WO2019176785A1 - Composition colorante photosensible négative, film durci et écran tactile l'utilisant - Google Patents

Composition colorante photosensible négative, film durci et écran tactile l'utilisant Download PDF

Info

Publication number
WO2019176785A1
WO2019176785A1 PCT/JP2019/009397 JP2019009397W WO2019176785A1 WO 2019176785 A1 WO2019176785 A1 WO 2019176785A1 JP 2019009397 W JP2019009397 W JP 2019009397W WO 2019176785 A1 WO2019176785 A1 WO 2019176785A1
Authority
WO
WIPO (PCT)
Prior art keywords
substrate
coloring composition
negative photosensitive
photosensitive coloring
partition
Prior art date
Application number
PCT/JP2019/009397
Other languages
English (en)
Japanese (ja)
Inventor
小林秀行
諏訪充史
飯塚英祐
東後行倫
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to KR1020207021151A priority Critical patent/KR102617582B1/ko
Priority to CN201980015528.7A priority patent/CN111771163B/zh
Priority to JP2019520658A priority patent/JP7306264B2/ja
Publication of WO2019176785A1 publication Critical patent/WO2019176785A1/fr

Links

Images

Classifications

    • 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means

Definitions

  • the present invention relates to a negative photosensitive coloring composition, a cured film, a production method thereof, and a touch panel using the same.
  • the projected capacitive touch panel has an ITO (Indium Tin Oxide) film pattern in the screen area, and further has a metal wiring portion such as molybdenum around the periphery thereof.
  • ITO Indium Tin Oxide
  • a black or white light-shielding pattern is often provided inside the cover glass of the projected capacitive touch panel.
  • higher-definition light-shielding patterns are required, and as a method for forming such light-shielding patterns, lithography capable of processing with higher resolution is possible instead of the conventional printing method.
  • the law is becoming mainstream (see, for example, Patent Document 1).
  • the white light-shielding pattern since the light-shielding property of the white pigment is generally low, thick film processing is required.
  • the touch panel system is an out-cell type in which a touch panel layer is formed between a cover glass and a liquid crystal panel, an on-cell type in which a touch panel layer is formed on the liquid crystal panel, and an in-cell type in which a touch panel layer is formed inside the liquid crystal panel.
  • Cell type and OGS (One Glass Solution) type that directly forms the touch panel layer on the cover glass.
  • OGS type touch panels have been actively developed because they can be made thinner and lighter than conventional ones.
  • a light-shielding pattern material is required to have a high heat resistance with few cracks and color change in the high-temperature processing.
  • a negative photosensitive coloring composition for example, see Patent Document 2 containing a white pigment, a polysiloxane having a specific structure, a polyfunctional acrylic monomer, a photo radical polymerization initiator, and an organic solvent, a white pigment
  • a negative photosensitive white composition for touch panel for example, see Patent Document 3 containing an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator has been proposed.
  • a photosensitive white composition containing a white pigment can easily form a high-definition and highly reflective partition wall pattern on a substrate by a lithography method. Therefore, as a technique for improving the light extraction efficiency of a light emitter, a display device Application to brightness enhancement technology is under consideration.
  • JP 2012-242928 A International Publication No. 2014/126013 International Publication No. 2015/12228
  • composition described in Patent Document 2 has a high refractive index of polysiloxane and a small difference in refractive index from the white pigment, reflection at the interface between the polysiloxane and the white pigment is insufficient. The reflectance of the light shielding pattern was insufficient.
  • the reflectance of the white light-shielding pattern is improved by the composition described in Patent Document 3, further improvement has been demanded.
  • the film thickness is large, cracks are likely to occur due to high-temperature treatment, and there is a problem that heat resistance is insufficient.
  • an object of the present invention is to provide a negative photosensitive coloring composition capable of forming a cured film having high resolution, high reflectance, and excellent heat resistance even if it is a thick film. .
  • the inventors of the present invention have made extensive studies by paying attention to the structure of a siloxane resin in a negative photosensitive coloring composition containing a white pigment.
  • a siloxane resin in which a structural unit derived from an alkoxysilane compound containing fluorine and a structural unit derived from a bifunctional alkoxysilane compound are contained. That is, the present invention has the following configuration.
  • a negative photosensitive coloring composition containing (A) a white pigment, (B) a siloxane resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an organic solvent, )
  • the siloxane resin includes at least a repeating unit represented by the following general formula (1) and / or a repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (3).
  • Negative photosensitive material containing a total of 40 to 80 mol% of the repeating unit represented by the following general formula (1) and the repeating unit represented by the following general formula (2) in all the repeating units of the (B) siloxane resin. Coloring composition.
  • R 1 represents an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 10 carbon atoms in which all or part of hydrogen is substituted with fluorine.
  • R 2 represents a single bond, —O—, —CH 2 —CO—, —CO— or —O—CO—.
  • R 3 represents a monovalent organic group having 1 to 20 carbon atoms.
  • R 4 may be the same or different and represents a monovalent organic group having 1 to 20 carbon atoms.
  • a thick cured film having high reflectivity, high resolution and excellent heat resistance can be formed.
  • the negative photosensitive coloring composition of the present invention contains (A) a white pigment, (B) a siloxane resin, (C) a photopolymerization initiator, (D) a photopolymerizable compound, and (E) an organic solvent.
  • the white pigment includes, for example, a compound selected from titanium dioxide, zirconium oxide, zinc oxide, barium sulfate and a composite compound thereof. Two or more of these may be contained. Among these, titanium dioxide is preferable because of its high reflectance and easy industrial use.
  • the crystal structure of titanium dioxide is classified into anatase type, rutile type and brookite type. Among these, rutile type titanium oxide is preferable because of its low photocatalytic activity.
  • the white pigment may be subjected to a surface treatment.
  • Surface treatment with Al, Si and / or Zr is preferable, and the dispersibility of the (A) white pigment in the negative photosensitive coloring composition can be improved, and the light resistance and heat resistance of the cured film can be further improved.
  • the median diameter of the white pigment is preferably from 100 to 500 nm, more preferably from 170 to 310 nm, from the viewpoint of further improving the reflectance.
  • the median diameter means the average primary particle diameter of the white pigment (A) calculated from the particle size distribution measured by the laser diffraction method.
  • Titanium dioxide pigments preferably used as white pigments include, for example, R960; manufactured by DuPont (rutile type, SiO 2 / Al 2 O 3 treatment, median diameter 210 nm), CR-97; Ishihara Sangyo Co., Ltd. ) (Rutile type, Al 2 O 3 / ZrO 2 treatment, median diameter 250 nm), JR-301; manufactured by Teika Co., Ltd. (rutile type, Al 2 O 3 treatment, median diameter 300 nm), JR-405; Co., Ltd.
  • the refractive index of the white pigment at a wavelength of 587.5 nm is preferably 2.00 to 2.70.
  • the refractive index of the white pigment is more preferably 2.40 or more.
  • the refractive index of the (A) white pigment to 2.70 or less, excessive interface reflection between the (A) white pigment and (B) the siloxane resin can be suppressed, and the resolution can be further improved.
  • the refractive index of the (A) white pigment can be measured using the Becke method defined in JIS K7142-2014 (established date: 2014/04/20).
  • the measurement wavelength is a standard 587.5 nm.
  • the content of the white pigment (A) in the negative photosensitive coloring composition of the present invention is preferably 20% by weight or more, more preferably 40% by weight or more in the solid content, from the viewpoint of further improving the reflectance. More preferably by weight.
  • the content of the (A) white pigment is preferably 65% by weight or less, and more preferably 60% by weight or less in the solid content from the viewpoint of suppressing development residue and forming a higher resolution pattern.
  • Solid content here means all the components except volatile components, such as a solvent, among the components contained in a negative photosensitive coloring composition. The amount of solid content can be determined by heating the negative photosensitive coloring composition at 170 ° C. for 30 minutes and measuring the residue obtained by evaporating volatile components.
  • the negative photosensitive coloring composition of the present invention may contain a pigment dispersant together with (A) the white pigment, and can improve the dispersibility of the (A) white pigment in the negative photosensitive coloring composition.
  • the pigment dispersant can be appropriately selected depending on the type of white pigment used and the surface state.
  • the pigment dispersant preferably contains an acidic group and / or a basic group. Examples of commercially available pigment dispersants include “Disperbyk” (registered trademark) 106, 108, 110, 180, 190, 2001, 1155, 140, and 145 (above, trade names, manufactured by BYK Chemie Co., Ltd.). . Two or more of these may be contained.
  • (B) Siloxane resin By containing the (B) siloxane resin having the specific structure described above, the refractive index difference between the (A) white pigment and the (B) siloxane resin is expanded, and the resulting cured film has a reflectivity. Can be further improved. Moreover, the (B) siloxane resin having the specific structure described above is excellent in heat resistance and can suppress color change and cracks in the cured film. Furthermore, a high resolution pattern can be formed.
  • Siloxane resin is a hydrolyzed / dehydrated condensate of organosilane.
  • the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) are characterized by containing fluorine.
  • the refractive index of (B) siloxane resin is reduced, the difference in refractive index from (A) white pigment is increased, and (A) between the white pigment and (B) siloxane resin.
  • the reflectance of the cured film can be improved by light reflection at the interface.
  • the repeating unit derived from the bifunctional alkoxysilane compound represented by the general formula (3) the excessive thermal polymerization (condensation) of the (B) siloxane resin in the heat treatment is suppressed, and the heat resistance is improved. Can do. Thereby, the crack and color change of the cured film in heat processing can be suppressed.
  • the (B) siloxane resin contains a total of 40 to 80 mol% of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2).
  • the total content of the repeating unit represented by the general formula (1) and the general formula (2) is preferably 50 mol% or more.
  • the total content of the repeating unit represented by the general formula (1) and the general formula (2) exceeds 80 mol%, (B) the phase with other components in the composition due to the hydrophobization of the siloxane resin.
  • the total content of the repeating unit represented by the general formula (1) and the general formula (2) is preferably 70 mol% or less. Further, the content of the repeating unit represented by the general formula (3) is preferably 50 mol% or less. When the content of the repeating unit represented by the general formula (3) is excessive, the cured film is not sufficiently crosslinked and the film characteristics are deteriorated. On the other hand, the content of the repeating unit represented by the general formula (3) is preferably 10 mol% or more. Since content of the repeating unit represented by General formula (3) is less than 10 mol%, since bridge
  • R 1 represents an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 10 carbon atoms in which all or part of hydrogen is substituted with fluorine.
  • R 2 represents a single bond, —O—, —CH 2 —CO—, —CO— or —O—CO—.
  • R 3 represents a monovalent organic group having 1 to 20 carbon atoms.
  • R 4 may be the same or different and represents a monovalent organic group having 1 to 20 carbon atoms.
  • R 1 is preferably an alkyl group in which all or part of hydrogen is substituted with fluorine from the viewpoint of further reducing the refractive index of the siloxane resin.
  • the alkyl group preferably has 1 to 6 carbon atoms.
  • R 3 and R 4 are preferably groups selected from an alkyl group having 1 to 6 carbon atoms and an acyl group having 2 to 10 carbon atoms from the viewpoint of further reducing the refractive index of the siloxane resin.
  • the repeating units represented by the general formulas (1) to (3) are derived from alkoxysilane compounds represented by the following general formulas (4) to (6), respectively. That is, the siloxane resin containing the repeating unit represented by the general formula (1) and / or the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3)
  • a plurality of alkoxysilane compounds including an alkoxysilane compound represented by the formula (4) and / or an alkoxysilane compound represented by the following general formula (5) and an alkoxysilane compound represented by the following general formula (6) Can be obtained by hydrolysis and polycondensation. Further, other alkoxysilane compounds may be used.
  • R 5 , R 6 , R 8 and R 9 are the same groups as R 1 , R 2 , R 3 and R 4 in the general formulas (1) to (3), respectively.
  • R 7 may be the same or different and represents a monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.
  • alkoxysilane compound represented by the general formula (4) examples include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane, and tridecafluorooctyltri Examples include methoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and the like. Two or more of these may be used.
  • alkoxysilane compound represented by the general formula (5) examples include bis (trifluoromethyl) dimethoxysilane, bis (trifluoropropyl) dimethoxysilane, bis (trifluoropropyl) diethoxysilane, trifluoropropylmethyldimethoxysilane, Examples include trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, and the like. Two or more of these may be used.
  • alkoxysilane compound represented by the general formula (6) examples include dimethyldimethoxysilane, dimethyldiethoxysilane, ethylmethyldimethoxysilane, ethylmethyldimethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, and diphenyldimethoxysilane.
  • alkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, Trifunctional alkoxysilane compounds such as 3-ureidopropyltriethoxysilane; tetramethoxysilane, te
  • the total content of the alkoxysilane compound represented by the general formula (4) and the alkoxysilane compound represented by the general formula (5) in the mixture of the alkoxysilane compounds as raw materials for the siloxane resin is (B ) 40 mol% or more is preferable from the viewpoint of setting the content of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) in all the repeating units of the siloxane resin within the above range. 50 mol% or more is more preferable.
  • the total content of the alkoxysilane compound represented by the general formula (4) and the alkoxysilane compound represented by the general formula (5) is preferably 80 mol% or less, and 70 mol% or less. More preferred.
  • the alkoxysilane compound may be included in the above range.
  • both the alkoxysilane compound represented by 4) and the alkoxysilane compound represented by the general formula (5) are included, the total of these may be included in the above range.
  • the weight average molecular weight (Mw) of the siloxane resin is preferably 1,000 or more, and more preferably 2,000 or more, from the viewpoint of coating properties.
  • the Mw of the (B) siloxane resin is preferably 50,000 or less, and more preferably 20,000 or less.
