light source and an exposure of 40mJ/cm through a photomask 2 (i-ray) exposure is performed. Then, development was performed for 50 seconds using an automatic developing apparatus ("AD-2000 (trade name)" manufactured by greenling industries, ltd.) using a 0.3 wt% tetramethylammonium aqueous solution, and then rinsing was performed for 30 seconds using water. Further, the resultant was heated in an oven (trade name: IHPS-222, manufactured by ESPEC corporation) at 230 ℃ in airAfter 30 minutes, a light-shielding tape partition substrate was obtained in which partition walls having an OD value of 2.0 when the height was 2.0 μm, the width was 20 μm, and the thickness was 1.0 μm were formed on a glass substrate in a lattice pattern with a pitch interval of 30 μm in the short side and 150 μm in the long side. Then, a substrate with partition walls was obtained in which partition walls having a height of 10 μm and a width of 20 μm were formed on the light-shielding partition walls in a lattice pattern similar to the light-shielding partition walls having a pitch interval of 30 μm on the short side and 150 μm on the long side in the same manner as in example 17. The color conversion luminescent material composition (CL-2) obtained in preparation example 22 was applied to the regions of the obtained substrate with partition walls partitioned by the partition walls by an ink jet method in a nitrogen atmosphere, and dried at 100 ℃ for 30 minutes to form pixels having a thickness of 5.0 μm, thereby obtaining a substrate with partition walls having a structure shown in fig. 9.
The structures of the examples and comparative examples are shown in tables 4 to 5.
[ Table 4]
Figure BDA0002850644660000641
[ Table 5]
Figure BDA0002850644660000651
The evaluation methods of the examples and comparative examples are as follows.
Refractive index of white pigment
The white pigments used in the examples and comparative examples were measured for refractive index by the method B (using the microscope immersion method (becker's method)) among the refractive index measurement methods for plastics prescribed in JIS K7142-2014 (2014/04/20, established year and month), and the measurement wavelength was 550nm, wherein "contact liquid" manufactured by shimadzu device (ltd) was used instead of the immersion liquid used in JIS K7142-2014, and the measurement was performed under the condition that the immersion liquid temperature was 20 ℃.
< refractive index of polysiloxane and Low refractive index layer >
Polysiloxane as a raw material of the partition wall-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 coated on a silicon wafer using a spin coater, and dried at 90 ℃ for 2 minutes using a hot plate (trade name SCW-636, manufactured by scr corporation, japan). Then, the resultant was heated in an oven (IHPS-222, espec, inc.) at 230 ℃ for 30 minutes in the air to prepare a cured film. The cured film was irradiated with light having a wavelength of 550nm from a direction perpendicular to the surface of the cured film under atmospheric pressure at 20 ℃ using a prism coupler (PC-2000, manufactured by Metricon corporation), the refractive index was measured, and the third decimal place was rounded.
Resolution
The resin composition for barrier ribs used in each of examples and comparative examples was spin-coated on an alkali-free glass substrate of 10cm square by using a spin coater (trade name 1H-360S, manufactured by Mikasa corporation) so that the thickness after heating was 10 μm, and dried at 90 ℃ for 2 minutes by using a hot plate (trade name SCW-636, manufactured by SCREEN, japan, ltd.) to prepare a dried film having a thickness of 10 μm.
The dry film thus produced was exposed to 200mJ/cm of light using a parallel light mask aligner (trade name: PLA-501F, manufactured by Canon Inc.) and an ultra-high pressure mercury lamp as a light source, with a mask having line and space patterns (line and space patterns) of widths of 100 μm, 80 μm, 60 μm, 50 μm, 40 μm, 30 μm and 20 μm interposed therebetween 2 (i-ray) and exposure was performed with a gap of 100 μm. Then, using an automatic developing apparatus ("AD-2000 (trade name)" manufactured by greenling industries, ltd.), 100 seconds of shower development was performed using 0.045 wt% potassium hydroxide aqueous solution, followed by 30 seconds of rinsing with water.
The developed pattern was observed under magnification using a microscope adjusted to a magnification of 100, and the narrowest line width of the pattern in which no residue was observed in the unexposed portion was used as the resolution. Here, the case where residue was present in unexposed portions near a pattern having a width of 100 μm was assumed to be "> 100. Mu.m".
< reflectance >
A solid film was formed on a glass substrate under the same conditions as in examples and comparative examples, except that a resin composition was formed on the partition walls used in examples and comparative examples, and the entire structure was exposed to light without a photomask interposed therebetween. The obtained solid film was used as a model of a partition wall of the substrate with a partition wall obtained in each example and comparative example, and a reflectance at a wavelength of 550nm was measured from the solid film side in an SCI mode using a spectrophotometer (trade name CM-2600d, manufactured by Konica Minolta). However, when cracks occur in the actual film, an accurate value cannot be obtained due to cracks or the like, and thus the reflectance is not measured.
