WO2023079622A1 - Inkjet ink for partition wall formation, inkjet ink set for partition wall formation, and led device manufacturing method - Google Patents

Inkjet ink for partition wall formation, inkjet ink set for partition wall formation, and led device manufacturing method Download PDF

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Publication number
WO2023079622A1
WO2023079622A1 PCT/JP2021/040575 JP2021040575W WO2023079622A1 WO 2023079622 A1 WO2023079622 A1 WO 2023079622A1 JP 2021040575 W JP2021040575 W JP 2021040575W WO 2023079622 A1 WO2023079622 A1 WO 2023079622A1
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meth
forming
partition
ink
white
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PCT/JP2021/040575
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French (fr)
Japanese (ja)
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貴宗 服部
香織 大野
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コニカミノルタ株式会社
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Priority to PCT/JP2021/040575 priority Critical patent/WO2023079622A1/en
Priority to TW111136468A priority patent/TW202328361A/en
Publication of WO2023079622A1 publication Critical patent/WO2023079622A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers

Definitions

  • the present invention relates to an inkjet ink for forming partitions, an inkjet ink set for forming partitions, and a method for manufacturing an LED device. More particularly, the present invention relates to an ink-jet ink for forming partition walls, which can form partition walls between LED chips with low damage, and the like, which does not reduce luminance.
  • Patent Document 1 discloses a technique for forming partitions with high light-shielding properties by photolithography.
  • partition walls having a high light-shielding property, the partition walls absorb the light from the LED chips, resulting in insufficient brightness.
  • Patent Document 2 discloses a technique of forming a partition wall having a reflective portion containing a white pigment.
  • the reflective portion improves the light extraction efficiency and solves the problem of insufficient brightness.
  • the present invention has been made in view of the above problems and circumstances, and the problem to be solved is an ink-jet ink for forming partitions, which is capable of forming partitions between LED chips with little damage that does not reduce luminance, and an inkjet ink for forming partitions.
  • An object of the present invention is to provide an ink set and a method for manufacturing an LED device using the ink set.
  • the present inventors have investigated the causes of the above problems, and found that the content of a solvent having a normal boiling point of 250 ° C. or less in a photopolymerizable composition and a white colorant is , 25% or less, it is possible to provide an inkjet ink for forming partitions that can form partitions between LED chips with low damage that does not reduce luminance. That is, the above problems related to the present invention are solved by the following means.
  • An inkjet ink for forming partitions for forming partitions between LED chips of an LED device, Containing a photopolymerizable composition and a white colorant
  • An inkjet ink for forming partition walls wherein the content of a solvent having a normal boiling point of 250° C. or less is 25% or less.
  • An inkjet ink set for forming partitions for forming partitions between LED chips of an LED device having a first partition-forming inkjet ink and a second partition-forming inkjet ink
  • the first inkjet ink for forming partition walls contains a photopolymerizable composition and a white colorant, and the content of a solvent having a normal boiling point of 250° C. or less is 25% or less
  • the second inkjet ink for forming partition walls contains a photopolymerizable composition and a black colorant, and the content of a solvent having a normal boiling point of 250° C. or less is 25% or less.
  • a method of manufacturing an LED device having partitions between LED chips comprising: A partition forming step of patterning the partition by an inkjet method, The partition forming step has at least a white partition forming step, In the step of forming white barrier ribs, an inkjet ink for forming barrier ribs containing a photopolymerizable composition and a white colorant and having a normal boiling point of 250° C. or less and a solvent content of 25% or less is used.
  • a method for manufacturing an LED device characterized by:
  • the partition wall forming step includes at least the white partition wall forming step and a black partition wall forming step of forming a black partition wall on the white partition wall formed in the white partition wall forming step, In the step of forming black partition walls, a partition-forming inkjet ink containing a photopolymerizable composition and a black colorant and containing 25% or less of a solvent having a normal boiling point of 250° C. or lower is used. 5.
  • an ink-jet ink for forming a partition wall By the means of the present invention, an ink-jet ink for forming a partition wall, an inkjet ink set for forming a partition wall, and a method for manufacturing an LED device using the same, which can form a partition wall between LED chips with low damage without lowering luminance are provided. can do.
  • the inkjet ink for forming partition walls of the present invention can form white partition walls or gray partition walls that do not reduce luminance by containing a white colorant.
  • the barrier ribs since it is an inkjet ink, it is possible to form the barrier ribs in a non-contact manner with respect to the LED device by an inkjet method by using the ink. In particular, since it is not necessary to use a developing solution unlike the photolithography method, damage to the LED device can be suppressed.
  • the inkjet ink for forming partition walls of the present invention contains 25% or less of a solvent having a normal boiling point (boiling point under 1 atm) of 250° C. or less, the solvent may damage the LED device. can be suppressed.
  • the ink-jet ink for forming partitions of the present invention can form partitions between LED chips with low damage that do not reduce the brightness due to these expression mechanisms or action mechanisms.
  • FIG. 1A is a schematic cross-sectional view of a part of an LED device for illustrating the appearance of partition walls formed by the ink of the present invention.
  • FIG. 2A is a schematic cross-sectional view of a part of an LED device for illustrating the appearance of partition walls formed by the ink of the present invention.
  • FIG. 3A is a schematic cross-sectional view of a part of an LED device for illustrating the appearance of partition walls formed by the ink of the present invention.
  • Schematic cross-sectional view 3B of a part of the LED device for illustrating the state of the partition formed by the ink of the present invention Schematic diagram showing an LED device without partitions
  • the inkjet ink for forming partition walls of the present invention is an inkjet ink for forming partition walls between LED chips of an LED device, which contains a photopolymerizable composition and a white colorant, and has a normal boiling point of The content of the solvent having a temperature of 250° C. or less is 25% or less.
  • This feature is a technical feature common to or corresponding to the following embodiments.
  • the ink-jet ink for forming partition walls of the present invention it is preferable to contain a (meth)acrylate compound as a component of the photopolymerizable composition from the viewpoint of the polymerization rate and degree of polymerization.
  • the partition-forming inkjet ink set of the present invention is an inkjet ink set for forming partitions between LED chips of an LED device, and comprises a first partition-forming inkjet ink and a second partition-forming inkjet ink.
  • an inkjet ink wherein the first inkjet ink for partition wall formation contains a photopolymerizable composition and a white colorant, and the content of a solvent having a normal boiling point of 250° C. or less is 25 % or less, and the second inkjet ink for forming partition walls contains a photopolymerizable composition and a black colorant, and the content of the solvent having a normal boiling point of 250° C. or less is 25% or less. It is characterized by
  • a method for manufacturing an LED device is a method for manufacturing an LED device having partitions between LED chips, comprising a partition formation step of patterning the partitions by an inkjet method, wherein the partition formation step includes at least: It has a white partition wall forming step, and in the white partition wall forming step, the content of a solvent containing a photopolymerizable composition and a white colorant and having a normal boiling point of 250 ° C. or lower is 25% or less. It is characterized by using a certain ink-jet ink for partition formation.
  • the partition forming step includes at least the white partition forming step and the black partition forming in which the black partition is formed on the white partition formed in the white partition forming step. and in the step of forming black partition walls, partition walls containing a photopolymerizable composition and a black colorant and having a normal boiling point of 250° C. or lower in a solvent content of 25% or less.
  • Forming inkjet inks are preferably used.
  • barrier ribs whose upper surface that contributes to an improvement in contrast is black and whose side surface that contributes to an improvement in luminance is partially white.
  • the partition-forming inkjet ink of the present invention (hereinafter also simply referred to as "ink”) is an inkjet ink for partition-forming for forming partitions between LED chips of an LED device, comprising a photopolymerizable composition,
  • the content of the white colorant and the solvent having a normal boiling point of 250° C. or less is 25% or less.
  • the ink of the present invention is a partition-forming inkjet ink for forming partitions between LED chips of an LED device.
  • the “partition wall” is formed between LED chips to prevent color mixing between adjacent pixels or between adjacent LED chips in an LED device, and is 25% or more of the height of the LED chip.
  • FIGS. 1A, B and 2A, B are schematic cross-sectional views of a part of an LED device for illustrating partition walls formed by the ink of the present invention.
  • the partition walls 4 (white partition walls 4) are arranged as shown in FIGS. It may be formed so as to cover the periphery of the LED chip, or as shown in FIGS. 1A, B and 2A, B also show a transparent encapsulant 5 and a cover glass 6 for encapsulating the LED chip.
  • the height of the partition wall with respect to the height of the LED chip is required to be 25% or more, but in order to further prevent color mixture, it is preferably 50% or more, more preferably 75% or more. Moreover, if the barrier ribs are too high, the luminance is lowered, so the height of the barrier ribs relative to the height of the LED chips is preferably 200% or less.