  • Mw of the (B) siloxane resin in the present invention refers to a polystyrene equivalent value measured by gel permeation chromatography (GPC).
  • the refractive index of the siloxane resin at a wavelength of 587.5 nm is preferably 1.35 to 1.55.
  • the refractive index of the siloxane resin is more preferably 1.40 or more.
  • the interface reflection between the (A) white pigment and the (B) siloxane resin can be increased, and the reflectance can be further improved.
  • the refractive index of the siloxane resin is more preferably 1.50 or less.
  • the refractive index of (B) siloxane resin is 20 ° C. under atmospheric pressure using a prism coupler (PC-2000 (manufactured by Metricon)) for a cured film of siloxane resin formed on a silicon wafer.
  • PC-2000 manufactured by Metricon
  • the measurement is performed by irradiating light having a wavelength of 587.5 nm from the direction perpendicular to the cured film surface.
  • the third decimal place will be rounded off.
  • the cured film of siloxane resin is spin-coated on a silicon wafer with a siloxane resin solution prepared by dissolving the siloxane resin in an organic solvent so that the solid content concentration is 40% by weight, and dried on a hot plate at 90 ° C. for 2 minutes. Then, it is prepared by curing in an air at 230 ° C. for 30 minutes using an oven.
  • a negative photosensitive coloring composition contains 2 or more types of (B) siloxane resin, it is preferable that at least 1 type of refractive index exists in the said range.
  • the difference in refractive index between (A) the white pigment and (B) the siloxane resin at a wavelength of 587.5 nm is preferably 1.16 to 1.26.
  • the difference in refractive index is more preferably 1.18 or more.
  • the refractive index difference is 1.26 or less, excessive interface reflection between (A) the white pigment and (B) the siloxane resin can be suppressed, and the resolution can be further improved.
  • the difference in refractive index is more preferably 1.24 or less.
  • the content of the (B) siloxane resin can be arbitrarily set depending on the desired film thickness and application, but in the negative photosensitive coloring composition, it is 10 to 60. % By weight is preferred. Further, the content of the (B) siloxane resin is preferably 10% by weight or more, and more preferably 20% by weight or more in the solid content of the negative photosensitive coloring composition. On the other hand, the content of the (B) siloxane resin is preferably 60% by weight or less, and more preferably 50% by weight or less in the solid content of the negative photosensitive coloring composition.
  • the siloxane resin can be obtained by hydrolyzing the aforementioned organosilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction in the presence of a solvent or without a solvent.
  • Various conditions in the hydrolysis can be set according to the physical properties suitable for the intended application in consideration of the reaction scale, the size and shape of the reaction vessel, and the like. Examples of various conditions include acid concentration, reaction temperature, reaction time, and the like.
  • an acid catalyst such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or its anhydride, or an ion exchange resin can be used.
  • an acidic aqueous solution containing formic acid, acetic acid and / or phosphoric acid is preferable.
  • the amount of the acid catalyst added is 0.05 wt.
  • the addition amount of the acid catalyst is preferably 20 parts by weight or less and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total alkoxysilane compound.
  • the total amount of the alkoxysilane compound means an amount including all of the alkoxysilane compound, its hydrolyzate and its condensate.
  • the hydrolysis reaction can be performed in an organic solvent.
  • the organic solvent can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the negative photosensitive coloring composition.
  • examples of the organic solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, and 3-methyl-3- Alcohols such as methoxy-1-butanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl Ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene Ethers such as
  • diacetone alcohol propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono- t-Butyl ether, ⁇ -butyrolactone and the like are preferably used.
  • the hydrolysis can be performed without a solvent. After completion of the hydrolysis reaction, it is also preferable to adjust the concentration to an appropriate concentration for use as a negative photosensitive coloring composition by further adding an organic solvent to the obtained composition. It is also possible to distill and remove all or part of the produced alcohol and the like after heating and / or under reduced pressure, and then add a suitable organic solvent.
  • the amount of the organic solvent added is preferably 50 parts by weight or more, and 80 parts by weight or more with respect to 100 parts by weight of the total alkoxysilane compound from the viewpoint of suppressing gel formation. More preferred.
  • the addition amount of the organic solvent is preferably 500 parts by weight or less and more preferably 200 parts by weight or less with respect to 100 parts by weight of the total alkoxysilane compound from the viewpoint of allowing hydrolysis to proceed more rapidly.
  • water used for the hydrolysis reaction ion-exchanged water is preferable.
  • the amount of water can be arbitrarily set, but is preferably 1.0 to 4.0 mol with respect to 1 mol of all alkoxysilane compounds.
  • Examples of the dehydration condensation method include a method of heating a silanol compound solution obtained by hydrolysis reaction of an organosilane compound as it is.
  • the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower, and the heating time is preferably 1 to 100 hours.
  • reheating or addition of a base catalyst may be performed.
  • an appropriate amount such as the generated alcohol may be distilled and removed under heating and / or reduced pressure, and then a suitable solvent may be added.
  • the siloxane resin solution after hydrolysis and dehydration condensation preferably does not contain the catalyst, and the catalyst can be removed as necessary.
  • the catalyst removal method water washing, treatment with an ion exchange resin, and the like are preferable from the viewpoint of easy operation and removability.
  • the water washing is a method in which an organic layer obtained by diluting a siloxane resin solution with an appropriate hydrophobic solvent and washing several times with water is concentrated with an evaporator or the like.
  • the treatment with an ion exchange resin is a method in which a siloxane resin solution is brought into contact with an appropriate ion exchange resin.
  • (C) Photopolymerization initiator By containing a photopolymerization initiator and (D) a photopolymerizable compound, (D) a photopolymerizable compound by radicals generated from (C) the photopolymerization initiator by light irradiation. As the polymerization proceeds, the exposed portion of the negative photosensitive coloring composition is insolubilized in the aqueous alkali solution, so that a negative pattern can be formed.
  • Any photopolymerization initiator may be used as long as it can be decomposed and / or reacted with light (including ultraviolet rays and electron beams) to generate radicals.
  • light including ultraviolet rays and electron beams
  • Any photopolymerization initiator may be used as long as it can be decomposed and / or reacted with light (including ultraviolet rays and electron beams) to generate radicals.
  • 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl ⁇ -aminoalkylphenone compounds such as -phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
  • Acylphosphine oxide compounds such as phosphine oxide, bis (2,
  • the negative photosensitive coloring composition of the present invention does not contain (A) a colorant other than the white pigment, (C) 2,4,6-trimethylbenzoylphenyl is used to suppress coloring by the photopolymerization initiator.
  • Acylphosphine oxide photopolymerization such as phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) -phosphine oxide Initiators are preferred.
  • the content of the (C) photopolymerization initiator in the negative photosensitive coloring composition of the present invention is preferably 0.01% by weight or more, preferably 1% by weight in the solid content from the viewpoint of effectively promoting radical curing. The above is more preferable.
  • the content of (C) the photopolymerization initiator is preferably 20% by weight or less in the solid content, 10% by weight or less is more preferable.
  • the photopolymerizable compound in the present invention refers to a compound having an ethylenically unsaturated double bond in the molecule.
  • the photopolymerizable compound preferably has two or more ethylenically unsaturated double bonds in the molecule.
  • the (D) photopolymerizable compound preferably has a (meth) acrylic group.
  • the double bond equivalent of the (D) photopolymerizable compound is preferably 400 g / mol or less from the viewpoint of further improving the sensitivity in pattern processing.
  • the double bond equivalent of the (D) photopolymerizable compound is preferably 80 g / mol or more from the viewpoint of further improving the resolution in pattern processing.
  • a photopolymerizable compound for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, Trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane
  • a compound having a fluorine atom is preferable from the viewpoint of further improving the reflectance.
  • the content of the (D) photopolymerizable compound in the negative photosensitive coloring composition of the present invention is preferably 1% by weight or more in the solid content from the viewpoint of effectively promoting radical curing.
  • the content of the photopolymerizable compound (D) is preferably 40% by weight or less in the solid content from the viewpoint of suppressing radical excess reaction and further improving the resolution.
  • the negative photosensitive coloring composition can be easily adjusted to a viscosity suitable for coating, and the uniformity of the coating film can be improved.
  • the organic solvent it is preferable to combine an organic solvent having a boiling point under atmospheric pressure of more than 150 ° C. and not more than 250 ° C. with an organic solvent having a boiling point of not more than 150 ° C. Since the negative photosensitive coloring composition contains an organic solvent having a boiling point of more than 150 ° C. and not more than 250 ° C., the organic solvent volatilizes appropriately at the time of coating, and the coating film is dried. The film thickness uniformity can be improved. Furthermore, by containing an organic solvent having a boiling point of 150 ° C. or lower under atmospheric pressure, it is possible to suppress the remaining of the organic solvent in the cured film of the present invention described later.
  • an organic solvent having a boiling point of 150 ° C. or lower under atmospheric pressure is 50% by weight or more of the total organic solvent It is preferable to contain.
  • organic solvents having a boiling point of 150 ° C. or less under atmospheric pressure include ethanol, isopropyl alcohol, 1-propyl alcohol, 1-butanol, 2-butanol, isopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol Monoethyl ether, methoxymethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, acetol, acetylacetone, Methyl isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, lactic acid , Toluene, cyclopentanone, cyclohexane, normal heptane, benzene, methyl acetate,
  • Examples of the organic solvent having a boiling point under atmospheric pressure of more than 150 ° C. and not more than 250 ° C. include ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono n-butyl ether, Propylene glycol mono-t-butyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, 3-ethoxypropion Ethyl acetate, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, diisobutyl ketone, diacetone alcohol, ethyl lactate, butyl lactate, dimethylformamide, Methylacetamide, .gamma.-butyrolactone,
  • the content of the organic solvent can be arbitrarily set according to the application method and the like.
  • the content of the organic solvent in the negative photosensitive coloring composition is preferably 50% by weight or more and 95% by weight or less.
  • the negative photosensitive coloring composition of the present invention may further contain an adhesion improver, an ultraviolet absorber, a polymerization inhibitor, a surfactant and the like, if necessary.
  • adhesion improver By including an adhesion improver in the negative photosensitive coloring composition, the adhesion to the substrate is improved, and a highly reliable cured film can be obtained.
  • adhesion improver include alicyclic epoxy compounds and silane coupling agents. Among these, since an alicyclic epoxy compound has high heat resistance, it can suppress the color change of the cured film after a heating more.
  • Examples of the alicyclic epoxy compound include 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-2,2-bis (hydroxymethyl) -1-butanol.
  • silane coupling agent a compound represented by the following general formula (7) is preferable.
  • each R 10 independently represents an alkyl group having 1 to 6 carbon atoms. From the viewpoint of reducing the refractive index, R 10 is preferably an alkyl group having 1 to 3 carbon atoms. p represents 0 or 1. From the viewpoint of further improving the adhesion with the substrate, p is preferably 0. R 11 represents a trivalent organic group having 3 to 30 carbon atoms, preferably a trivalent hydrocarbon group having 3 to 10 carbon atoms.
  • R 12 each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. From the viewpoint of reducing the refractive index, R 12 is preferably an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms.
  • Examples of the silane coupling agent represented by the general formula (7) include 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (tert-butylamino) -2 -Oxoethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (isopropylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (isopropylamino) -2-oxoethyl) -5- (tri Methoxysilyl) pentanoic acid, 3- (isobutylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 3- (tert-pentylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (tert- Pentylamino
  • the content of the adhesion improving agent in the negative photosensitive coloring composition is preferably 0.1% by weight or more, more preferably 1% by weight or more in the solid content from the viewpoint of further improving the adhesion to the substrate.
  • the content of the adhesion improver is preferably 20% by weight or less, and more preferably 10% by weight or less in the solid content from the viewpoint of further suppressing color change due to heating.
  • UV absorbers include 2- (2H-benzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -4,6-tert-pentyl from the viewpoint of further suppressing color change due to heating.
  • Benzotriazole compounds such as phenol, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole; benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone; 2- (4,6 -Diphenyl-1,3,5triazin-2-yl) -5-[(hexyl) oxy] -phenol Triazine compounds are preferably used. Two or more of these may be contained.
  • the resolution of the cured film obtained can be improved.
  • the polymerization inhibitor include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol.
  • Commercially available polymerization inhibitors include “IRGANOX” (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, 295 (above, trade names, BASF Japan Ltd.). Two or more of these may be contained.
  • Surfactants include, for example, fluorine-based surfactants such as “Megafac” (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (above, trade name, manufactured by DIC Corporation). Silicone surfactants such as “BYK” (registered trademark) -333, 301, 331, 345, 307 (above, trade name, manufactured by Big Chemie Japan Co., Ltd.); polyalkylene oxide surfactants; And a (meth) acrylate surfactant. Two or more of these may be contained.
  • fluorine-based surfactants such as “Megafac” (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (above, trade name, manufactured by DIC Corporation). Silicone surfactants such as “BYK” (registered trademark) -333, 301, 331, 345, 307 (above, trade
  • the solid content concentration of the negative photosensitive coloring composition can be arbitrarily set according to the coating method and the like.