< crack resistance >
The resin compositions for forming the partition walls used in the examples and comparative examples were spin-coated so that the film thicknesses after heating were 5 μm, 10 μm, 15 μm, and 20 μm, respectively. In the subsequent steps, processing was performed under the same conditions as in each of examples and comparative examples except that the entire body was exposed without a photomask interposed therebetween at the time of exposure, and a solid film was produced on the glass substrate. The obtained solid films were used as a model of the partition walls of the substrate with partition walls obtained in each example and comparative example, and 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 is observed, it is determined that the film has no crack resistance at the thickness. For example, when there is no crack at a film thickness of 15 μm and there is a crack at a film thickness of 20 μm, the crack-resistant film thickness is determined to be ≧ 15 μm. The cracking resistance was set by determining the cracking resistance film thickness of ≧ 20 μm when no crack was present even at 20 μm, and determining the cracking resistance film thickness of ≧ 5 μm when cracks were present even at 5 μm.
< OD value >
As a model of the partition wall of the substrate with the partition wall obtained in each of examples and comparative examples, a solid film was produced on a glass substrate in the same manner as in the evaluation of the reflectance. The intensity of incident light and transmitted light was measured for the obtained glass substrate having a solid film using an optical densitometer (361T (visual); manufactured by X-rite Co., ltd.), and the OD value was calculated from the above formula (1). The OD values before the heating step and the OD values after the heating step were measured, and the differences thereof are shown in tables 6 to 7.
In example 37, a solid film was produced on a glass substrate in the same manner as a mold for the light-shielding partition (a-2). The intensity of incident light and transmitted light was measured with respect to the obtained glass substrate having a solid film using an optical densitometer (361T (visual); manufactured by X-rite Co., ltd.), and the calculation was performed based on the above formula (1).
< taper angle >
In each of examples and comparative examples, an arbitrary cross section of the substrate with partition walls before pixel formation was observed at an acceleration voltage of 3.0kV using an optical microscope (FE-SEM (S-4800); (manufactured by Hitachi Co., ltd.) to measure the taper angle.
< surface contact Angle >
As a model of the partition wall in the substrate with the partition wall obtained in each of examples and comparative examples, a real mulching film was produced on a glass substrate in the same manner as the evaluation of the reflectance, and the surface of the obtained real mulching film was subjected to the following processing using DM-700 manufactured by synergetics interface science corporation, a micro syringe: a contact angle meter manufactured by Kyowa interface science (Co., ltd.) was coated with a Teflon (registered trademark) needle 22G, and the surface contact angle was measured at 25 ℃ in the atmosphere according to the wettability test method of the substrate glass surface specified in JIS R3257 (1999/04/20 in established years and months). In this case, the contact angle between the surface of the real film and propylene glycol monomethyl ether acetate was measured using propylene glycol monomethyl ether acetate instead of water.
< ink-jet coatability >
In the substrates with partition walls before forming the pixels obtained in the examples and comparative examples, inkjet coating was performed on the pixel portions surrounded by the lattice-shaped partition walls using PGMEA as ink by using an inkjet coating apparatus (InkjetLabo, cluster Technology, ltd.). The PGMEA of 160pL was applied in a lattice pattern for 1 cell, and the presence or absence of a collapse (a phenomenon in which ink crosses over the barrier ribs and enters the adjacent pixel portions) was observed, and the ink jet coatability was evaluated by the following criteria. The less the collapse, the higher the liquid repellency and the more excellent the ink jet coatability.
A: ink does not overflow from the pixels.
B: in some of the portions, the ink overflows from the pixels to the upper surfaces of the partition walls.
C: the ink overflows from the inside of the pixel to the upper surface of the partition wall over the entire surface.
< thickness >
The thickness of the pixel (B) was measured by measuring the height of the structure before and after formation of the pixel (B) using a SURFCOM stylus film thickness measuring apparatus for the substrate with the partition wall obtained in each of the examples and comparative examples, and calculating the difference. The film thickness of the low refractive index layer (C) was also measured in the same manner as in examples 29 to 31, the film thickness of the color filter was also measured in the same manner as in examples 32 to 36, and the thickness (height) of the light-shielding partition was also measured in the same manner as in example 37.
In examples 30 to 31 and 33 to 34, the thicknesses of the inorganic protective layers I to IV were measured by exposing a cross section perpendicular to the base substrate using a polishing apparatus such as a cross-section polisher, and observing the cross section under magnification using a scanning electron microscope or a transmission electron microscope.
< luminance >
A substrate with a partition wall obtained in each of examples and comparative examples was provided so that a pixel portion was on the light source side, with a planar light-emitting device having a commercially available LED backlight (peak wavelength 465 nm) mounted thereon as a light source. The planar light-emitting device was supplied with a current of 30mA to turn on the LED elements, and the luminance (unit: cd/m) based on the CIE1931 standard was measured using a spectral radiance meter (CS-1000, manufactured by Konica Minolta Co., ltd.) 2 ) And set as the initial brightness. The evaluation of luminance was performed by setting the initial luminance of example 45 to a relative value of standard 100.
Further, after the LED elements were turned on at room temperature (23 ℃) for 48 hours, the luminance was measured in the same manner, and the change in luminance with time was evaluated. The evaluation of luminance was performed by setting the initial luminance of example 45 to a relative value of standard 100.