  • FIGS. 1A,B and 2A,B show an LED device formed with a partition having a height relative to the height of the LED chip of about 150%
  • FIGS. Figure 3 shows an LED device formed with a barrier rib having a thickness of about 50%.
  • FIG. 4 shows an LED device without partitions
  • FIGS. 5-7 show LED devices with partitions formed in different patterns.
  • 4 to 7 are all schematic diagrams of a part of the LED device viewed from above, and four pixels are shown, with a set consisting of a red LED chip 3R, a green LED chip 3G, and a blue LED chip 3B as one pixel. area.
  • each LED It shows a pattern in which a partition wall 4 is formed so as to cover the periphery of the chip.
  • FIG. 6 corresponds to a state in which FIGS. 2A and 2B are viewed from above (the transparent sealant 5 and the cover glass 6 are not shown), and partition walls are formed so as to cover the pixels composed of LED chips of three colors. 4 shows the pattern in which 4 is formed.
  • partition walls 4 are formed so as to cover the periphery of each LED chip as in FIG. It shows a pattern that
  • 1 to 7 illustrate embodiments, and do not limit the pattern of partition walls formed by the ink of the present invention or the arrangement of LED chips in an LED device using the ink of the present invention. .
  • the cross-sectional shape of the partition wall in the width direction may be a shape in which the widths of the lower part and the upper part are substantially constant, or may be a tapered shape with a wide lower part or a reverse tapered shape with a wide upper part. There may be.
  • the width of the partition is not particularly limited.
  • the color of the barrier ribs formed using the ink of the present invention is white or gray, but by further using an ink other than the present invention, the barrier ribs are formed by stacking barrier ribs of two or more different colors.
  • the partition walls 4 are made up of a white partition wall 4Wh and a black partition wall 4Bl located thereon, so that the upper surface that contributes to the improvement of the contrast is made black.
  • the side surfaces that contribute to the improvement of luminance can be partially made white, luminance and contrast can be improved at the same time.
  • the above dimensions such as height and width indicate the dimensions of the partition as a whole.
  • white refers to a color with a brightness of 8.0 or more and a saturation of 2.0 or less in the Munsell color system (JIS Z 8721).
  • black refers to a color having a brightness of 2.0 or less and a saturation of 2.0 or less in the Munsell color system (JIS Z 8721).
  • Gram refers to a mixture of white and black.
  • the ink of the present invention is an ink used to form the partition walls as described above.
  • the ink of the present invention contains a photopolymerizable composition and a white colorant, and is characterized by containing 25% or less of a solvent having a normal boiling point of 250° C. or less. Details of the components are described below.
  • the photopolymerizable composition according to the present invention preferably contains at least a polymerizable compound as a component and, if necessary, a photopolymerization initiator.
  • the content of the polymerizable compound is preferably within the range of 1 to 97% by mass, more preferably within the range of 30 to 90% by mass, based on the total ink.
  • the polymerizable compound is not particularly limited, and in the presence or absence of a photopolymerization initiator, the polymerization reaction is initiated by irradiation with active energy rays (electron beams, ultraviolet rays, ⁇ rays, ⁇ rays, X rays, etc.). , a compound that cures by polymerization and cross-linking can be used.
  • the polymerizable compound may be any of monomers, polymerizable oligomers, prepolymers and mixtures thereof.
  • Examples of the polymerizable compound include cationically polymerizable compounds, radically polymerizable compounds, and mixtures thereof. From the viewpoint of polymerization rate and degree of polymerization, radically polymerizable compounds are preferred, and (meth)acrylates are preferred. Compounds are more preferred.
  • Radar polymerizable compound refers to a compound having an ethylenically unsaturated double bond in the molecule.
  • the radically polymerizable compound may be either monofunctional or polyfunctional.
  • Examples of radically polymerizable compounds include (meth)acrylate compounds, which are unsaturated carboxylic acid ester compounds.
  • (meth)acrylate refers to acrylate or methacrylate.
  • the "(meth)acrylate compound” includes a compound containing a (meth)acryloyl group in the main chain, a compound having a (meth)acryloyl group as a side chain, and a compound having a (meth)acryloyl group as a side chain. Included are compounds containing as substituents having
  • Examples of (meth)acrylate compounds without acidic groups include isoamyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isomyrstyl (meth)acrylate , isostearyl (meth)acrylate, 2-ethylhexyl-diglycol (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene monofunctional acrylates, including glycol (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, and t-butylcyclohex
  • Examples of (meth)acrylate compounds having a carboxy group include (meth)acrylate compounds having a hydroxy group and (meth)acrylates obtained by adding an acid anhydride to an oligomer composed of these.
  • the acid anhydride include phthalic anhydride, isophthalic anhydride, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, hymic anhydride, maleic anhydride, and trimellit anhydride. acids, methylcyclohexene tricarboxylic anhydride, and pyromellitic anhydride.
  • (meth)acrylate compounds having a carboxy group include 2-carboxyethyl acrylate, 4-(meth)acryloyloxyethoxycarbonylphthalic acid, 4-(meth)acryloyloxybutoxycarbonylphthalic acid, 4-( meth) acryloyloxyhexyloxycarbonyl phthalic acid, 4-(meth) acryloyloxydecyloxycarbonyl phthalic acid and other (meth) acryloyloxyalkoxycarbonyl phthalates, 4-(meth) acryloyloxyethoxyethoxycarbonyl phthalic acid and other (meth) ) acryloyloxyalkoxyalkoxycarbonyl phthalic acids, mono-2-(acryloyloxy)ethyl succinate, 2,2-bis(acryloylamido)acetic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acrylic royloxyethyl
  • (Meth)acrylate compounds having a phosphoric acid group include, for example, bis(2-(meth)acryloyloxyethyl) phosphate, 2-hydroxyethyl (meth)acrylate acid phosphate, ethyl (meth)acrylate acid phosphate, 3 -chloro-2-acid phosphooxypropyl (meth)acrylate, polyoxyethylene glycol (meth)acrylate acid phosphate, 2-(meth)acryloyloxyethyl caproate acid phosphate, mono-2-(methacryloyloxy)ethyl phosphate is mentioned.
  • 2-(meth)acryloyloxyethyl phosphate meaning 2-acryloyloxyethyl phosphate or 2-methacryloyloxyethyl phosphate, hereinafter according to this abbreviation
  • 2-(meth)acryloyloxypropyl Phosphate 3-(meth)acryloyloxypropyl phosphate
  • 4-(meth)acryloyloxybutyl phosphate 6-(meth)acryloyloxyhexyl phosphate
  • 8-(meth)acryloyloxyoctyl phosphate ester 10-(meth)acryloyloxydecyl phosphate, 12-(meth)acryloyloxylauryl phosphate, 16-(meth)acryloyloxycetyl phosphate, 18-(meth)acryloyloxystearyl phosphate
  • (meth)acryloyloxy alkyl phosphates such as 20-(meth)acryloyloxyprop
  • Examples of (meth)acrylate compounds having a sulfonic acid group include methallylsulfonic acid, bis(3-sulfopropyl)itaconic acid, 2-(sulfoxy)ethyl methacrylic acid, 2-acrylamido-2-methyl-1- Propanesulfonic acid, 3-sulfopropylacrylic acid, 3-sulfopropylmethacrylic acid, acrylamido-2-methyl-2-propanesulfonic acid and the like.
  • Examples of (meth)acrylate compounds having a monofunctional hydroxy group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 1-methyl-2-hydroxyethyl (meth)acrylate. , 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate , 4-hydroxymethylcyclohexylmethyl (meth)acrylate, p-hydroxymethylphenylmethyl (meth)acrylate, 2-(hydroxyethoxy)ethyl (meth)acrylate, 2-(hydroxyethoxyethoxy) (meth)acrylate Ethyl, 2-(hydroxyethoxyethoxyethoxy)ethyl (meth)acrylate, methyl ⁇ -hydroxymethyl acrylate, ethyl ⁇ -hydroxymethyl acrylate, hydroxyalkyl
  • Examples of the (meth)acrylate compound having a polyfunctional hydroxy group include 2-hydroxy-3-acryloyloxypropyl methacrylate, dipentaerythritol penta(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, tri Methylolpropane diacrylate, glycerin di(meth)acrylate, glycerin acrylate methacrylate, pentaerythritol di(meth)acrylate, neopentylglycol hydroxypivalate di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol propionate Tri(meth)acrylate, hydroxypivalaldehyde-modified dimethylolpropane tri(meth)acrylate, sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate
  • (Meth)acrylate may be a modified product.