  • the solid content concentration is preferably 5% by weight or more and 50% by weight or less.
  • the negative photosensitive coloring composition of the present invention can be obtained by mixing the aforementioned components (A) to (E) and other components as necessary. More specifically, for example, first, a mixed liquid of (A) a white pigment, (B) a siloxane resin, and (E) an organic solvent is dispersed using a mill-type disperser filled with zirconia beads, thereby dispersing the pigment. It is preferable to obtain a liquid.
  • the cured film of the present invention is a cured product of the aforementioned negative photosensitive coloring composition of the present invention.
  • the cured film of the present invention can be suitably used as a light shielding pattern in an OGS type touch panel or a partition pattern of an image display device.
  • the thickness of the cured film is preferably 10 ⁇ m or more.
  • the method for producing a cured film of the present invention comprises (I) a step of applying a negative photosensitive coloring composition of the present invention on a substrate to form a coating film, (II) a step of exposing and developing the coating film, And (III) It is preferable to have a step of heating the coated film after the development. Below, each process is demonstrated.
  • the negative photosensitive coloring composition of the present invention is applied to form a coating film.
  • the coating method include spin coating, slit coating, screen printing, inkjet coating, and bar coater coating.
  • pre-bake After forming the coating film, it is preferable to dry (pre-bake) the substrate coated with the negative photosensitive coloring composition.
  • drying method include reduced pressure drying and heat drying.
  • the heating device include a hot plate and an oven. The heating temperature is preferably 60 to 150 ° C., and the heating time is preferably 30 seconds to 3 minutes.
  • the film thickness of the coating film after pre-baking is preferably 5 to 20 ⁇ m.
  • the exposure may be performed through a desired mask or may be performed without using a mask.
  • Examples of the exposure machine include a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (hereinafter referred to as “PLA”), and the like.
  • the exposure intensity is preferably about 10 to 4000 J / m 2 (wavelength 365 nm exposure amount conversion).
  • Examples of the exposure light source include ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like.
  • Examples of the developing method include methods such as showering, dipping, and paddle.
  • the immersion time in the developer is preferably 5 seconds to 10 minutes.
  • Examples of the developer include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates; amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine; tetramethyl Examples thereof include aqueous solutions of quaternary ammonium salts such as ammonium hydroxide and choline. It is preferable to rinse with water after development. Subsequently, dry baking may be performed at 50 to 140 ° C.
  • the coated film is cured to obtain a patterned processed substrate.
  • the patterned processed substrate refers to a substrate having a patterned cured film.
  • Examples of the heating device include a hot plate and an oven.
  • the heating temperature is preferably 120 to 250 ° C.
  • the heating time is preferably 15 minutes to 2 hours.
  • the patterned processed substrate of the present invention has a pattern made of the above-described cured film of the present invention on the substrate. Since such a pattern has high resolution and high reflectance, it can be suitably used as a white shading pattern for a touch panel.
  • Examples of the substrate include those exemplified in the method for producing a cured film of the present invention.
  • the total reflection (incident angle 8 °, light source: D-65 (2 ° field of view)) of the light shielding pattern is CIE 1976 (L *, a *, b *).
  • the cured film pattern having the color characteristics can be obtained, for example, by pattern processing using the above-described preferable production method using the above-described negative photosensitive coloring composition of the present invention.
  • the substrate with a partition wall of the present invention has a patterned partition wall (hereinafter sometimes referred to as “partition wall (F-1)”) made of the above-described cured film on the substrate.
  • partition wall (F-1) patterned partition wall
  • the partition wall refers to one having a repetitive pattern corresponding to the number of pixels of the image display device.
  • Examples of the number of pixels of the image display device include 4000 vertically and 2000 horizontally.
  • the number of pixels affects the resolution (fineness) of the displayed image. For this reason, it is necessary to form a number of pixels according to the required image resolution and the screen size of the image display device, and it is preferable to determine the pattern formation dimensions of the partition wall accordingly.
  • the substrate has a function as a support in the substrate with a partition wall.
  • the partition has a function of preventing light color mixing between adjacent pixels when a layer containing a color conversion luminescent material, which will be described later, is formed between adjacent partitions and a pixel containing the color conversion luminescent material is configured.
  • the partition wall (F-1) preferably has a reflectance of 60% to 90% per 10 ⁇ m thickness at a wavelength of 550 nm. By setting the reflectance to 60% or more, the luminance of the display device can be improved by utilizing the reflection on the side wall of (F-1) partition wall. On the other hand, from the viewpoint of improving pattern formation accuracy, the reflectance is preferably 90% or less.
  • FIG. 1 shows a cross-sectional view of one embodiment of a substrate with a partition wall of the present invention having a patterned partition wall.
  • a patterned partition wall 2 is provided on a substrate 1.
  • the substrate examples include a glass plate, a resin plate, a resin film, and the like.
  • the material of the glass plate alkali-free glass is preferable.
  • polyester, (meth) acrylic polymer, transparent polyimide, polyether sulfone, and the like are preferable.
  • the thickness of the glass plate and the resin plate is preferably 1 mm or less, and preferably 0.8 mm or less.
  • the thickness of the resin film is preferably 100 ⁇ m or less.
  • the partition wall (F-1) preferably has a reflectance of 60 to 90% per 10 ⁇ m thickness at a wavelength of 550 nm.
  • the thickness of the partition wall (F-1) refers to the length of the partition wall (F-1) perpendicular to the substrate (in the height direction).
  • the thickness of the partition walls 2 is represented by the symbol X.
  • the length of the partition wall (F-1) in the horizontal direction is the width of the partition wall (F-1).
  • the width of the partition walls 2 is represented by the symbol L.
  • the reflection on the side wall of the partition contributes to improvement of the luminance of the display device.
  • the reflectance per thickness is considered to be the same regardless of the thickness direction and the width direction, the present invention focuses on the reflectance per partition wall thickness.
  • the thickness of the partition wall (F-1) is preferably 0.5 to 50 ⁇ m, and the width is preferably 5 to 40 ⁇ m. Therefore, in the present invention, 10 ⁇ m is selected as the representative value of the thickness of the partition wall (F-1), and attention is paid to the reflectance per 10 ⁇ m thickness.
  • the reflectance per 10 ⁇ m thickness is less than 60%, the reflection on the side wall of the partition wall becomes small, and the luminance of the display device becomes insufficient.
  • the reflectance is preferably 90% or less.
  • the reflectance per 10 ⁇ m thickness of the partition wall (F-1) at a wavelength of 550 nm is measured from the top surface of the partition wall (F-1) having a thickness of 10 ⁇ m in the height direction (for example, CM-2600d manufactured by Konica Minolta Co., Ltd.).
  • the same composition as the partition wall (F-1) is obtained.
  • a solid film having a thickness of 10 ⁇ m may be prepared, and the reflectance of the solid film may be measured instead of the partition wall (F-1).
  • the material for forming the partition wall (F-1) forming a solid film under the same processing conditions as the formation of the partition wall (F-1) except that the thickness is 10 ⁇ m and no pattern is formed.
  • the reflectance of the film may be similarly measured from the upper surface.
  • a means for making a reflectance into the said range it can obtain by patterning a partition with the above-mentioned preferable manufacturing method, for example using the above-mentioned negative photosensitive coloring composition of this invention. .
  • the thickness of the partition wall (F-1) is such that the substrate with the partition wall contains a (G) color conversion luminescent material described later (hereinafter referred to as “layer containing a color conversion luminescent material (G)”). When it has, it is preferable that it is larger than the thickness of the layer (G) containing a color conversion luminescent material.
  • the thickness of the partition wall (F-1) is preferably 0.5 ⁇ m or more, and more preferably 10 ⁇ m or more.
  • the thickness of the partition wall (F-1) is preferably 50 ⁇ m or less and more preferably 20 ⁇ m or less from the viewpoint of more efficiently extracting light emitted from the bottom of the layer (G) containing the color conversion light-emitting material.
  • the width of the partition wall (F-1) is sufficient to improve the luminance by utilizing light reflection on the side wall of the partition wall and to suppress the color mixture of the layer (G) containing the adjacent color conversion luminescent material due to light leakage. Anything is acceptable.
  • the width of the partition wall is preferably 5 ⁇ m or more, and more preferably 15 ⁇ m or more.
  • the width of the partition wall (F-1) is preferably 50 ⁇ m or less, and more preferably 40 ⁇ m or less, from the viewpoint of securing a large light emitting region of the layer (G) containing the color conversion light emitting material and further improving the luminance.
  • the surface contact angle of the partition wall (F-1) with respect to propylene glycol monomethyl ether acetate is preferably 10 ° or more, and preferably 20 ° or more from the viewpoint of improving the ink-jet coating property and facilitating the color conversion light-emitting material. More preferably, it is 40 ° or more.
  • the surface contact angle of the partition (F-1) is preferably 70 ° or less, and more preferably 60 ° or less.
  • the surface contact angle of the partition wall (A-1) conforms to the wettability test method for the surface of the substrate glass defined in JIS R3257 (established date: 1999/04/20) with respect to the upper part of the partition wall. Can be measured.
  • a method for setting the surface contact angle of the partition wall (F-1) in the above range for example, in the above-described negative photosensitive coloring composition of the present invention, a negative type containing a photopolymerizable compound having a fluorine atom is used.
  • a photosensitive coloring composition can be obtained by patterning a partition wall by the above-mentioned preferable manufacturing method.
  • the optical density per thickness of 1.0 ⁇ m is further 0.1 to 4.0 between the substrate and the partition wall (F-1). It is preferable to have a patterned light-shielding partition (hereinafter sometimes referred to as “light-shielding partition (F-2)”).
  • the light-shielding partition (F-2) is preferably formed in the same pattern shape as the partition (F-1).
  • FIG. 9 shows a cross-sectional view of one embodiment of a substrate with a partition wall according to the present invention having a light shielding partition wall.
  • a patterned partition wall 2 and a patterned light shielding partition wall 10 are provided, and a layer 3 containing a color conversion light emitting material is arranged in a region separated by the partition wall 2 and the light shielding partition wall 10.
  • the light shielding partition (F-2) has an optical density of 0.1 to 4.0 per 1.0 ⁇ m thickness.
  • the thickness of the light shielding partition (F-2) is preferably 0.5 to 10 ⁇ m, as will be described later. Therefore, in the present invention, 1.0 ⁇ m is selected as the representative value of the thickness of the partition wall (F-2), and attention is paid to the optical density per 1.0 ⁇ m thickness.
  • the optical density per 1.0 ⁇ m thickness is more preferably 0.5 or more.
  • the pattern processability can be improved.
  • the optical density per 1.0 ⁇ m thickness is more preferably 3.0 or less.
  • the optical density (OD value) of the light-shielding partition wall (F-2) was measured by measuring the intensity of incident light and transmitted light using an optical densitometer (361T (visual); manufactured by X-rite), and the following formula (11) Can be calculated.
  • the light shielding partition (F-2) may have a preferable composition described later.
  • the thickness of the light shielding partition (F-2) is preferably 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more, from the viewpoint of improving the light shielding property. On the other hand, from the viewpoint of improving flatness, the thickness of the light shielding partition (F-2) is preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less.
  • the width of the light shielding partition (F-2) is preferably about the same as that of the partition (F-1).
  • the light shielding partition (F-2) preferably contains a resin and a black pigment.
  • the resin has a function of improving crack resistance and light resistance of the partition walls.
  • the black pigment has a function of absorbing incident light and reducing emitted light.
  • the resin examples include epoxy resin, (meth) acrylic polymer, polyurethane, polyester, polyimide, polyolefin, polysiloxane, and the like. Two or more of these may be contained. Among these, polyimide is preferable because of excellent heat resistance and solvent resistance.
  • black pigments include black organic pigments, mixed color organic pigments, and inorganic pigments.
  • black organic pigments include carbon black, perylene black aniline black, and benzofuranone pigments. These may be coated with a resin.
  • the mixed color organic pigment include those obtained by mixing two or more pigments such as red, blue, green, violet, yellow, magenta and / or cyan to be pseudo black.
  • black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver; metal oxides; metal composite oxides; metal sulfides; Metal oxynitrides; metal carbides and the like.
  • a method for patterning the light shielding partition (F-2) on the substrate for example, a photosensitive material described in JP-A-2015-1654 is used, and the photosensitive property is the same as that of the partition (F-1) described above.
  • a method of forming a pattern by a paste method is preferred.
  • a layer (G) containing a color conversion light-emitting material is formed between the adjacent partition walls (F-1).
  • the layer containing the color conversion light-emitting material has a function of performing color display by converting at least part of the wavelength region of incident light and emitting emitted light in a wavelength region different from the incident light.
  • the layer (G) containing a color conversion luminescent material may be generally called a pixel.
  • FIG. 2 shows a cross-sectional view of one embodiment of a substrate with a partition wall of the present invention having a patterned partition wall and a layer (G) containing a color conversion luminescent material.
  • a patterned partition wall 2 is provided, and a layer 3 containing a color conversion luminescent material is arranged in a region separated by the partition wall 2.
  • the color conversion luminescent material preferably contains an inorganic phosphor and / or an organic phosphor.
  • a region corresponding to a red pixel Preferably contains a red phosphor that emits red fluorescence when excited by blue excitation light, and the region corresponding to the green pixel emits green fluorescence when excited by blue excitation light. It is preferable that the fluorescent material is contained, and it is preferable that the region corresponding to the blue pixel does not contain the fluorescent material.
  • the substrate with a partition wall of the present invention can also be used for a display device using a blue micro LED corresponding to each pixel separated by a white partition wall as a backlight.