< color characteristics >
The partition-equipped substrates obtained in each of examples and comparative examples were provided on a commercially available white reflection plate so that pixels were disposed on the white reflection plate side. A spectrum including the regular reflection light was measured by irradiating light from the base substrate side of the substrate with a partition wall with a spectrocolorimeter (CM-2600 d, manufactured by Konica Minolta, ltd., measurement diameter. Phi.8 mm).
For a color gamut defined by color standard bt.2020 that can approximately reproduce colors in nature, red, green, and blue on a spectrum locus shown in a chromaticity diagram are defined as three primary colors, and the wavelengths of red, green, and blue correspond to 630nm, 532nm, and 467nm, respectively. The reflectance (R) at three wavelengths of 470nm, 530nm and 630nm of the obtained reflectance spectrum was evaluated for the emission color of the pixel according to the following criteria.
A：R 530 /(R 630 +R 530 +R 470 )≥0.55
B：R 530 /(R 630 +R 530 +R 470 )＜0.55。
< display characteristics >
The display characteristics of the display devices produced by combining the partition-equipped substrates obtained in the examples and comparative examples with the organic EL elements were evaluated based on the following criteria.
A: the green display is very vivid, and is a clear display device with excellent contrast.
B: although the color was observed to be slightly unnatural, it was a problem-free display device.
< color mixing >
In the partition-provided substrates before formation of the pixels obtained in examples and comparative examples, a color conversion luminescent material composition (CL-2) was applied to a part of the pixel portion surrounded by the lattice-shaped partition by an ink-jet method, and dried at 100 ℃ for 30 minutes to form a pixel having a thickness of 5.0 μm. Then, in the pixel portion surrounded by the lattice-like partition walls, the color-converting luminescent material composition (CL-3) was applied to the adjacent area of the area to which the color-converting luminescent material composition (CL-2) was applied by an ink-jet method, and dried at 100 ℃ for 30 minutes to form a pixel having a thickness of 5.0. Mu.m.
On the other hand, a blue organic EL cell having the same width as the pixel portion surrounded by the lattice-shaped partition walls was prepared, and the substrate with the partition walls was opposed to the blue organic EL cell and bonded with a sealant to obtain a display device having the configuration shown in fig. 10.
In the blue organic EL cell 11 of fig. 10, the absorption intensity a (630 nm) at a wavelength of 630nm was measured for the portion of the pixel 3 (CL-3) formed from the color conversion luminescent material composition (CL-3) using a microspectrophotometer LVmicro-V (manufactured by Lambda Vision) in a state where only the blue organic EL cell adhered to the pixel 3 (CL-2) formed from the color conversion luminescent material composition (CL-2) directly below was lit. The smaller the value of the absorption intensity A (630 nm), the less the color mixture is likely to occur. The color mixture was determined by the following criteria.
A：A(630nm)＜0.01
B：0.01≤A(630nm)≤0.5
C：0.5＜A(630nm)。
The evaluation results of the examples and comparative examples are shown in tables 6 to 7.
[ Table 6]
Figure BDA0002850644660000721
[ Table 7]
Figure BDA0002850644660000731
Description of the reference numerals
1: base substrate
2: partition wall
3: pixel
3 (CL-2): pixel formed by color conversion luminescent material composition (CL-2)
3 (CL-3): pixel formed by color conversion luminescent material composition (CL-3)
4: 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: shading partition wall
11: blue organic EL unit
H: thickness of the partition wall
L: width of the partition wall
θ: angle of taper

Claims (7)

1. A resin composition comprising:
a resin; and
an organometallic compound containing at least 1 metal selected from the group consisting of silver, gold, platinum and palladium; and
a photopolymerization initiator or a quinonediazide compound; and
white pigments and/or black pigments; and
a solvent, a water-soluble organic solvent,
the white pigment is selected from titanium dioxide, zirconium oxide, zinc oxide, barium sulfate and composite compounds thereof,
the black pigment is selected from titanium nitride, zirconium nitride and mixed pigment with the weight ratio of the red pigment to the blue pigment being 20/80-80/20.
2. The resin composition according to claim 1, further comprising a coordinating compound having a phosphorus atom.
3. The resin composition according to claim 1 or 2, wherein the resin is a resin selected from the group consisting of polysiloxane, polyimide precursor, polybenzoxazole precursor and (meth) acrylic polymer.
4. The resin composition according to any one of claims 1 to 3, wherein the resin is a polysiloxane.
5. The resin composition according to any one of claims 1 to 4, further comprising a photobase generator.
6. A light-shielding film obtained by curing the resin composition according to any one of claims 1 to 5.
7. A method for manufacturing a light-shielding film, comprising the steps of:
a film-forming step of coating the resin composition according to any one of claims 1 to 5 on a base substrate and drying the coating to obtain a dried film;
an exposure step of pattern-exposing the obtained dried film;
a developing step of dissolving and removing a developer-soluble portion of the exposed dry film; and
a heating step of heating the developed dry film to cure the film,
in the heating step, the dried film after development is heated at a temperature of 120 ℃ to 250 ℃, thereby increasing the OD value at a film thickness of 10 μm by 0.3 or more.
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