  • modified (meth)acrylates include ethylene oxide-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetraacrylate, ethylene oxide-modified (meth)acrylates, caprolactone-modified trimethylolpropane tri( Caprolactone-modified (meth)acrylates including meth)acrylates and caprolactam-modified (meth)acrylates including caprolactam-modified dipentaerythritol hexa(meth)acrylates and the like are included.
  • the (meth)acrylate may be a polymerizable oligomer.
  • (meth)acrylates that are polymerizable oligomers include epoxy (meth)acrylate oligomers, aliphatic urethane (meth)acrylate oligomers, aromatic urethane (meth)acrylate oligomers, polyester (meth)acrylate oligomers, and linear ( meth)acrylic oligomers and the like are included.
  • a “cationically polymerizable compound” refers to a compound having a cationically polymerizable group in its molecule.
  • Examples of cationic polymerizable compounds include epoxy compounds, vinyl ether compounds and oxetane compounds.
  • epoxy compounds include alicyclic epoxy compounds (3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene monoepoxide, ⁇ -caprolactone-modified 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, 1-methyl-4-(2-methyloxiranyl)-7-oxabicyclo[4,1,0]heptane, 2 -(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexanone-meta-dioxane, and bis(2,3-epoxycyclopentyl) ether), aliphatic epoxy compounds (1,4- diglycidyl ether of butanediol, diglycidyl ether of 1,6-hex
  • vinyl ether compounds include ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether.
  • dodecyl vinyl ether diethylene glycol monovinyl ether, octadecyl vinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether vinyl ether, cyclohexanedimethanol divinyl ether, trimethylolpropane trivinyl ether, and the like.
  • oxetane compounds include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3-hydroxymethyl-3-n-butyloxetane, 3- Hydroxymethyl-3-phenyloxetane, 3-hydroxymethyl-3-benzyloxetane, 3-hydroxyethyl-3-methyloxetane, 3-hydroxyethyl-3-ethyloxetane, 3-hydroxyethyl-3-propyloxetane, 3- Hydroxyethyl-3-phenyloxetane, 3-hydroxypropyl-3-methyloxetane, 3-hydroxypropyl-3-ethyloxetane, 3-hydroxypropyl-3-propyloxetane, 3-hydroxypropyl-3-phenyloxetane, 3- Hydroxybutyl-3-methyloxetane, 1,4 bis ⁇ [(3-ethyl-3-oxetany
  • the photopolymerizable composition according to the present invention preferably contains a photopolymerization initiator as necessary.
  • the content of the photopolymerization initiator can be arbitrarily set within a range in which the ink is sufficiently cured by the irradiation of the active energy ray and the inkjet ejection stability of the ink is not lowered.
  • the content of the photopolymerization initiator is preferably within the range of 0.1 to 20% by mass, more preferably within the range of 1.0 to 12% by mass, relative to the total ink.
  • any photopolymerization initiator may be used as long as it can initiate the polymerization of the polymerizable compound.
  • the photopolymerization initiator is a radical photopolymerization initiator
  • the photopolymerization initiator is a cationic photopolymerization initiator.
  • photopolymerization initiator Only one type of photopolymerization initiator may be used alone, or two or more types may be used in combination. Also, both the radical photopolymerization initiator and the cationic photopolymerization initiator may be combined.
  • Radical photopolymerization initiators include an intramolecular bond cleavage type and an intramolecular hydrogen abstraction type.
  • Examples of the intramolecular bond cleavage type radical photopolymerization initiator include acetophenone photopolymerization initiators (diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1 -(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino(4-methylthiophenyl)propan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, etc.), benzoin-based photopolymerization initiators (benzoin , benzoin methyl ether, and benzoin isopropyl ether), acylphosphine oxide photopolymerization initiators (2,4,6-trimethylbenzoy
  • acylphosphine oxide-based photopolymerization initiators are preferable from the viewpoint of further improving the curability of the polymerizable compound, and particularly from the viewpoint of further improving the curability of the curing process by UV-LED light.
  • acylphosphine oxide photopolymerization initiators include, for example, IRGACURE (registered trademark) 819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), IRGACURE (registered trademark) 1800 (bis -(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 1-hydroxy-cyclohexyl-phenylketone in a mass ratio of 25:75), IRGACURE® TPO (2, 4,6-trimethylbenzoyldiphenylphosphine oxide) and the like.
  • IRGACURE registered trademark 819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide)
  • IRGACURE (registered trademark) 1800 bis -(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 1-hydroxy-cyclohexyl-phenylketone in
  • intramolecular hydrogen abstraction type radical photopolymerization initiators examples include benzophenone photopolymerization initiators (benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4 -benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone, etc.), Thioxanthone photoinitiators (2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, etc.), aminobenzophenone photoinitiators (Michler ketone, 4,4'- diethylaminobenzoph
  • Examples of cationic photopolymerization initiators include photoacid generators.
  • Further examples of photoacid generators include aromatic onium compounds B(C 6 F 5 ) 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ including diazonium, ammonium, iodonium, sulfonium, and phosphonium. , CF 3 SO 3 -salts , sulfonates that generate sulfonic acids, halides that photogenerate hydrogen halides, and iron allene complexes.
  • the ink of the present invention is characterized by containing a white colorant.
  • the white colorant may be a pigment or a dye.
  • the white content is not particularly limited, but is preferably in the range of 2 to 30% by mass, more preferably in the range of 5 to 20% by mass, and more preferably in the range of 6 to 15% by mass. It is more preferable to be within the mass % range.
  • the white pigment suitably used as the white colorant contained in the ink of the present invention will be specifically described below.
  • white pigments include calcium carbonate, barium sulfate, titanium oxide, zinc oxide, zinc sulfide, antimony oxide, zirconium oxide, white hollow resin particles, and polymer particles.
  • titanium oxide and zirconium oxide are preferred, and titanium oxide is more preferred.
  • Examples of commercially available titanium oxide that can be used in the present invention include CR-EL, CR-50, CR-80, CR-90, R-780, and R-930 (all manufactured by Ishihara Sangyo Co., Ltd.), TCR-52, R-25, R-32, R-310 (all manufactured by Sakai Chemical Industry Co., Ltd.), KR-310, KR-380 and KR-380N (all manufactured by Titan Kogyo Co., Ltd.) and the like are included.
  • zirconium oxide examples include commercially available Zirconeo (manufactured by Aitec, "Zirconeo" is a registered trademark of the company).
  • Dispersion of pigments can be carried out by, for example, ball mills, sand mills, attritors, roll mills, agitators, Henschel mixers, colloid mills, ultrasonic homogenizers, pearl mills, wet jet mills, and paint shakers.
  • the average dispersed particle diameter of the pigment particles is in the range of 50 to 150 nm, and the maximum particle diameter is in the range of 300 to 1000 nm, from the viewpoint of further improving the ejection property from the inkjet head. preferably within A more preferable average dispersed particle size is in the range of 80 to 130 nm.
  • the average dispersed particle size of pigment particles in the present invention means a value obtained by a dynamic light scattering method using Datasizer Nano ZSP, manufactured by Malvern.
  • the ink containing the coloring material has a high density and does not transmit light in this measurement device, so the measurement is performed after diluting the ink by 200 times.
  • the measurement temperature is normal temperature (25°C).
  • the dispersion of the pigment is adjusted by the pigment, dispersant, dispersion medium, dispersion conditions, filtration conditions, and the like.
  • the ink of the present invention may further contain a dispersant in order to improve the dispersibility of the pigment.
  • dispersants include carboxylic acid esters having hydroxy groups, salts of long-chain polyaminoamides and high-molecular-weight acid esters, salts of high-molecular-weight polycarboxylic acids, salts of long-chain polyaminoamides and polar acid esters, high-molecular-weight unsaturated acid esters, polymer copolymers, modified polyurethanes, modified polyacrylates, polyether ester type anionic surfactants, naphthalene sulfonic acid formalin condensate salts, aromatic sulfonic acid formalin condensate salts, polyoxyethylene alkyl phosphate esters, Polyoxyethylene nonylphenyl ether, stearylamine acetate, and the like are included.
  • examples of commercially available dispersants include Solsperse series from Avecia, PB
  • the ink of the present invention may contain a dispersing aid as necessary when using a pigment as a coloring material.
  • a dispersing aid may be selected according to the pigment.
  • the total amount of the dispersant and dispersing aid is preferably within the range of 1 to 50% by mass based on the pigment.
  • the ink of the present invention may contain a dispersion medium for dispersing the pigment, if necessary.
  • a solvent may be used as the dispersing medium, but in order to suppress damage to the LED chip, it is preferable to use a polymerizable compound (especially a monomer having a low viscosity) as the dispersing medium.
  • the ink of the present invention may further contain a colorant other than the white colorant as long as the effects of the present invention can be obtained.