  • Each pixel can be turned on / off by turning on / off the blue micro LED, and no liquid crystal is required.
  • the inorganic phosphor emits each color such as green and red depending on the peak wavelength of the emission spectrum.
  • the inorganic phosphor include those excited by excitation light having a wavelength of 400 to 500 nm and having a peak in the region of the emission spectrum of 500 to 700 nm, and inorganic semiconductor fine particles called quantum dots.
  • the shape of the former inorganic phosphor include a spherical shape and a columnar shape.
  • Examples of such inorganic phosphors include YAG phosphors, TAG phosphors, sialon phosphors, and Mn 4+ activated fluoride complex phosphors. Two or more of these may be used.
  • quantum dots are preferable. Since the quantum dot has a smaller average particle diameter than other phosphors, the surface of the layer (G) containing the color conversion light-emitting material can be smoothed and light scattering on the surface can be suppressed. The extraction efficiency can be further improved and the luminance can be further improved.
  • Examples of the material of the quantum dots include II-IV, III-V, IV-VI, and IV group semiconductors.
  • these inorganic semiconductors include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, GeS, GeSe, GeTe Examples thereof include SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si 3 N 4 , Ge 3 N 4 , and Al 2 O 3 .
  • the quantum dot may contain a p-type dopant or an n-type dopant.
  • the quantum dot may have a core-shell structure.
  • any appropriate functional layer may be formed around the shell according to the purpose, and surface treatment and / or chemical modification may be performed on the shell surface. .
  • the shape of the quantum dot examples include a spherical shape, a columnar shape, a flake shape, a plate shape, and an indeterminate shape.
  • the average particle diameter of the quantum dots can be selected according to the desired emission wavelength, and is preferably 1 to 30 nm. If the average particle diameter of the quantum dots is 1 to 10 nm, the peak in the emission spectrum can be made sharper in each of blue, green and red. For example, blue light is emitted when the average particle diameter of the quantum dots is about 2 nm, green light is emitted when it is about 3 nm, and red light is emitted when it is about 6 nm.
  • the average particle size of the quantum dots is preferably 2 nm or more, and preferably 8 nm or less.
  • the average particle diameter of the quantum dots can be measured by a dynamic light scattering method. Examples of the measuring device for the average particle diameter include a dynamic light scattering photometer DLS-8000 (manufactured by Otsuka Electronics Co., Ltd.).
  • Examples of the organic phosphor include a pyromethene derivative having a basic skeleton represented by the following structural formula (8), a phosphor that emits red fluorescence when excited by blue excitation light, and a green phosphor that is excited by blue excitation light.
  • Examples of the fluorescent substance that emits fluorescence include a pyromethene derivative having a basic skeleton represented by the following structural formula (9).
  • perylene derivatives, porphyrin derivatives, oxazine derivatives, pyrazine derivatives, and the like that emit red or green fluorescence by selecting a substituent. Two or more of these may be contained. Among these, pyromethene derivatives are preferable because of their high quantum yield.
  • the pyromethene derivative can be obtained, for example, by the method described in JP2011-241160A.
  • a layer (G) containing a color conversion light-emitting material having a desired thickness can be easily formed.
  • the thickness of the layer (G) containing the color conversion luminescent material is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, from the viewpoint of improving color characteristics.
  • the thickness of the layer (G) containing the color conversion luminescent material is preferably 30 ⁇ m or less, and more preferably 20 ⁇ m or less, from the viewpoint of thinning the display device and curved surface processability.
  • the size of the layer containing the color conversion luminescent material is generally about 20 to 200 ⁇ m.
  • the layer (G) containing the color conversion luminescent material is preferably arranged separated by a partition wall (F-1).
  • a partition wall (F-1) By providing the partition between the layers (G) containing the adjacent color conversion light-emitting material, diffusion and color mixing of emitted light can be further suppressed.
  • the layer (G) containing the color conversion luminescent material for example, there is a method of filling the space separated by the partition wall (F-1) with the color conversion luminescent material coating liquid containing the color conversion luminescent material.
  • the color conversion light emitting material coating liquid may further contain a resin or a solvent.
  • an inkjet coating method or the like is preferable from the viewpoint of easily applying different types of color conversion luminescent materials to each pixel.
  • the obtained coating film may be dried under reduced pressure and / or heat.
  • the drying temperature under reduced pressure is preferably 80 ° C. or lower in order to prevent the drying solvent from recondensing on the inner wall of the vacuum chamber.
  • the vacuum drying pressure is preferably not higher than the vapor pressure of the solvent contained in the coating film, and preferably 1 to 1000 Pa.
  • the drying time under reduced pressure is preferably 10 to 600 seconds.
  • the heating and drying apparatus include an oven and a hot plate.
  • the heating and drying temperature is preferably 60 to 200 ° C.
  • the heat drying time is preferably 1 to 60 minutes.
  • the substrate with a partition wall of the present invention is further provided on a layer (G) containing a color-converting light-emitting material and (H) a low refractive index layer (hereinafter referred to as “a refractive index of 1.20 to 1.35 at a wavelength of 550 nm”). It may preferably be described as “low refractive index layer (H)”.
  • a refractive index of 1.20 to 1.35 at a wavelength of 550 nm It may preferably be described as “low refractive index layer (H)”.
  • FIG. 3 shows a cross-sectional view of one embodiment of the substrate with a partition wall of the present invention having a low refractive index layer.
  • a patterned partition wall 2 and a layer 3 containing a color conversion light emitting material are provided, and a low refractive index layer 4 is further provided thereon.
  • the refractive index of the low-refractive index layer (H) is 1. from the viewpoint of allowing light to be efficiently incident on the layer (G) containing the color conversion light-emitting material with moderate reflection of light from the backlight. 20 or more is preferable, and 1.23 or more is more preferable.
  • the refractive index of the low refractive index layer (H) is preferably 1.35 or less, and more preferably 1.30 or less.
  • the refractive index of the low refractive index layer (H) is perpendicular to the cured film surface using a prism coupler (PC-2000 (manufactured by Metricon)) at 20 ° C. under atmospheric pressure. To irradiate light with a wavelength of 550 nm.
  • the low refractive index layer (H) preferably contains polysiloxane and silica particles having no hollow structure.
  • Polysiloxane is highly compatible with inorganic particles such as silica particles and functions as a binder capable of forming a transparent layer.
  • silica particles it is possible to efficiently form minute voids in the low refractive index layer (H) to reduce the refractive index, and to easily adjust the refractive index to the above range. Can do.
  • silica particles that do not have a hollow structure as silica particles cracks can be suppressed because there is no hollow structure that is liable to cause cracks during curing shrinkage.
  • the polysiloxane and the silica particles having no hollow structure may be contained independently, or the polysiloxane and the silica particles having no hollow structure are combined. It may be contained. From the viewpoint of uniformity of the low refractive index layer (H), the polysiloxane and the silica particles having no hollow structure are preferably contained in a combined state.
  • the polysiloxane contained in the low refractive index layer (H) preferably contains fluorine.
  • the refractive index of the low refractive index layer (H) can be easily adjusted to 1.20 to 1.35.
  • the fluorine-containing polysiloxane can be obtained by hydrolysis and polycondensation of an alkoxysilane compound including a fluorine-containing alkoxysilane compound represented by the following general formula (10). Further, other alkoxysilane compounds may be used.
  • R 13 represents a fluoroalkyl group having 3 to 17 fluorine atoms.
  • R 7 represents the same group as R 7 in formulas (4) to (6).
  • m represents 1 or 2.
  • 4-m R 7 and m R 13 may be the same or different.
  • fluorine-containing alkoxysilane compound represented by the general formula (10) examples include trifluoroethyltrimethoxysilane, trifluoroethyltriethoxysilane, trifluoroethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, and trifluoro.
  • the content of polysiloxane in the low refractive index layer (H) is preferably 4% by weight or more from the viewpoint of suppressing cracks.
  • the content of the polysiloxane is 32% by weight or less from the viewpoint of ensuring thixotropy due to the network between silica particles and maintaining a moderate air layer in the low refractive index layer (H) to further reduce the refractive index. preferable.
  • silica particles having no hollow structure in the low refractive index layer (H) examples include “Snowtex” (registered trademark) and “organosilica sol” (registered trademark) series (isopropyl alcohol dispersions) manufactured by Nissan Chemical Industries, Ltd.
  • Ethylene glycol dispersion Ethylene glycol dispersion, methyl ethyl ketone dispersion, dimethylacetamide dispersion, methyl isobutyl ketone dispersion, propylene glycol monomethyl acetate dispersion, propylene glycol monomethyl ether dispersion, methanol dispersion, ethyl acetate dispersion, butyl acetate dispersion, xylene -N-butanol dispersion, toluene dispersion, etc., such as PGM-ST, PMA-ST, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP). Two or more of these may be contained.
  • the content of silica particles having no hollow structure in the low refractive index layer (H) ensures thixotropy due to the network between the silica particles, and an air layer is appropriately kept in the low refractive index layer (H). From the viewpoint of further reducing the amount, 68% by weight or more is preferable. On the other hand, the content of silica particles having no hollow structure is preferably 96% by weight or less from the viewpoint of suppressing cracks.
  • the thickness of the low refractive index layer (H) is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, from the viewpoint of suppressing the generation of defects by covering the steps of the layer (G) containing the color conversion luminescent material. preferable.
  • the thickness of the low refractive index layer (H) is preferably 20 ⁇ m or less and more preferably 10 ⁇ m or less from the viewpoint of reducing stress that causes cracks in the low refractive index layer (H).
  • a coating method is preferable because the forming method is easy.
  • a low refractive index resin composition containing polysiloxane and silica particles is applied on a layer (G) containing a color conversion light-emitting material, dried and then heated, whereby a low refractive index layer (H ) Can be formed.
  • the substrate with a partition wall of the present invention preferably further comprises (I-1) an inorganic protective layer I having a thickness of 50 to 1,000 nm on the low refractive index layer (H).
  • I-1 an inorganic protective layer I having a thickness of 50 to 1,000 nm on the low refractive index layer (H).
  • FIG. 4 shows a cross-sectional view of one embodiment of a substrate with a partition wall of the present invention having a low refractive index layer and an inorganic protective layer I.
  • a patterned partition wall 2 and a layer 3 containing a color conversion luminescent material are provided, and a low refractive index layer 4 and an inorganic protective layer I (5) are further provided in this order.
  • the substrate with a partition wall of the present invention preferably further comprises (I-2) an inorganic protective layer II having a thickness of 50 to 1,000 nm under the low refractive index layer (H).
  • an inorganic protective layer II having a thickness of 50 to 1,000 nm under the low refractive index layer (H).
  • FIG. 5 shows a cross-sectional view of one embodiment of a substrate with a partition wall of the present invention having a low refractive index layer and an inorganic protective layer II.
  • a patterned partition wall 2 and a layer 3 containing a color conversion light-emitting material are provided, and an inorganic protective layer II (6) and a low refractive index layer 4 are further provided in this order.
  • the substrate with a partition wall of the present invention is further provided with (J) a color filter having a thickness of 1 to 5 ⁇ m (hereinafter referred to as “color filter (J)”) between the substrate and the layer (G) containing the color conversion luminescent material. It may be preferred to have).
  • the color filter (J) has a function of transmitting visible light in a specific wavelength range to make the transmitted light have a desired hue. By having the color filter (J), the color purity can be improved. By setting the thickness of the color filter (J) to 1 ⁇ m or more, the color purity can be further improved. On the other hand, the brightness of the display device can be further improved by setting the thickness of the color filter (J) to 5 ⁇ m or less.
  • FIG. 6 shows a cross-sectional view of one embodiment of the substrate with a partition wall of the present invention having a color filter.
  • the substrate 1 has a patterned partition wall 2 and a color filter 7, and the color filter 7 has a layer 3 containing a color conversion luminescent material.
  • the color filter for example, a color filter using a pigment-dispersed material in which a pigment is dispersed in a photoresist used for a flat panel display such as a liquid crystal display can be used. More specifically, a blue color filter that selectively transmits wavelengths of 400 nm to 550 nm, a green color filter that selectively transmits wavelengths of 500 nm to 600 nm, a yellow color filter that selectively transmits wavelengths of 500 nm or more, Examples thereof include a red color filter that selectively transmits a wavelength of 600 nm or more.
  • the color filter may be laminated
  • the substrate with a partition wall of the present invention further comprises (I-3) an inorganic protective layer III having a thickness of 50 to 1,000 nm between the color filter (J) and the layer (G) containing a color conversion light emitting material. It is preferable to have.
  • an inorganic protective layer III By containing the inorganic protective layer III, it is difficult for the color filter (J) forming material to reach the layer (G) containing the color conversion luminescent material from the color filter (J). The luminance fluctuation of the layer (G) to be performed can be suppressed.
  • FIG. 7 shows a cross-sectional view of one embodiment of a substrate with a partition wall of the present invention having a color filter and an inorganic protective layer III.
  • a patterned partition wall 2 and a color filter 7 are provided, on which an inorganic protective layer III (8) is provided and separated by a partition wall 2 covered with the inorganic protective layer III (8).
  • a layer 3 containing the arranged and color-converting luminescent material is provided on the substrate 1, a patterned partition wall 2 and a color filter 7 are provided, on which an inorganic protective layer III (8) is provided and separated by a partition wall 2 covered with the inorganic protective layer III (8).
  • a layer 3 containing the arranged and color-converting luminescent material.
  • the substrate with a partition wall of the present invention preferably further comprises (I-4) an inorganic protective layer IV having a thickness of 50 to 1,000 nm on the substrate.
  • the inorganic protective layer IV acts as a refractive index adjusting layer, and can extract light emitted from the layer (G) containing the color conversion light-emitting material more efficiently and further improve the luminance of the display device. It is more preferable to have the inorganic protective layer IV between the substrate and the partition wall (F) and the layer (G) containing the color conversion luminescent material.
  • FIG. 8 shows a cross-sectional view of one embodiment of the substrate with a partition wall of the present invention having the inorganic protective layer IV.
  • the substrate 1 has the inorganic protective layer IV (9), the partition wall 2 and the color filter 7 patterned thereon, and the patterned partition wall 2 and the color conversion light-emitting material formed thereon.
  • Examples of materials constituting the inorganic protective layers I to IV include metal oxides such as silicon oxide, indium tin oxide, and gallium zinc oxide; metal nitrides such as silicon nitride; fluorides such as magnesium fluoride, and the like. . Two or more of these may be contained. Among these, one or more selected from silicon nitride and silicon oxide is more preferable because of low water vapor permeability and high permeability.
  • the thickness of the inorganic protective layers I to IV is preferably 50 nm or more, and more preferably 100 nm or more, from the viewpoint of sufficiently suppressing permeation of substances such as water vapor.
  • the thickness of the inorganic protective layers I to IV is preferably 800 nm or less, and more preferably 500 nm or less.
  • a polishing apparatus such as a cross section polisher to expose a cross section perpendicular to the substrate, and observe the cross section with a scanning electron microscope or a transmission electron microscope. Can be measured.
  • Examples of the method for forming the inorganic protective layers I to IV include a sputtering method.
  • the display apparatus of this invention has the said board
  • the light source is preferably a light source selected from a liquid crystal cell, an organic EL cell, a mini LED cell, and a micro LED cell.
  • An organic EL cell is more preferable because of its excellent emission characteristics.
  • the manufacturing method of the display device of the present invention will be described with reference to an example of the display device having the substrate with partition walls and the organic EL cell of the present invention.
  • a photosensitive polyimide resin is applied on a glass substrate, and an insulating film is formed by a photolithography method. After aluminum is sputtered as the back electrode layer, patterning is performed by photolithography to form a back electrode layer in the opening having no insulating film.
  • Alq3 tris (8-quinolinolato) aluminum
  • Alq3 tris (8-quinolinolato) aluminum
  • dicyanomethylenepyran, quinacridone, 4,4′-bis (2 , 2-diphenylvinyl) biphenyl is formed to form a white light emitting layer.
  • N, N′-diphenyl-N, N′-bis ( ⁇ -naphthyl) -1,1′-biphenyl-4,4′-diamine is deposited as a hole transport layer by vacuum deposition.
  • ITO is formed as a transparent electrode by sputtering to produce an organic EL cell having a white light emitting layer.
  • the organic EL cell obtained in this way was opposed to the above-mentioned substrate with a partition wall and bonded with a sealant to produce a display device.
  • the touch panel of the present invention has the above-mentioned substrate with a pattern of the present invention, a transparent electrode, a metal wiring, and a transparent film.
  • FIG. 10 shows an example of a cross section of the touch panel of the present invention.
  • the glass substrate 11 has the white light-shielding cured film 12 made of the cured film of the present invention and the transparent electrode 13, and the transparent electrode 13 has the transparent insulating film 14 and the metal wiring 15.
  • an ITO electrode or the like is preferable because it is difficult to be visually recognized.
  • Examples of the material constituting the metal wiring include materials having a low electric resistance value such as copper, MAM (molybdenum / aluminum / molybdenum laminated film), and silver.
  • a transparent insulating film that prevents conduction due to contact between metal wirings is preferable.
  • a negative photosensitive film containing an inorganic film such as silicon oxide or silicon nitride, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator. And a cured film of the transparent conductive resin composition.
  • Examples of the method for manufacturing a touch panel of the present invention include a method of forming a transparent electrode, a transparent insulating film, and a metal wiring on the above-described patterned substrate of the present invention.
  • a method of forming a transparent electrode, a transparent insulating film, and a metal wiring on the above-described patterned substrate of the present invention include a method of forming a transparent electrode, a transparent insulating film, and a metal wiring on the above-described patterned substrate of the present invention.
  • typical manufacturing methods will be described.
  • FIG. 11 shows an example of the touch panel manufacturing method of the present invention.
  • FIG. 11 a is a top view of the patterned processed substrate of the present invention having the white light-shielding cured film 12 on the glass substrate 1.
  • a transparent electrode 13 is formed on the glass substrate 11. Examples of a method for forming the transparent electrode 13 include a method in which ITO is formed by sputtering, a photoresist is formed, a pattern is formed by etching, and the photoresist is peeled off.
  • FIG. 11 b shows a top view after forming the transparent electrode. Next, the transparent insulating film 14 is formed at a predetermined position.
  • a manufacturing method of a transparent insulating film when the transparent insulating film is an inorganic film, for example, a CVD (Chemical Vapor Deposition) method is exemplified.
  • a CVD (Chemical Vapor Deposition) method is exemplified.
  • the transparent insulating film is a cured film of a negative photosensitive transparent resin composition, for example, a method using a lithography method may be mentioned.
  • FIG. 11c shows a top view after forming the transparent insulating film. Thereafter, the metal wiring 15 is formed.
  • FIG. 11d shows a top view after forming the metal wiring.
  • the solid content concentrations of the siloxane resin solutions in Synthesis Examples 1 to 9 and the acrylic resin in Synthesis Example 10 were determined by the following method. 1.5 g of siloxane resin solution or acrylic resin solution was weighed in an aluminum cup and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid. The weight of the solid content remaining in the heated aluminum cup was weighed, and the solid content concentration of the siloxane resin solution or the acrylic resin solution was determined from the ratio to the weight before the heating.
  • the weight average molecular weights of the siloxane resins in Synthesis Examples 1 to 9 and the acrylic resin in Synthesis Example 10 were determined by the following method. Using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation) and using tetrahydrofuran as a fluidized bed, GPC analysis was performed based on “JIS K7252-3 (established date: 2008/03/20)” The weight average molecular weight in terms of polystyrene was measured.
  • the content ratio of each repeating unit in the siloxane resins in Synthesis Examples 1 to 9 was determined by the following method.
  • a siloxane resin solution is injected into an “Teflon” (registered trademark) NMR sample tube having a diameter of 10 mm to perform 29 Si-NMR measurement, and Si derived from a specific organosilane with respect to the integrated value of the entire Si derived from organosilane.
  • the content ratio of each repeating unit was calculated from the ratio of the integrated value of.
  • the 29 Si-NMR measurement conditions are shown below.
  • Apparatus Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.) Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6669 MHz ( 29 Si nucleus) Spectrum width: 20000Hz Pulse width: 12 ⁇ s (45 ° pulse) Pulse repetition time: 30.0 seconds Solvent: Acetone-d6 Reference substance: Tetramethylsilane Measurement temperature: 23 ° C Sample rotation speed: 0.0 Hz.
  • the flask was immersed in a 70 ° C. oil bath and stirred for 90 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes.
  • the solution temperature (internal temperature) reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a siloxane resin solution.
  • a mixed gas of 95 volume% nitrogen and 5 volume% oxygen was flowed at 0.05 liter / minute.
  • a total of 131.35 g of methanol and water as by-products were distilled out.
  • siloxane resin (B-1) was added to the obtained siloxane resin solution so that the solid content concentration was 40% by weight to obtain a siloxane resin (B-1) solution.
  • the resulting siloxane resin (B-1) had a weight average molecular weight of 4,000 (polystyrene conversion).
  • siloxane resin (B-2) had a weight average molecular weight of 3,200 (in terms of polystyrene).
  • siloxane resin (B-3) had a weight average molecular weight of 3,500 (polystyrene conversion).
  • siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 130.05 g of methanol and water as by-products were distilled. PGMEA was added to the obtained siloxane resin solution so that the solid content concentration was 40% by weight to obtain a siloxane resin (B-4) solution.
  • the resulting siloxane resin (B-4) had a weight average molecular weight of 3,800 (polystyrene conversion).
  • the resulting siloxane resin (B-5) had a weight average molecular weight of 4,100 (in terms of polystyrene). From the 29 Si-NMR measurement results, trifluoropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3- ( The molar ratios of repeating units derived from 3,4-epoxycyclohexyl) propyltrimethoxysilane were 67.5 mol%, 17.5 mol%, 10 mol%, and 5 mol%, respectively.
  • siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 139.50 g of methanol and water as by-products were distilled out. PGMEA was added to the obtained siloxane resin solution so that the solid concentration was 40% by weight to obtain a siloxane resin (B-6) solution.
  • the resulting siloxane resin (B-6) had a weight average molecular weight of 5,000 (polystyrene conversion).
  • siloxane resin (B-7) had a weight average molecular weight of 3,900 (polystyrene conversion).
  • siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 136.90 g of methanol and water as by-products were distilled out. PGMEA was added to the obtained siloxane resin solution so that the solid concentration was 40% by weight to obtain a siloxane resin (B-8) solution.
  • the resulting siloxane resin (B-8) had a weight average molecular weight of 4,600 (polystyrene conversion).
  • the siloxane resin (B-8) was repeatedly derived from trifluoropropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride.
  • the molar ratio of the units was 85 mol%, 7.5 mol%, and 7.5 mol%, respectively.
  • siloxane resin solution was obtained in the same manner as in Synthesis Example 1. During the reaction, a total of 136.90 g of methanol and water as by-products were distilled out. PGMEA was added to the obtained siloxane resin solution so that the solid concentration was 40% by weight to obtain a siloxane resin (B-9) solution.
  • the resulting siloxane resin (B-9) had a weight average molecular weight of 2,800 (polystyrene conversion).
  • PGMEA was added to the obtained solution so that the solid content concentration was 20% by weight, and 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (tert-butyl) was added.
  • a silane coupling agent (G-1) which is a mixed solution of amino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid was obtained.
  • the obtained reaction product was purified by silica gel chromatography to obtain a white solid of 3,5-bis (4-tert-butylphenyl) benzaldehyde (3.5 g).
  • 3,5-bis (4-t-butylphenyl) benzaldehyde (1.5 g) and 2,4-dimethylpyrrole (0.7 g) were placed in a flask and dehydrated dichloromethane (200 mL) and trifluoroacetic acid (1 The mixture was stirred for 4 hours under a nitrogen atmosphere.
  • a dehydrated dichloromethane solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.85 g) was added, and the mixture was further stirred for 1 hour.
  • Synthesis Example 13 Silica Particle-Containing Polysiloxane Solution (LS-1) In a 500 ml three-necked flask, 0.05 g (0.4 mmol) of methyltrimethoxysilane, 0.66 g (3.0 mmol) of trifluoropropyltrimethoxysilane, and 0.10 g of trimethoxysilylpropyl succinic anhydride (0 .4 mmol), 7.97 g (34 mmol) of ⁇ -acryloxypropyltrimethoxysilane, and an isopropyl alcohol dispersion of 15.6 wt% silica particles (IPA-ST-UP: manufactured by Nissan Chemical Industries, Ltd.) 224 .37 g was mixed, and 163.93 g of ethylene glycol mono-t-butyl ether was added.
  • IPA-ST-UP manufactured by Nissan Chemical Industries, Ltd.
  • the resulting silica particle-containing polysiloxane solution (LS-1) had a solid content concentration of 24.3% by weight, and the contents of polysiloxane and silica particles in the solid content were 15% by weight and 85% by weight, respectively.
  • Polysiloxanes in the resulting silica particle-containing polysiloxane (LS-1) were converted to methyltrimethoxysilane, trifluoropropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, and ⁇ -acryloxypropyltrimethoxysilane.
  • the molar ratio of the derived repeating units was 1.0 mol%, 8.0 mol%, 1.0 mol%, and 90.0 mol%, respectively.
  • Negative photosensitive coloring composition P-1) 4.
  • A Titanium dioxide pigment (R-960; manufactured by BASF Japan Ltd.) 5.00 g as a white pigment, and
  • siloxane resin B-1) solution obtained in Synthesis Example 1 as a siloxane resin. Dispersion was carried out using a mill type disperser filled with zirconia beads mixed with 00 g to obtain a pigment dispersion (MW-1).
  • Negative photosensitive coloring compositions (P-2) to (P-4) A negative photosensitive coloring composition (P) was prepared in the same manner as in Preparation Example 1, except that the siloxane resins (B-2) to (B-4) were used instead of the siloxane resin (B-1) solution. -2) to (P-4) were obtained.
  • Negative photosensitive coloring composition (P-5) instead of 1.00 g of a 40 wt% PGMEA diluted solution of a photopolymerizable fluorine-containing compound (“Megafac” (registered trademark) RS-76-E), pentaerythritol acrylate (“light acrylate” (registered trademark) PE-3A)
  • the negative photosensitive coloring composition (P-5) was obtained in the same manner as in Preparation Example 1 except that 1.00 g of a 40 wt% PGMEA diluent was used.
  • Negative photosensitive coloring composition (P-6) Instead of 1.00 g of a 40 wt% PGMEA diluted solution of a photoreactive fluorine-containing compound (“Megafac” (registered trademark) RS-76-E (trade name) manufactured by DIC Corporation), 2,2,2- The same procedure as in Preparation Example 1, except that 1.00 g of a 40 wt% PGMEA diluted solution of trifluoroethyl acrylate (“Biscoat” (registered trademark) -3F (trade name), manufactured by Osaka Organic Chemical Co., Ltd.) was used. A negative photosensitive coloring composition (P-6) was obtained.
  • Negative photosensitive coloring composition (P-7) Negative-type photosensitivity was obtained in the same manner as in Preparation Example 1 except that a titanium dioxide pigment (CR-97; manufactured by Ishihara Sangyo Co., Ltd.) was used instead of the titanium dioxide pigment (R-960; manufactured by BASF Japan Ltd.). Sex coloring composition (P-7) was obtained.
  • Negative photosensitive coloring composition (P-8) Instead of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (“Irgacure” -127), “Irgacure” (registered trademark) -MBF (trade name), BASF Japan ( Except for using 0.100 g), a negative photosensitive coloring composition (P-8) was obtained in the same manner as in Preparation Example 1.
  • Negative photosensitive coloring compositions (P-9) to (P-13) A negative photosensitive coloring composition (P-) was prepared in the same manner as in Preparation Example 1, except that the siloxane resins (B-5) to (B-9) were used instead of the siloxane resin (B-1) solution. 9) to (P-13) were obtained.
  • Negative photosensitive coloring composition (P-14) A negative photosensitive coloring composition (P-14) was obtained in the same manner as in Preparation Example 1, except that the acrylic resin (b) solution was used instead of the resin (B-1) solution.
  • Negative photosensitive coloring composition (P-15) 8.00 g of pigment dispersion (MW-1), 1.615 g of the polysiloxane (B-1) solution obtained in Synthesis Example 1, and ethanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (“Irgacure” (registered trademark) OXE-02 (trade name) manufactured by BASF Japan Ltd.