  • Pigments suitably used as colorants other than the white colorant will be specifically described below.
  • black pigments examples include pigments selected from Pigment Black 7, 28, 26, or mixtures thereof.
  • black pigments examples include Black Pigment (manufactured by Mikuni), Chromo Fine Black A-1103 (manufactured by Dainichi Seika Kogyo Co., Ltd.), Colortex Black 702, U905 (manufactured by Sanyo Color Co., Ltd.), carbon black #2600, #2400, #2350, #2200, #1000, #990, #980, #970, #960, #950, #850, MCF88, #750, #650, MA600, MA7, MA8, MA11, MA100, MA100R, MA77, #52, #50, #47, #45, #45L, #40, #33, #32, #30, #25, #20, #10, #5, #44, and CF9 (Mitsubishi chemical company) and the like.
  • Black Pigment manufactured by Mikuni
  • Chromo Fine Black A-1103 manufactured by Dainichi Seika Kogyo Co., Ltd.
  • Colortex Black 702, U905 manufactured by Sanyo Color Co.
  • red or magenta pigments examples include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53 : 1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144 , 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Pigments selected from Orange 13, 16, 20, and 36, or mixtures thereof, etc. are included.
  • blue or cyan pigments examples include Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36 , and 60, or mixtures thereof, and the like.
  • green pigments examples include pigments selected from Pigment Green 7, 26, 36, and 50, or mixtures thereof.
  • yellow pigments examples include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137 , 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, and 193, or mixtures thereof, and the like.
  • Examples of commercially available pigments include, in addition to those listed above, Chromofine Yellow 2080, 5900, 5930, AF-1300, 2700L, Chromofine Orange 3700L, 6730, Chromofine Scarlet 6750, Chromofine Magenta 6880, 6886 , 6891N, 6790, 6887, Chromofine Violet RE, Chromofine Red 6820, 6830, Chromofine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, 5000P, Chromo Fine Green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400 (B), 2500, 2600, ZAY-260, 2700
  • the ink of the present invention is characterized in that the content of a solvent having a normal boiling point (boiling point under 1 atm) of 250° C. or less is 25% or less. As a result, damage to the LED chip can be suppressed, and environmental load can be reduced.
  • the content of the solvent having a normal boiling point of 250° C. or less is more preferably 10% or less, more preferably 1% or less.
  • solvents having a normal boiling point of 250° C. or lower include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol; cellosolve solvents such as methoxy alcohol and ethoxy alcohol; Carbitol solvents such as ethanol and ethoxyethoxyethanol; Ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate; Ketone solvents such as acetone, methyl isobutyl ketone, and cyclohexanone.
  • alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol
  • cellosolve solvents such as methoxy alcohol and ethoxy alcohol
  • Carbitol solvents such as ethanol and ethoxyethoxyethanol
  • Ester solvents such as e
  • cellosolve acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate
  • carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butyl carbitol acetate (BCA)
  • ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, and tetrahydrofuran
  • N Aprotic amide solvents such as , N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone
  • Lactone solvents such
  • the ink of the present invention may further contain other components including a polymerization inhibitor and a surfactant as long as the effects of the present invention can be obtained.
  • the ink of the present invention may contain only one type of these components, or two or more types thereof.
  • polymerization inhibitors examples include (alkyl)phenol, hydroquinone, catechol, resorcinol, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone.
  • nitrosobenzene 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cupferron, aluminum N-nitrosophenylhydroxyamine, tri-p-nitrophenylmethyl, N-(3-oxyanilino- 1,3-dimethylbutylidene)aniline oxide, dibutyl cresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime and cyclohexanone oxime.
  • polymerization inhibitors examples include Irgastab UV10 (manufactured by BASF) and Genorad 18 (manufactured by Rahn AG).
  • the amount of the polymerization inhibitor can be arbitrarily set within the range where the effects of the present invention can be obtained.
  • the amount of the polymerization inhibitor can be, for example, 0.001% by mass or more and less than 1.0% by mass with respect to the entire ink.
  • surfactants include anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates and fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols and polyoxy Nonionic surfactants such as ethylene/polyoxypropylene block copolymers, cationic surfactants such as alkylamine salts and quaternary ammonium salts, and silicone-based and fluorine-based surfactants are included.
  • anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates and fatty acid salts
  • polyoxyethylene alkyl ethers polyoxyethylene alkyl allyl ethers
  • acetylene glycols acetylene glycols
  • Nonionic surfactants such as ethylene/polyoxypropylene block copolymers
  • silicone-based surfactants include polyether-modified polysiloxane compounds, specifically Tegorad 2250 (manufactured by Evonik), KF-351A, KF-352A, KF-642 and X-22-4272 ( BYK307, BYK345, BYK347 and BYK348 (manufactured by Big Chemie, "BYK” is a registered trademark of the same company), and TSF4452 (manufactured by Momentive Performance Materials).
  • Tegorad 2250 manufactured by Evonik
  • KF-351A KF-352A
  • KF-642 and X-22-4272 BYK307, BYK345, BYK347 and BYK348 (manufactured by Big Chemie, "BYK” is a registered trademark of the same company)
  • TSF4452 manufactured by Momentive Performance Materials
  • Fluorine-based surfactants mean those in which some or all of the hydrogen atoms in the hydrophobic groups of ordinary surfactants are replaced with fluorine.
  • fluorine-based surfactants include Megafac F (manufactured by DIC, “Megafac” is a registered trademark of the company), Surflon (manufactured by AGC Seikagaku, “Surflon” is a registered trademark of the company), Fluorad FC (3M company, “Fluorad” is a registered trademark of the company), Monflor (manufactured by Imperial Chemical Industries), Zonyls (manufactured by EI Dupont Nemerus and Company), Licowet VPF (manufactured by Lubewerke Hoechst) , and FTERGENT (manufactured by Neos, "FTERGENT” is a registered trademark of the same company).
  • the amount of surfactant can be arbitrarily set within the range where the effects of the present invention can be obtained.
  • the amount of surfactant can be, for example, 0.001% by mass or more and less than 1.0% by mass with respect to the entire ink.
  • the color of the ink of the present invention is preferably white or gray, particularly preferably white.
  • the color of the ink can be adjusted by the content of the colorant of each color.
  • the ink of the present invention can be prepared by mixing the above-mentioned photopolymerizable composition, pigment, etc. while heating by a known method.
  • the inkjet ink set for forming partitions of the present invention (hereinafter also referred to simply as "ink set”) is an inkjet ink set for forming partitions for forming partitions between LED chips of an LED device. It has a forming inkjet ink and a second partition-forming inkjet ink, wherein the first partition-forming inkjet ink contains a photopolymerizable composition and a white colorant, and has a normal boiling point of The content of the solvent having a temperature of 250° C. or less is 25% or less, the second inkjet ink for forming partition walls contains a photopolymerizable composition and a black colorant, and has a normal boiling point of 250° C. The content of the following solvent is 25% or less.
  • the components and the like contained in the first inkjet ink for forming partition walls are as described above.
  • the second inkjet ink for forming partition walls is characterized by containing a black colorant.
  • the color of the first inkjet ink for forming partition walls is preferably white or gray, and particularly preferably white. Further, the color of the second inkjet ink for forming partition walls is preferably black. By using such an ink set, it is possible to form white partition walls or partition walls composed of gray partition walls and black partition walls, which will be described later.
  • the color of the ink can be adjusted by the content of the colorant of each color.
  • the content of the black colorant in the second ink-jet ink for forming partition walls is preferably in the range of 1 to 20% by mass, more preferably in the range of 1.5 to 15% by mass, based on the total ink. is more preferable, and more preferably within the range of 2 to 10% by mass.
  • the black colorant may be either a pigment or a dye.
  • a black colorant may be used alone, or a black colorant may be obtained by mixing colorants such as red, green, and blue.
  • the second inkjet ink for forming partition walls may further contain a coloring material other than the white coloring material and other components as long as the effects of the present invention can be obtained.
  • a method for manufacturing an LED device of the present invention is a method for manufacturing an LED device having partitions between LED chips, comprising a partition forming step of patterning the partitions by an inkjet method, wherein the partitions
  • the forming step has at least a white partition forming step, and in the white partition forming step, the content of a solvent containing a photopolymerizable composition and a white coloring material and having a normal boiling point of 250° C. or lower is 25% or less.
  • a method for manufacturing an LED device of the present invention is a method for manufacturing an LED device having partitions between LED chips, comprising a partition forming step of patterning the partitions by an inkjet method,
  • the partition wall forming step has at least a gray partition wall forming step, and in the gray partition wall forming step, a solvent containing a photopolymerizable composition and a white colorant and having a normal boiling point of 250 ° C. or less It is characterized by using an ink-jet ink for forming partition walls having a content of 25% or less.