  • DPH liquid repellent compound
  • a photopolymerizable fluorine-containing compound (“Megafac” (registered trademark) RS-76-E (trade name) manufactured by DIC Corporation (hereinafter “RS-76-E”) )
  • RS-76-E photopolymerizable fluorine-containing compound
  • PGMEA a photopolymerizable fluorine-containing compound
  • PGMEA a photopolymerizable fluorine-containing compound
  • IRGANOX1010 acrylic surfactant
  • BY (Registered trademark) 352 (trade name), manufactured by Big Chemie Japan Co., Ltd.
  • PGMEA 10 wt% diluted solution 0.100 g (corresponding to a concentration of 500 ppm) is dissolved in a mixed solvent of DAA 1.200 g and PGMEA 7.281 g, Stir. Next, the mixture was filtered through a 5.0 ⁇ m filter to obtain a negative photosensitive coloring composition (P-15).
  • Negative photosensitive coloring composition (P-16) A negative photosensitive coloring composition (P-16) was obtained in the same manner as in Preparation Example 15, except that the polysiloxane (B-5) solution was used instead of the polysiloxane (B-1) solution.
  • Negative photosensitive coloring composition (P-17) Negative type as in Preparation Example 15 except that the amount of RS-76-E 40 wt% PGMEA diluted solution was changed to 0.01 g and the amount of polysiloxane (B-1) solution was changed to 1.705 g. A photosensitive colored composition (P-17) was obtained.
  • Negative photosensitive coloring composition (P-18) Negative photosensitive coloring similar to Preparation Example 15 except that 0.100 g of 40 wt% PGMEA diluted solution of RS-76-E was not added and the amount of polysiloxane (B-1) solution was changed to 1.715 g. A composition (P-18) was obtained.
  • Negative photosensitive coloring composition (P-19) The amount of addition of pigment dispersion (MW-1) was changed to 4.00 g, the amount of addition of polysiloxane (B-1) solution was changed to 8.615 g, and a mixed solvent of 1.200 g DAA and 1.881 g PGMEA was used. In the same manner as in Preparation Example 15, a negative photosensitive coloring composition (P-19) was obtained.
  • Negative photosensitive coloring composition (P-20) The addition amount of the pigment dispersion (MW-1) was changed to 3.20 g, the addition amount of the polysiloxane (B-1) solution was changed to 10.15 g, and a mixed solvent of 1.200 g DAA and 3.681 g PGMEA was used. In the same manner as in Preparation Example 15, a negative photosensitive coloring composition (P-20) was obtained.
  • Negative photosensitive coloring composition (P-21) The addition amount of the pigment dispersion (MW-1) was changed to 1.60 g, the addition amount of the polysiloxane (B-1) solution was changed to 12.815 g, and a mixed solvent of 1.200 g DAA and 2.481 g PGMEA was used. In the same manner as in Preparation Example 15, a negative photosensitive coloring composition (P-21) was obtained.
  • compositions of Preparation Examples 1 to 21 are summarized in Table 3, Table 4, and Table 5.
  • Color Conversion Luminescent Material Composition 20 parts by weight of a 0.5 wt% toluene solution of a green quantum dot material (Lumidot 640 CdSe / ZnS, average particle size 6.3 nm: manufactured by Aldrich), 45 parts by weight of DPHA, “Irgacure” (registered trademark) 907 ( 5 parts by weight of BASF Japan Co., Ltd.), 166 parts by weight of 30% by weight PGMEA solution of acrylic resin (SPCR-18 (trade name), Showa Denko Co., Ltd.) and 97 parts by weight of toluene are mixed and stirred. And dissolved uniformly.
  • a green quantum dot material Limidot 640 CdSe / ZnS, average particle size 6.3 nm: manufactured by Aldrich
  • DPHA green quantum dot material
  • Irgacure registered trademark
  • a color conversion luminescent material composition (CL-1) was prepared by filtration through a 0.45 ⁇ m syringe filter.
  • Preparation Example 23 Color Conversion luminescent Material Composition (CL-2) In the same manner as in Preparation Example 22, except that 0.4 part by weight of the green phosphor G-1 obtained in Synthesis Example 12 was used instead of the green quantum dot material, and the amount of toluene added was changed to 117 parts by weight.
  • a converted luminescent material composition (CL-2) was prepared.
  • Color filter forming material C. I. 90 g of CI Pigment Green 59, C.I. I. 60 g of Pigment Yellow 150, 75 g of a polymeric dispersant (“BYK” (registered trademark) -6919 (trade name) manufactured by Big Chemie), and binder resin (“ADEKA ARKLES” (registered trademark) WR301 (trade name) (stock) ) 100 g of ADEKA) and 675 g of PGMEA were mixed to prepare a slurry.
  • a polymeric dispersant (“BYK” (registered trademark) -6919 (trade name) manufactured by Big Chemie)
  • binder resin (“ADEKA ARKLES” (registered trademark) WR301 (trade name) (stock)
  • the beaker containing the slurry was connected with a dyno mill and a tube, and zirconia beads having a diameter of 0.5 mm were used as media, and dispersion treatment was performed for 8 hours at a peripheral speed of 14 m / s. Was made.
  • Pigment Green 59 dispersion (GD-1) 56.54 g, acrylic resin ("Cyclomer” (registered trademark) P (ACA) Z250 (trade name) manufactured by Daicel Ornex Co., Ltd. (hereinafter "P (ACA) Z250”) )) 3.14 g, DPHA 2.64 g, photopolymerization initiator (“Optomer” (registered trademark) NCI-831 (trade name) manufactured by ADEKA Corporation (hereinafter “NCI-831”)) 0.330 g, 0.04 g of a surfactant (BYK "(registered trademark) -333 (trade name) manufactured by Big Chemie), 0.01 g of BHT as a polymerization inhibitor, and 37.30 g of PGMEA as a solvent were added, and a color filter forming material ( CF-1) was produced.
  • a surfactant BYK "(registered trademark) -333 (trade name) manufactured by Big Chemie
  • Preparation Example 25 Resin Composition for Light-shielding Partition Carbon Black (MA100 (trade name) manufactured by Mitsubishi Chemical Corporation) 150 g, 75 g of polymer dispersant BYK (registered trademark) -6919, 100 g of P (ACA) Z250, PGMEA A slurry was prepared by mixing 675 g. Connect the beaker containing the slurry with a dyno mill and a tube, and use a zirconia bead with a diameter of 0.5 mm as the media to perform a dispersion treatment for 8 hours at a peripheral speed of 14 m / s to prepare a pigment dispersion (MB-1). did.
  • MA100 Light-shielding Partition Carbon Black
  • 0.01 g of tertiary butyl catechol and 37.30 g of PGMEA were added to prepare a resin composition for a light shielding partition.
  • Preparation Example 26 Low Refractive Index Layer-Forming Material 5.350 g of the silica particle-containing polysiloxane solution (LS-1) obtained in Synthesis Example 13 was mixed with 1.170 g of ethylene glycol mono-t-butyl ether and 3.48 g of DAA. Then, it filtered with a 0.45 micrometer syringe filter, and prepared the low refractive index layer forming material.
  • the refractive index of the siloxane resin or acrylic resin used in each example and comparative example was determined by the following method.
  • the siloxane resin solution in Synthesis Examples 1 to 9 or the acrylic resin solution in Synthesis Example 10 was applied with a spinner and dried on a hot plate at 90 ° C. for 2 minutes. Thereafter, using an oven (IHPS-222; manufactured by Espec Corp.), the film was cured in air at 230 ° C. for 30 minutes to prepare a cured film.
  • a parallel light mask aligner (trade name: PLA-501F, manufactured by Canon Inc.) and an ultra-high pressure mercury lamp as a light source, lines of each width of 100 ⁇ m, 80 ⁇ m, 60 ⁇ m, 50 ⁇ m, 40 ⁇ m and 30 ⁇ m And it exposed with the gap of 100 micrometers with the exposure amount of 150 mJ / cm ⁇ 2 > (i line) through the mask which has a space pattern.
  • AD-2000 automatic developing device
  • shower development is performed for 100 seconds using a 0.045 wt% aqueous potassium hydroxide solution, and then water is used for 30 seconds. Rinse for 2 seconds.
  • the developed pattern was enlarged and observed, and the narrowest line width among the patterns in which no residue was observed in the unexposed area was defined as the resolution. However, if there is a residue even in an unexposed portion near the pattern having a width of 100 ⁇ m, “> 100 ⁇ m” was set.
  • ⁇ Visual reflectance> Using a spin coater (trade name 1H-360S, manufactured by Mikasa Co., Ltd.), the negative photosensitive coloring composition obtained in each Example and Comparative Example was cured on a 10 cm square alkali-free glass substrate. The film was spin-coated so as to have a film thickness of 10 ⁇ m, and prebaked at a temperature of 90 ° C. for 2 minutes using a hot plate (SCW-636) to form a prebaked film. The prepared pre-baked film was exposed, developed and rinsed in the same manner as in the above-described ⁇ Resolution> evaluation method except that no mask was interposed. Furthermore, using an oven (trade name: IHPS-222, manufactured by Espec Corp.), curing was performed in air at a temperature of 230 ° C. for 30 minutes to prepare a cured film.
  • an oven trade name: IHPS-222, manufactured by Espec Corp.
  • the reflection chromaticity of the cured film was measured from the glass substrate side using a spectrocolorimeter (trade name CM-2600d, manufactured by Konica Minolta Co., Ltd.), and the CIE Y value (Evaluation of luminous reflectance)
  • CM-2600d manufactured by Konica Minolta Co., Ltd.
  • CIE Y value Evaluation of luminous reflectance
  • the reflectance at a wavelength of 550 nm was measured in the SCI mode from the solid film side using a spectrocolorimeter (trade name CM-2600d, manufactured by Konica Minolta Co., Ltd.).
  • CM-2600d manufactured by Konica Minolta Co., Ltd.
  • the produced cured film was visually observed to evaluate the occurrence of cracks. When even one crack was confirmed, it was judged that there was no crack resistance at that film thickness. For example, when there was no crack at a film thickness of 15 ⁇ m and there was a crack at a film thickness of 20 ⁇ m, the crack-resistant film thickness was determined as “ ⁇ 15 ⁇ m”. Further, the crack-resistant film thickness when there is no crack even at 20 ⁇ m was determined as “ ⁇ 20 ⁇ m”, and the crack-resistant film thickness when there was a crack even when 5 ⁇ m was determined as “ ⁇ 5 ⁇ m”, respectively.
  • the cured film with no cracks was further subjected to additional curing in air at a temperature of 240 ° C. for 2 hours using an oven (IHPS-222), and the presence or absence of cracks was similarly evaluated. Later resistance to cracking.
  • ⁇ Heat resistance-2 color change> Using a spin coater (1H-360S; manufactured by Mikasa Co., Ltd.), the negative photosensitive coloring composition obtained in each Example and Comparative Example was applied to a 10 cm square non-alkali glass substrate after curing. The coating was applied so that the thickness was 10 ⁇ m, and a cured film was produced in the same manner as in the above-described evaluation method of ⁇ Heat resistance-1 Crack resistance>. However, when cracks occurred in the cured film, the remaining evaluation was not performed.
  • the reflection chromaticity of the cured film was measured from the glass substrate side using a spectrocolorimeter (trade name CM-2600d, manufactured by Konica Minolta Co., Ltd.), and CIE1976. (L *, a *, b *) The yellowness was evaluated based on the value of b * when displayed in the color space, and the color characteristics before additional curing were used. A C light source was used as the light source.
  • X1, X2, and X3 are as follows.
  • L * (0), a * (0), and b * (0) respectively indicate the values of L *, a *, and b * before additional curing
  • b * (1) indicate the values of L *, a *, and b * after additional curing, respectively.
  • ⁇ OD value> As a model of the partition wall of the substrate with a partition wall obtained in each example and comparative example, a solid film was formed on a glass substrate in the same manner as the above-described evaluation method of ⁇ reflectance>. About the glass substrate which has the obtained solid film, the intensity
  • strength of incident light and transmitted light was measured using the optical densitometer (361T (visual); X-rite company make), and optical density ( OD value) was calculated. OD value log 10 (I 0 / I) Expression (10) I 0 : Incident light intensity I: Transmitted light intensity.
  • ⁇ Surface contact angle> As a model of the partition wall of the substrate with a partition wall obtained in each example and comparative example, a solid film was formed on a glass substrate in the same manner as the above-described evaluation method of ⁇ reflectance>.
  • DM-700 manufactured by Kyowa Interface Science Co., Ltd.
  • the surface contact angle with respect to propylene glycol monomethyl ether acetate was measured in accordance with a wettability test method for the surface of a substrate glass specified in JIS R3257 (Established date: 1999/04/20).
  • PGMEA is used as an ink for the pixel portion surrounded by the grid-like barrier ribs.
  • Inkjet coating was performed using an inkjet coating apparatus (InkjetLab, manufactured by Cluster Technology Co., Ltd.). 160 pL of PGMEA was applied per grid pattern, and the presence or absence of breakage (a phenomenon in which ink crosses the partition wall and enters the adjacent pixel portion) was observed, and the inkjet coating property was evaluated according to the following criteria. The liquid repellency is so high that it does not break, indicating that the ink jet coating property is excellent.
  • the thickness of the structure before and behind formation of the layer (G) containing a color conversion luminescent material was measured using the surfcom stylus type film thickness measuring device, By calculating the difference, the thickness of the layer (G) containing the color conversion luminescent material was measured.
  • the thickness of the low refractive index layer (H) is further set.
  • the thickness of the color filter is set.
  • the thickness (height) of the light shielding partition is set. It measured similarly.
  • Example 21 to 22 and 24 to 25 a cross section perpendicular to the substrate was exposed using a polishing apparatus such as a cross section polisher, and the cross section was enlarged and observed with a scanning electron microscope or a transmission electron microscope. As a result, the thickness of each of the inorganic protective layers I to IV was measured.
  • a planar light emitting device equipped with a commercially available LED backlight (peak wavelength: 465 nm) as a light source
  • a substrate with a partition wall obtained by each Example and Comparative Example so that the layer containing the color conversion light emitting material is on the light source side It installed on the planar light-emitting device.
  • a current of 30 mA is passed through the planar light emitting device to turn on the LED element, and using a spectral radiance meter (CS-1000, manufactured by Konica Minolta), luminance (unit: cd / m 2 ) based on the CIE1931 standard is obtained. Measurement was made as the initial luminance.
  • CS-1000 spectral radiance meter
  • the luminance was measured in the same manner, and the change with time of the luminance was evaluated. However, the evaluation of the luminance was performed by a relative value with the initial luminance of Comparative Example 9 as 100.
  • Color standard BT That can reproduce almost natural colors.
  • the color gamut defined by 2020 is defined with the three primary colors red, green, and blue on the spectral locus shown in the chromaticity diagram, and the wavelengths of red, green, and blue correspond to 630 nm, 532 nm, and 467 nm, respectively.
  • R reflectance
  • the emission color of the layer containing the color conversion luminescent material was evaluated according to the following criteria.
  • B 0.55> R 530 / (R 630 + R 530 + R 470 ).
  • ⁇ Display characteristics> The display characteristics of the display device produced by combining the substrate with partition walls obtained in each Example and Comparative Example and the organic EL element were evaluated based on the following criteria.
  • Substrate 2 Partition wall 3: Layer containing color conversion light emitting material 4: Low refractive index layer 5: Inorganic protective layer I 6: Inorganic protective layer II 7: Color filter 8: Inorganic protective layer III 9: Inorganic protective layer IV 10: light shielding partition X: partition thickness L: partition width a: top view of patterned substrate of the present invention b: top view after forming transparent electrode c: top view after forming transparent insulating film d: metal wiring formation Rear view 11: Glass substrate 12: White light-blocking cured film 13: Transparent electrode 14: Transparent insulating film 15: Metal wiring