  • the ink-jet ink for partition formation used in the manufacturing method of the LED device is as described above.
  • the partition is patterned by the inkjet method. Specifically, droplets of ink are ejected from an inkjet head and landed on positions where partition walls are to be formed on the substrate for patterning. The landed ink is irradiated with an active energy ray to cure the ink and form partition walls.
  • the barrier ribs By patterning the barrier ribs by the inkjet method, unlike the photolithographic method, the LED chips are not damaged, and fine barrier ribs can be formed, which is difficult with the screen printing method or the coating method.
  • the ejection method from the inkjet head may be either an on-demand method or a continuous method.
  • On-demand inkjet heads include electro-mechanical conversion methods such as single-cavity, double-cavity, bender, piston, shear mode and shared wall types, as well as thermal inkjet and bubble jet (bubble jet is A registered trademark of Canon Inc.) may be used.
  • Ejection stability can be improved by ejecting the ink droplets from the inkjet head in a heated state.
  • the temperature of the ink when ejected is preferably in the range of 40 to 100° C., and more preferably in the range of 40 to 90° C. in order to further improve the ejection stability.
  • the method of heating the ink is not particularly limited.
  • at least one of an ink tank constituting the head carriage, an ink supply system such as a supply pipe and an ink tank in the front chamber immediately before the head, a pipe with a filter, a piezo head, etc. is heated by a panel heater, a ribbon heater, or thermal water. be able to.
  • the amount of ink droplets to be ejected is preferably within the range of 2 to 20 pL.
  • the active energy ray can be selected from, for example, electron beams, ultraviolet rays, ⁇ rays, ⁇ rays, and X rays, but ultraviolet rays are preferred.
  • Curing of the ink by irradiation with active energy rays may be performed collectively after all the ink necessary for forming the partition walls has landed, or may be performed in multiple steps by repeating ejection of the ink and irradiation with the active energy rays. may When forming high partition walls or when forming high-precision partition walls, it is preferable to perform the step in multiple steps.
  • a water-cooled LED manufactured by Phoseon Technology can be used under the condition of a wavelength of 395 nm.
  • an LED As a light source, it is possible to suppress poor curing of the ink due to melting of the ink by the radiant heat of the light source.
  • the peak illumination intensity in the case of irradiating ultraviolet rays as active energy rays can be appropriately adjusted depending on the material and amount of the ink to be cured, and can be, for example, within the range of 0.1 to 4.0 W/cm 2 .
  • the amount of light when irradiating ultraviolet rays as active energy rays can be appropriately adjusted depending on the material and amount of the ink to be cured, and can be, for example, within the range of 100 to 5000 mJ/cm 2 .
  • the partition forming step includes at least the white partition forming step, so that white partitions for improving luminance can be formed.
  • the gray partition wall formation step includes at least the gray partition wall formation step, so that the gray partition wall can be formed in which the reflectance and the contrast can be controlled.
  • the partition forming step includes at least a white partition forming step and a black partition forming step of forming black partitions on the white partitions formed in the white partition forming step.
  • the barrier ribs may be formed such that the upper surface that contributes to the improvement is black and the side surface that contributes to the improvement of luminance is partially white.
  • the irradiation with the active energy ray may be performed in each of the white barrier rib formation process and the black barrier rib formation process, or may be collectively performed after the black barrier rib formation process.
  • a gray barrier rib formation process may be added between the white barrier rib formation process and the black barrier rib formation process, or a gray barrier rib formation process may be performed instead of the white barrier rib formation process.
  • LED chips can be used, and mini LED chips and micro LED chips can also be used.
  • a transparent sealant Polyvinylcarbazole and resin such as epoxy resin can be used as the transparent sealant.
  • Substrates, cover glasses, electrodes, circuits, wirings, and other members that the LED device may have are not particularly limited, and known members can be used. Furthermore, a configuration including a wavelength conversion layer and a color filter can be used as necessary.
  • the color of the substrate is preferably black because areas where partition walls and the like are not formed may affect the contrast.
  • the black substrate can further improve the contrast.
  • a substrate formed using a black material or a substrate blackened by sputtering or the like can be used as the black substrate.
  • a black pigment dispersion, a white pigment dispersion A, and a white pigment dispersion B were prepared by the following procedure.
  • the resulting mixed solution was placed in a glass bottle together with 220 g of zirconia beads (diameter: 0.5 mm), sealed, and subjected to dispersion treatment in a paint shaker for 5 hours. After that, the zirconia beads were removed from the mixture to obtain a white pigment dispersion A.
  • the resulting mixed solution was placed in a glass bottle together with 220 g of zirconia beads (diameter: 0.5 mm), sealed, and subjected to dispersion treatment in a paint shaker for 5 hours. After that, the zirconia beads were removed from the mixture to obtain a white pigment dispersion B.
  • the resulting mixed solution was placed in a glass bottle together with 200 g of zirconia beads (diameter: 0.5 mm), sealed, and subjected to dispersion treatment in a paint shaker for 5 hours. After that, the zirconia beads were removed from the mixture to obtain a black pigment dispersion.
  • a black pigment ink and a white pigment ink were prepared by the following procedures.
  • Black pigment inks 1 to 7 The materials shown in Table II were placed in a stainless steel beaker and stirred for 1 hour while being heated to 80° C. on a hot plate. Black pigment inks 1 to 7 were obtained by filtering the resulting solution through a Teflon (registered trademark) 3 ⁇ m membrane filter manufactured by ADVATEC while heating.
  • a white pigment 5.00 g of a titanium dioxide pigment (R-960, manufactured by BASF Japan) is mixed with 5.00 g of a polysiloxane solution as a resin, and dispersed using a mill-type disperser filled with zirconia beads, A pigment dispersion was obtained.
  • pigment dispersion liquid 0.71 g of DAA (diacetone alcohol), 1.57 g of polysiloxane solution, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl) as a photopolymerization initiator -9H-carbazol-3-yl]-,1-(o-acetyloxime) (manufactured by BASF Japan) 0.050 g, bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF Japan) ) 0.400 g, and 0.100 g of 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium 2-(3-benzoylphenyl)propionate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a photobase generator.
  • DAA diacetone alcohol
  • polysiloxane solution ethanone
  • a photopolymerizable compound dipentaerythritol hexaacrylate (manufactured by Shinnihon Yakugyo Co., Ltd.) 1.20 g, as a liquid-repellent compound, a photopolymerizable fluorine-containing compound (“Megafac” (registered trademark) RS-76-E, 1.00 g of a 40% by weight PGMEA diluted solution of DIC Corporation), 0.100 g of 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (manufactured by Daicel Corporation), ethylene bis(oxyethylene) bis[ 3-(5-tert-butyl-4-hydroxy-m-tolyl) propionate] (manufactured by BASF Japan) 0.030 g, acrylic surfactant (“BYK” (registered trademark) 352, manufactured by BYK Chemie Japan) was dissolved in 4.76 g
  • the preliminary dispersion was supplied to an Ultra Apex mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 0.05 mm ⁇ zirconia beads at 75%, and dispersed at a rotation speed of 8 m/s for 3 hours to obtain a solid content concentration of 25.
  • a black pigment dispersion of black pigment/resin (mass ratio) 80/20 was obtained.
  • a black pigment resist having a total solid concentration of 20% and a black pigment/resin (mass ratio) of 58/42 was prepared by adding 56.98 g of a black pigment dispersion to this photosensitive resist.
  • a micro LED chip with a size of 100 ⁇ m ⁇ 100 ⁇ m ⁇ 100 ⁇ m was used as the LED chip.
  • the number of pixels composed of micro LED chips of three colors was 80 ⁇ 80, and a total of 80 ⁇ 80 ⁇ 3 micro LED chips were used.
  • the arrangement of the micro LED chips in the pixel is such that three color micro LED chips are arranged side by side as shown in FIGS. 4 and 7 .
  • the interval between adjacent micro LED chips in the same pixel was set to 250 ⁇ m.
  • the pixel pitch was set to 1300 ⁇ m.
  • the driving substrate used is a non-alkali glass substrate with a size of 200 mm ⁇ 200 mm, on which TFTs (thin film transistors), wiring, and Cu electrode pads corresponding to the number of micro LED chips are formed. board. A blackening treatment was performed by sputtering except for the bonding portion of the driving substrate with the micro LED chip.
  • a non-alkali glass substrate with a thickness of 0.7 mm and the same size as the drive substrate was used for the relay substrate.
  • PDMS (dimethylpolysiloxane) resin was formed with a thickness of 10 ⁇ m on the relay substrate.
  • the PDMS resin was applied to the surface of the substrate in a uniform film thickness by lamination and heated in an oven at 100°C for 1 hour to thermally crosslink the PDMS resin.