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Polymerisation Methods In General (AREA)
  • Optical Filters (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

L'invention concerne une composition colorante photosensible négative comprenant : (A) un pigment blanc, (B) une résine de siloxane, (C) un initiateur de photopolymérisation, (D) un composé photopolymérisable, et (E) un solvant organique, la (B) résine de siloxane comprenant au moins un motif récurrent exprimé par la formule générale (1) et/ou un motif récurrent exprimé par la formule générale (2) ainsi qu'un motif récurrent exprimé par la formule générale (3), et la somme du motif récurrent exprimé par la formule générale (1) et du motif récurrent exprimé par la formule générale (2) est de 40 à 80 % en moles par rapport à tous les motifs récurrents dans la (B) résine de siloxane. Dans les formules générales (1) à (3), R1 représente un groupe alkyle, un groupe alcényle, un groupe aryle ou un groupe arylalkyle ayant de 1 à 10 atomes de carbone et dans lequel l'hydrogène est partiellement ou entièrement substitué par du fluor ; R2 représente une liaison simple, -O-, -CH2-CO, -CO- ou –O-CO- ; R3 représente un groupe organique monovalent ayant de 1 à 20 atomes de carbone ; et les R4 peuvent être identiques ou différents, chacun représentant un groupe organique monovalent ayant de 1 à 20 atomes de carbone. L'utilisation de cette composition colorante photosensible négative permet de former un film durci qui présente une haute résolution, une réflectivité élevée et une résistance à la chaleur élevée même lorsque le film est épais.
PCT/JP2019/009397 2018-03-14 2019-03-08 Composition colorante photosensible négative, film durci et écran tactile l'utilisant WO2019176785A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020207021151A KR102617582B1 (ko) 2018-03-14 2019-03-08 네거티브형 감광성 착색 조성물, 경화막, 그것을 이용한 터치 패널
CN201980015528.7A CN111771163B (zh) 2018-03-14 2019-03-08 负型感光性着色组合物、固化膜、使用了它们的触摸面板
JP2019520658A JP7306264B2 (ja) 2018-03-14 2019-03-08 ネガ型感光性着色組成物、硬化膜、それを用いたタッチパネル