  • the PDMS resin Shin-Etsu Silicone SIM360 and CAT360 manufactured by Shin-Etsu Chemical Co., Ltd. were blended to adjust the finished hardness.
  • the hardness of the finished product was a rubber hardness Shore A60.
  • the micro LED chip was diced from the sapphire substrate on which the semiconductor layer was formed, transferred to the holding substrate, and then transferred to the relay substrate.
  • a chip-side electrode was formed on the micro LED chip, and a micro-bump with a height of 5 ⁇ m was formed on the chip-side electrode by solder.
  • SAC SnAgCu
  • flux was applied to the surface of the driving substrate on which the micro LED chip was temporarily bonded, and heat treatment was performed in a reflow furnace at a temperature higher than the melting temperature of the solder. A micro LED chip was mounted by this reflow.
  • red, green, and blue micro LED chips were arranged on the substrate to form an LED device without partition walls.
  • barrier ribs having a width of 200 ⁇ m and a total height of 100 ⁇ m were formed in the pattern shown in FIG. formed.
  • the specific procedure is as follows.
  • Droplets of the white pigment ink 1 were ejected using an inkjet device, and uncured barrier ribs having a height of 20 ⁇ m after curing were formed while patterning.
  • the temperature of the ink during ejection was adjusted to 80°C.
  • the amount of ink droplets to be ejected was set to 5 pL.
  • the uncured barrier ribs were irradiated with ultraviolet rays at a light amount of 1000 mJ/cm 2 to form barrier ribs with a height of 20 ⁇ m.
  • uncured barrier ribs having a height of 20 ⁇ m after curing.
  • the uncured barrier ribs were irradiated with ultraviolet rays at a light intensity of 1000 mJ/cm 2 to make the height of the barrier ribs 40 ⁇ m.
  • barrier ribs with a width of 200 ⁇ m and a total height of 100 ⁇ m.
  • the partition forming step of patterning the partition by the inkjet method was performed.
  • the LED chip was filled with polyvinyl carbazole as a transparent sealant using a dispenser, and laminated with a cover glass.
  • the LED device 1 was produced according to the above procedure.
  • LED devices 2 to 7 were produced by changing the ink as shown in Table III.
  • a white pigment resist was applied to the thus-formed LED device without partition walls using a spin coater, and pre-baked at 90° C. for 10 minutes.
  • a mask aligner PEM-6M manufactured by Union Optical Co., Ltd.
  • this coating film was exposed to ultraviolet rays at an exposure amount of 100 mJ/cm 2 (i-line exposure amount conversion: full wavelength exposure) through a photomask.
  • an alkaline developer of 0.5 mass % aqueous solution of tetramethylammonium hydroxide, and then washed with pure water.
  • the LED chip was filled with polyvinylcarbazole as a transparent sealant using a dispenser, and laminated with a cover glass.
  • the LED device 8 was produced by the above procedure.
  • LED devices 9 and 10 were produced by changing the curing temperature as shown in Table III.
  • Red, green, and blue micro LED chips were arranged on a substrate in the same manner as above to form an LED device without partition walls.
  • Droplets of the white pigment ink 1 were ejected using an inkjet device, and uncured barrier ribs having a height of 20 ⁇ m after curing were formed while patterning.
  • the temperature of the ink during ejection was adjusted to 80°C.
  • the amount of ink droplets to be ejected was set to 5 pL.
  • the uncured barrier ribs were irradiated with ultraviolet rays at a light amount of 1000 mJ/cm 2 to form barrier ribs with a height of 20 ⁇ m.
  • uncured barrier ribs having a height of 20 ⁇ m after curing.
  • the uncured barrier ribs were irradiated with ultraviolet rays at a light intensity of 1000 mJ/cm 2 to make the height of the barrier ribs 40 ⁇ m.
  • barrier ribs having a height of 20 ⁇ m after curing.
  • the uncured barrier ribs were irradiated with ultraviolet rays at a light intensity of 1000 mJ/cm 2 to form black barrier ribs with a height of 20 ⁇ m.
  • barrier ribs having a width of 200 ⁇ m and a total height of 100 ⁇ m were formed.
  • a partition forming step including a white partition forming step and a black partition forming step of forming a black partition on the white partition formed in the white partition forming step was performed.
  • the LED chip was filled with polyvinyl carbazole as a transparent sealant using a dispenser, and laminated with a cover glass.
  • the LED device 11 was produced by the above procedure.
  • LED devices 12 to 17 were produced by changing the ink as shown in Table III.
  • a white pigment resist was applied to the thus-formed LED device without partition walls using a spin coater, and pre-baked at 90° C. for 10 minutes.
  • a mask aligner PEM-6M manufactured by Union Optical Co., Ltd.
  • this coating film was exposed to ultraviolet rays at an exposure amount of 100 mJ/cm 2 (i-line exposure amount conversion: full wavelength exposure) through a photomask.
  • an alkaline developer of 0.5 mass % aqueous solution of tetramethylammonium hydroxide, and then washed with pure water.
  • a black pigment resist was applied by a spin coater onto the substrate on which the white barrier ribs were formed, and prebaked at 90° C. for 10 minutes.
  • a mask aligner PEM-6M manufactured by Union Optical Co., Ltd.
  • this coating film was exposed to ultraviolet rays at an exposure amount of 100 mJ/cm 2 (i-line exposure amount conversion: full wavelength exposure) through a photomask.
  • an alkaline developer of 0.5 mass % aqueous solution of tetramethylammonium hydroxide, and then washed with pure water.
  • barrier ribs having a total height of 100 ⁇ m and a width of 200 ⁇ m were formed.
  • the LED chip was filled with polyvinyl carbazole as a transparent sealant using a dispenser, and laminated with a cover glass.
  • the LED device 18 was produced by the above procedure.
  • LED devices 19 and 20 were fabricated by changing the curing temperature as shown in Table III.
  • the LED device was turned on and the brightness was measured. For the LED devices 1 to 10, the luminance of the LED device 1 was taken as 100, and the relative luminance values were calculated and used as the relative luminance. Similarly, for the LED devices 11 to 20, the relative luminance was calculated with the luminance of the LED device 11 set to 100.
  • Relative brightness is 90 or more
  • Relative brightness is 80 or more and less than 90
  • Relative brightness is less than 80
  • Luminance maintenance rate [%] Luminance after storage/Luminance before storage ⁇ 100
  • the present invention can be applied to an ink jet ink for forming a partition wall, an inkjet ink set for forming a partition wall, and a method for manufacturing an LED device using the same, which can form a partition wall between LED chips with low damage without reducing luminance. can.

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Abstract

The present invention addresses the problem of providing: an inkjet ink for partition wall formation and an inkjet ink set for partition wall formation that make it possible to form, with low damage, a partition wall which does not decrease luminance, the partition wall being formed between LED chips; and an LED device manufacturing method using the foregoing.　This inkjet ink for partition wall formation is used for forming a partition wall between LED chips in an LED device, and is characterized by: including a photopolymerizable composition and a colorant; and containing 25% or less of a solvent having a standard boiling point of 250℃ or lower.

Description

隔壁形成用インクジェットインク、隔壁形成用インクジェットインクセット、及びＬＥＤデバイスの製造方法Inkjet ink for forming barrier ribs, inkjet ink set for forming barrier ribs, and method for manufacturing LED device
　本発明は、隔壁形成用インクジェットインク、隔壁形成用インクジェットインクセット、及びＬＥＤデバイスの製造方法に関する。
　より詳しくは、輝度を低下させない隔壁をＬＥＤチップ間に低ダメージで形成することができる隔壁形成用インクジェットインク等に関する。 The present invention relates to an inkjet ink for forming partitions, an inkjet ink set for forming partitions, and a method for manufacturing an LED device.
More particularly, the present invention relates to an ink-jet ink for forming partition walls, which can form partition walls between LED chips with low damage, and the like, which does not reduce luminance.
　ＬＥＤディスプレイ（light emitting diode）等のＬＥＤデバイスにおいて、隣接するＬＥＤチップ間で生じる混色を防止するために、ＬＥＤチップ間に隔壁を設ける技術が用いられている。このような隔壁を形成する手段として、例えば特許文献１では、フォトリソグラフィ法にて遮光性の高い隔壁を形成する技術が開示されている。しかしながら、遮光性の高い隔壁の場合、ＬＥＤチップからの光を隔壁が吸収してしまうため、輝度が不十分となる問題があった。 In LED devices such as LED displays (light emitting diodes), a technique of providing partition walls between LED chips is used in order to prevent color mixing that occurs between adjacent LED chips. As means for forming such partitions, for example, Patent Document 1 discloses a technique for forming partitions with high light-shielding properties by photolithography. However, in the case of partition walls having a high light-shielding property, the partition walls absorb the light from the LED chips, resulting in insufficient brightness.