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2018046394 2018-03-14
JP2018-046394 2018-03-14
JP2018-113520 2018-06-14
JP2018113520 2018-06-14
JP2018-128004 2018-07-05
JP2018128004 2018-07-05

Publications (1)

Publication Number Publication Date
WO2019176785A1 true WO2019176785A1 (fr) 2019-09-19

Family

ID=67907094

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/009397 WO2019176785A1 (fr) 2018-03-14 2019-03-08 Composition colorante photosensible négative, film durci et écran tactile l'utilisant

Country Status (5)

Country Link
JP (1) JP7306264B2 (fr)
KR (1) KR102617582B1 (fr)
CN (1) CN111771163B (fr)
TW (1) TWI808137B (fr)
WO (1) WO2019176785A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021106684A1 (fr) * 2019-11-28 2021-06-03
CN113025306A (zh) * 2019-12-09 2021-06-25 上海航空电器有限公司 自带复合抛物面集光能力的荧光体及其制备方法
WO2021235541A1 (fr) * 2020-05-22 2021-11-25 セントラル硝子株式会社 Procédé de production d'éléments électroluminescents
KR20220030052A (ko) * 2020-09-02 2022-03-10 삼성전자주식회사 디스플레이 장치
WO2023048016A1 (fr) * 2021-09-24 2023-03-30 東レ株式会社 Composition de résine, film de protection contre la lumière et substrat doté d'une paroi de séparation

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20220122372A (ko) * 2021-02-26 2022-09-02 동우 화인켐 주식회사 격벽 형성용 감광성 수지 조성물, 이를 이용하여 제조된 격벽 구조물 및 상기 격벽 구조물을 포함하는 표시 장치
KR20230072570A (ko) * 2021-11-17 2023-05-25 삼성디스플레이 주식회사 감광성 수지 조성물, 이를 이용하여 제조된 표시 패널 및 이의 제조 방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007002194A (ja) * 2005-06-27 2007-01-11 Nippon Kayaku Co Ltd フッ素含有ポリシロキサン、それを用いる感光性樹脂組成物及びその硬化物
WO2014126013A1 (fr) * 2013-02-14 2014-08-21 東レ株式会社 Composition de coloration photosensible de type négatif, film durci, motif écran à la lumière pour panneau tactile, et procédé de fabrication de panneau tactile
WO2015012228A1 (fr) * 2013-07-25 2015-01-29 東レ株式会社 Composition blanche photosensible de type négatif pour panneau tactile, et panneau tactile ainsi que procédé de fabrication de celui-ci
WO2017057281A1 (fr) * 2015-09-30 2017-04-06 東レ株式会社 Composition de résine photosensible négative, film durci, élément et dispositif d'affichage ayant chacun un film durci et procédé de fabrication de dispositif d'affichage
WO2017159190A1 (fr) * 2016-03-14 2017-09-21 富士フイルム株式会社 Composition, film ainsi que procédé de fabrication de celui-ci, film durci, et capteur optique

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1942150B1 (fr) * 2005-10-28 2018-08-22 Toray Industries, Inc. Composition de resine de siloxane et son procede de production
JP5617476B2 (ja) * 2010-09-22 2014-11-05 Jsr株式会社 シロキサンポリマー組成物、硬化膜及び硬化膜の形成方法
KR20140007799A (ko) * 2010-10-29 2014-01-20 스미또모 가가꾸 가부시키가이샤 감광성 수지 조성물, 패턴 구조물, 표시 장치 및 격벽
CN103502888B (zh) * 2011-04-28 2016-05-25 旭硝子株式会社 负型感光性树脂组合物、固化膜、分隔壁和黑色矩阵及其制造方法、滤色器以及有机el元件
JP2012242928A (ja) 2011-05-17 2012-12-10 Toppan Printing Co Ltd 加飾透明保護基板一体型タッチパネル
JP2013050549A (ja) * 2011-08-30 2013-03-14 Asahi Glass Co Ltd ネガ型感光性樹脂組成物、隔壁、光学素子
JP6065497B2 (ja) * 2011-09-29 2017-01-25 Jsr株式会社 パターン形成方法及びポリシロキサン組成物
TWI577739B (zh) * 2015-05-25 2017-04-11 奇美實業股份有限公司 白色感光性樹脂組成物及其應用
JP6701324B2 (ja) * 2016-04-06 2020-05-27 富士フイルム株式会社 組成物、膜、硬化膜、光学センサおよび膜の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007002194A (ja) * 2005-06-27 2007-01-11 Nippon Kayaku Co Ltd フッ素含有ポリシロキサン、それを用いる感光性樹脂組成物及びその硬化物
WO2014126013A1 (fr) * 2013-02-14 2014-08-21 東レ株式会社 Composition de coloration photosensible de type négatif, film durci, motif écran à la lumière pour panneau tactile, et procédé de fabrication de panneau tactile
WO2015012228A1 (fr) * 2013-07-25 2015-01-29 東レ株式会社 Composition blanche photosensible de type négatif pour panneau tactile, et panneau tactile ainsi que procédé de fabrication de celui-ci
WO2017057281A1 (fr) * 2015-09-30 2017-04-06 東レ株式会社 Composition de résine photosensible négative, film durci, élément et dispositif d'affichage ayant chacun un film durci et procédé de fabrication de dispositif d'affichage
WO2017159190A1 (fr) * 2016-03-14 2017-09-21 富士フイルム株式会社 Composition, film ainsi que procédé de fabrication de celui-ci, film durci, et capteur optique

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021106684A1 (fr) * 2019-11-28 2021-06-03
WO2021106684A1 (fr) * 2019-11-28 2021-06-03 東京応化工業株式会社 Composition photosensible, et objet durci ainsi que procédé de fabrication de celui-ci
JP7313472B2 (ja) 2019-11-28 2023-07-24 東京応化工業株式会社 感光性組成物、硬化物、及び硬化物の製造方法
CN113025306A (zh) * 2019-12-09 2021-06-25 上海航空电器有限公司 自带复合抛物面集光能力的荧光体及其制备方法
CN113025306B (zh) * 2019-12-09 2023-07-21 上海航空电器有限公司 自带复合抛物面集光能力的荧光体及其制备方法
WO2021235541A1 (fr) * 2020-05-22 2021-11-25 セントラル硝子株式会社 Procédé de production d'éléments électroluminescents
KR20220030052A (ko) * 2020-09-02 2022-03-10 삼성전자주식회사 디스플레이 장치
WO2022050530A1 (fr) * 2020-09-02 2022-03-10 삼성전자주식회사 Appareil d'affichage comprenant une zone de faible luminosité
KR102541836B1 (ko) * 2020-09-02 2023-06-09 삼성전자주식회사 디스플레이 장치
WO2023048016A1 (fr) * 2021-09-24 2023-03-30 東レ株式会社 Composition de résine, film de protection contre la lumière et substrat doté d'une paroi de séparation

Also Published As

Publication number Publication date
TWI808137B (zh) 2023-07-11
JP7306264B2 (ja) 2023-07-11
CN111771163A (zh) 2020-10-13
KR102617582B1 (ko) 2023-12-27
JPWO2019176785A1 (ja) 2021-01-14
CN111771163B (zh) 2023-06-02
KR20200132843A (ko) 2020-11-25
TW201939164A (zh) 2019-10-01

Similar Documents

Publication Publication Date Title
JP7201062B2 (ja) 隔壁付き基板および表示装置
WO2019176785A1 (fr) Composition colorante photosensible négative, film durci et écran tactile l'utilisant
JP6295950B2 (ja) 感光性樹脂組成物、保護膜又は絶縁膜、タッチパネル及びその製造方法
CN106415393B (zh) 负型感光性树脂组合物、使其固化而成的固化膜及其制造方法、以及具有其的光学设备及背面照射型cmos图像传感器
JP2021161401A (ja) 樹脂組成物、遮光膜、遮光膜の製造方法および隔壁付き基板
JP2021005083A (ja) 黄色カラーフィルターおよび黄色カラーフィルター付き基板
JP7115635B2 (ja) 樹脂組成物、遮光膜、および隔壁付き基板
JP2021162860A (ja) ネガ型感光性着色組成物、硬化膜、硬化膜の製造方法、隔壁付き基板、および画像表示装置
JP2022150305A (ja) 樹脂組成物、紫外線吸収層および紫外線吸収層付き基板
WO2023048016A1 (fr) Composition de résine, film de protection contre la lumière et substrat doté d'une paroi de séparation
WO2023157713A1 (fr) Composition de résine, film de blocage de lumière, procédé de production de film de blocage de lumière, substrat sur lequel une paroi de séparation est fixée, et dispositif d'affichage
WO2022196261A1 (fr) Dispositif d'affichage électroluminescent organique
JP2023119574A (ja) 樹脂組成物、遮光膜、遮光膜の製造方法、隔壁付き基板および表示装置
JP2023031448A (ja) 隔壁付き基板、波長変換基板、波長変換基板の製造方法および表示装置

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2019520658

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19766901

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19766901

Country of ref document: EP

Kind code of ref document: A1