　上記問題を解決するために、特許文献２では、白色顔料を含有する反射部を有する隔壁を形成する技術が開示されている。この技術では、反射部によって光の取り出し効率が向上し、輝度が不十分となる問題を解決している。 In order to solve the above problem, Patent Document 2 discloses a technique of forming a partition wall having a reflective portion containing a white pigment. In this technology, the reflective portion improves the light extraction efficiency and solves the problem of insufficient brightness.
　上記のとおり、特許文献１で開示されている技術を用いることで、隣接するＬＥＤチップ間で生じる混色を防止することができ、さらに特許文献２で開示されている技術を用いることで、輝度が低下する問題も解決し得る。しかしながら、いずれの技術においても、隔壁の形成はフォトリソグラフィ法を用いて行っていることから、現像液や溶剤によってＬＥＤデバイスにダメージがあることが懸念されており、ＬＥＤデバイスの製造歩留まりや耐久性（特に高温耐久性）を向上させるために、ＬＥＤデバイスへのダメージが小さい隔壁形成技術が求められていた。 As described above, by using the technology disclosed in Patent Document 1, color mixing that occurs between adjacent LED chips can be prevented. It can also solve the declining problem. However, in any technology, since the formation of the barrier ribs is performed using the photolithography method, there is a concern that the LED device may be damaged by the developer or solvent, and the manufacturing yield and durability of the LED device are greatly reduced. In order to improve (in particular, high temperature durability), a technique for forming barrier ribs that causes less damage to LED devices has been desired.
特開２０１８－１８２２８２号公報JP 2018-182282 A 特開２０２０－２０５４１７号公報JP 2020-205417 A
　本発明は、上記問題・状況に鑑みてなされたものであり、その解決課題は、輝度を低下させない隔壁をＬＥＤチップ間に低ダメージで形成することができる隔壁形成用インクジェットインク、隔壁形成用インクジェットインクセット、及びそれを用いたＬＥＤデバイスの製造方法を提供することである。 The present invention has been made in view of the above problems and circumstances, and the problem to be solved is an ink-jet ink for forming partitions, which is capable of forming partitions between LED chips with little damage that does not reduce luminance, and an inkjet ink for forming partitions. An object of the present invention is to provide an ink set and a method for manufacturing an LED device using the ink set.
　本発明者は、上記課題を解決すべく、上記課題の原因等について検討した結果、光重合性組成物と、白色色材とを含有させ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下であるインクとすることで、輝度を低下させない隔壁をＬＥＤチップ間に低ダメージで形成することができる隔壁形成用インクジェットインクを提供することができることを見いだし本発明に至った。
　すなわち、本発明に係る上記課題は、以下の手段により解決される。 In order to solve the above problems, the present inventors have investigated the causes of the above problems, and found that the content of a solvent having a normal boiling point of 250 ° C. or less in a photopolymerizable composition and a white colorant is , 25% or less, it is possible to provide an inkjet ink for forming partitions that can form partitions between LED chips with low damage that does not reduce luminance.
That is, the above problems related to the present invention are solved by the following means.
　１．ＬＥＤデバイスのＬＥＤチップ間に隔壁を形成するための隔壁形成用インクジェットインクであって、
　光重合性組成物と、白色色材とを含有し、
　標準沸点が２５０℃以下である溶剤の含有量が、２５％以下である
　ことを特徴とする隔壁形成用インクジェットインク。 1. An inkjet ink for forming partitions for forming partitions between LED chips of an LED device,
Containing a photopolymerizable composition and a white colorant,
An inkjet ink for forming partition walls, wherein the content of a solvent having a normal boiling point of 250° C. or less is 25% or less.
　２．前記光重合性組成物の成分として、（メタ）アクリレート化合物を含有する
　ことを特徴とする第１項に記載の隔壁形成用インクジェットインク。 2. 2. The inkjet ink for forming partition walls according to Item 1, wherein the photopolymerizable composition contains a (meth)acrylate compound as a component.
　３．ＬＥＤデバイスのＬＥＤチップ間に隔壁を形成するための隔壁形成用インクジェットインクセットであって、
　第１の隔壁形成用インクジェットインクと、第２の隔壁形成用インクジェットインクとを有し、
　前記第１の隔壁形成用インクジェットインクが、光重合性組成物と、白色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下であり、
　前記第２の隔壁形成用インクジェットインクが、光重合性組成物と、黒色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下である
　ことを特徴とする隔壁形成用インクジェットインクセット。 3. An inkjet ink set for forming partitions for forming partitions between LED chips of an LED device,
having a first partition-forming inkjet ink and a second partition-forming inkjet ink,
The first inkjet ink for forming partition walls contains a photopolymerizable composition and a white colorant, and the content of a solvent having a normal boiling point of 250° C. or less is 25% or less,
The second inkjet ink for forming partition walls contains a photopolymerizable composition and a black colorant, and the content of a solvent having a normal boiling point of 250° C. or less is 25% or less. An inkjet ink set for forming partition walls.
　４．ＬＥＤチップ間に隔壁を有するＬＥＤデバイスの製造方法であって、
　インクジェット法によって前記隔壁のパターニングを行う隔壁形成工程を有し、
　前記隔壁形成工程が、少なくとも、白色隔壁形成工程を有し、
　前記白色隔壁形成工程において、光重合性組成物と、白色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下である隔壁形成用インクジェットインクを用いる
　ことを特徴とするＬＥＤデバイスの製造方法。 4. A method of manufacturing an LED device having partitions between LED chips, comprising:
A partition forming step of patterning the partition by an inkjet method,
The partition forming step has at least a white partition forming step,
In the step of forming white barrier ribs, an inkjet ink for forming barrier ribs containing a photopolymerizable composition and a white colorant and having a normal boiling point of 250° C. or less and a solvent content of 25% or less is used. A method for manufacturing an LED device, characterized by:
　５．前記隔壁形成工程が、少なくとも、前記白色隔壁形成工程と、前記白色隔壁形成工程で形成した白色隔壁の上に黒色隔壁を形成する黒色隔壁形成工程とを有し、
　前記黒色隔壁形成工程において、光重合性組成物と、黒色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下である隔壁形成用インクジェットインクを用いる
　ことを特徴とする第４項に記載のＬＥＤデバイスの製造方法。 5. The partition wall forming step includes at least the white partition wall forming step and a black partition wall forming step of forming a black partition wall on the white partition wall formed in the white partition wall forming step,
In the step of forming black partition walls, a partition-forming inkjet ink containing a photopolymerizable composition and a black colorant and containing 25% or less of a solvent having a normal boiling point of 250° C. or lower is used. 5. A method for manufacturing an LED device according to claim 4, characterized in that:
　本発明の上記手段により、輝度を低下させない隔壁をＬＥＤチップ間に低ダメージで形成することができる隔壁形成用インクジェットインク、隔壁形成用インクジェットインクセット、及びそれを用いたＬＥＤデバイスの製造方法を提供することができる。 By the means of the present invention, an ink-jet ink for forming a partition wall, an inkjet ink set for forming a partition wall, and a method for manufacturing an LED device using the same, which can form a partition wall between LED chips with low damage without lowering luminance are provided. can do.
　本発明の効果の発現機構又は作用機構については、明確にはなっていないが、以下のように推察している。 Although the expression mechanism or action mechanism of the effects of the present invention has not been clarified, it is speculated as follows.
　本発明の隔壁形成用インクジェットインクは、白色色材を含有することによって、輝度を低下させない白色隔壁又は灰色隔壁を形成することができる。 The inkjet ink for forming partition walls of the present invention can form white partition walls or gray partition walls that do not reduce luminance by containing a white colorant.
　また、インクジェットインクであることから、当該インクを用いることによって、インクジェット法でＬＥＤデバイスに対して非接触で隔壁を形成することができる。特にフォトリソグラフィ法のように現像液を用いる必要がないことから、ＬＥＤデバイスへのダメージを抑えることができる。 In addition, since it is an inkjet ink, it is possible to form the barrier ribs in a non-contact manner with respect to the LED device by an inkjet method by using the ink. In particular, since it is not necessary to use a developing solution unlike the photolithography method, damage to the LED device can be suppressed.
　また、本発明の隔壁形成用インクジェットインクは、標準沸点（１気圧下での沸点）が２５０℃以下である溶剤の含有量が２５％以下であることから、溶剤による、ＬＥＤデバイスへのダメージも抑えることができる。 In addition, since the inkjet ink for forming partition walls of the present invention contains 25% or less of a solvent having a normal boiling point (boiling point under 1 atm) of 250° C. or less, the solvent may damage the LED device. can be suppressed.
　これらの発現機構又は作用機構により、本発明の隔壁形成用インクジェットインクは、輝度を低下させない隔壁をＬＥＤチップ間に低ダメージで形成することができると考えられる。 It is believed that the ink-jet ink for forming partitions of the present invention can form partitions between LED chips with low damage that do not reduce the brightness due to these expression mechanisms or action mechanisms.
本発明のインクによって形成される隔壁の様子を例示するためのＬＥＤデバイスの一部の断面模式図１ＡFIG. 1A is a schematic cross-sectional view of a part of an LED device for illustrating the appearance of partition walls formed by the ink of the present invention. 本発明のインクによって形成される隔壁の様子を例示するためのＬＥＤデバイスの一部の断面模式図１ＢSchematic cross-sectional view 1B of a part of the LED device for illustrating the state of the partition formed by the ink of the present invention 本発明のインクによって形成される隔壁の様子を例示するためのＬＥＤデバイスの一部の断面模式図２ＡFIG. 2A is a schematic cross-sectional view of a part of an LED device for illustrating the appearance of partition walls formed by the ink of the present invention. 本発明のインクによって形成される隔壁の様子を例示するためのＬＥＤデバイスの一部の断面模式図２ＢSchematic cross-sectional view 2B of a part of the LED device for illustrating the state of the partition formed by the ink of the present invention 本発明のインクによって形成される隔壁の様子を例示するためのＬＥＤデバイスの一部の断面模式図３ＡFIG. 3A is a schematic cross-sectional view of a part of an LED device for illustrating the appearance of partition walls formed by the ink of the present invention. 本発明のインクによって形成される隔壁の様子を例示するためのＬＥＤデバイスの一部の断面模式図３Ｂ Schematic cross-sectional view 3B of a part of the LED device for illustrating the state of the partition formed by the ink of the present invention 隔壁が形成されていないＬＥＤデバイスを示す模式図Schematic diagram showing an LED device without partitions それぞれのＬＥＤチップの周囲を覆うように隔壁が形成されているパターンを示す模式図A schematic diagram showing a pattern in which partition walls are formed so as to cover the periphery of each LED chip. ３色のＬＥＤチップからなる画素の周囲を覆うように隔壁が形成されているパターンを示す模式図Schematic diagram showing a pattern in which partition walls are formed so as to cover the periphery of pixels composed of LED chips of three colors. それぞれのＬＥＤチップの周囲を覆うように隔壁が形成されているが、隔壁はある幅で形成され、画素間には隔壁が形成されていない領域も存在するパターンを示す模式図Schematic diagram showing a pattern in which partition walls are formed to cover the periphery of each LED chip, but the partition walls are formed with a certain width, and there are regions between pixels where no partition walls are formed.
　本発明の隔壁形成用インクジェットインクは、ＬＥＤデバイスのＬＥＤチップ間に隔壁を形成するための隔壁形成用インクジェットインクであって、光重合性組成物と、白色色材とを含有し、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下であることを特徴とする。
　この特徴は、下記実施形態に共通する又は対応する技術的特徴である。 The inkjet ink for forming partition walls of the present invention is an inkjet ink for forming partition walls between LED chips of an LED device, which contains a photopolymerizable composition and a white colorant, and has a normal boiling point of The content of the solvent having a temperature of 250° C. or less is 25% or less.
This feature is a technical feature common to or corresponding to the following embodiments.
　本発明の隔壁形成用インクジェットインクの実施形態としては、重合速度及び重合度等の観点から、前記光重合性組成物の成分として、（メタ）アクリレート化合物を含有することが好ましい。 As an embodiment of the ink-jet ink for forming partition walls of the present invention, it is preferable to contain a (meth)acrylate compound as a component of the photopolymerizable composition from the viewpoint of the polymerization rate and degree of polymerization.
　本発明の隔壁形成用インクジェットインクセットは、ＬＥＤデバイスのＬＥＤチップ間に隔壁を形成するための隔壁形成用インクジェットインクセットであって、第１の隔壁形成用インクジェットインクと、第２の隔壁形成用インクジェットインクとを有し、前記第１の隔壁形成用インクジェットインクが、光重合性組成物と、白色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下であり、前記第２の隔壁形成用インクジェットインクが、光重合性組成物と、黒色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下であることを特徴とする。 The partition-forming inkjet ink set of the present invention is an inkjet ink set for forming partitions between LED chips of an LED device, and comprises a first partition-forming inkjet ink and a second partition-forming inkjet ink. an inkjet ink, wherein the first inkjet ink for partition wall formation contains a photopolymerizable composition and a white colorant, and the content of a solvent having a normal boiling point of 250° C. or less is 25 % or less, and the second inkjet ink for forming partition walls contains a photopolymerizable composition and a black colorant, and the content of the solvent having a normal boiling point of 250° C. or less is 25% or less. It is characterized by
　本発明のＬＥＤデバイスの製造方法は、ＬＥＤチップ間に隔壁を有するＬＥＤデバイスの製造方法であって、インクジェット法によって前記隔壁のパターニングを行う隔壁形成工程を有し、前記隔壁形成工程が、少なくとも、白色隔壁形成工程を有し、前記白色隔壁形成工程において、光重合性組成物と、白色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下である隔壁形成用インクジェットインクを用いることを特徴とする。 A method for manufacturing an LED device according to the present invention is a method for manufacturing an LED device having partitions between LED chips, comprising a partition formation step of patterning the partitions by an inkjet method, wherein the partition formation step includes at least: It has a white partition wall forming step, and in the white partition wall forming step, the content of a solvent containing a photopolymerizable composition and a white colorant and having a normal boiling point of 250 ° C. or lower is 25% or less. It is characterized by using a certain ink-jet ink for partition formation.
　本発明のＬＥＤデバイスの製造方法の実施形態としては、前記隔壁形成工程が、少なくとも、前記白色隔壁形成工程と、前記白色隔壁形成工程で形成した白色隔壁の上に黒色隔壁を形成する黒色隔壁形成工程とを有し、前記黒色隔壁形成工程において、光重合性組成物と、黒色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下である隔壁形成用インクジェットインクを用いることが好ましい。これによって、コントラストの向上に寄与する上面は黒色であり、輝度の向上に寄与する側面は部分的に白色である隔壁を形成することができる。 As an embodiment of the LED device manufacturing method of the present invention, the partition forming step includes at least the white partition forming step and the black partition forming in which the black partition is formed on the white partition formed in the white partition forming step. and in the step of forming black partition walls, partition walls containing a photopolymerizable composition and a black colorant and having a normal boiling point of 250° C. or lower in a solvent content of 25% or less. Forming inkjet inks are preferably used. As a result, it is possible to form barrier ribs whose upper surface that contributes to an improvement in contrast is black and whose side surface that contributes to an improvement in luminance is partially white.
　以下、本発明とその構成要素、及び本発明を実施するための形態・態様について詳細な説明をする。なお、本願において、「～」は、その前後に記載される数値を下限値及び上限値として含む意味で使用する。 The following is a detailed description of the present invention, its components, and the forms and modes for carrying out the present invention. In the present application, "-" is used to mean that the numerical values before and after it are included as the lower limit and the upper limit.
＜１　隔壁形成用インクジェットインク＞
　本発明の隔壁形成用インクジェットインク（以下、単に「インク」ともいう。）は、ＬＥＤデバイスのＬＥＤチップ間に隔壁を形成するための隔壁形成用インクジェットインクであって、光重合性組成物と、白色色材と含有し、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下であることを特徴とする。 <1 Inkjet ink for partition formation>
The partition-forming inkjet ink of the present invention (hereinafter also simply referred to as "ink") is an inkjet ink for partition-forming for forming partitions between LED chips of an LED device, comprising a photopolymerizable composition, The content of the white colorant and the solvent having a normal boiling point of 250° C. or less is 25% or less.
＜１．１　インクの用途＞
　本発明のインクは、ＬＥＤデバイスのＬＥＤチップ間に隔壁を形成するための隔壁形成用インクジェットインクである。 <1.1 Use of ink>
The ink of the present invention is a partition-forming inkjet ink for forming partitions between LED chips of an LED device.
　本発明において、「隔壁」とは、ＬＥＤデバイスにおいて、隣接する画素間、又は隣接するＬＥＤチップ間の混色を防止するためにＬＥＤチップ間に形成され、ＬＥＤチップの高さに対して２５％以上の高さがある壁のことをいう。 In the present invention, the “partition wall” is formed between LED chips to prevent color mixing between adjacent pixels or between adjacent LED chips in an LED device, and is 25% or more of the height of the LED chip. A wall with a height of
　図１Ａ、Ｂ及び図２Ａ、Ｂは、本発明のインクによって形成される隔壁の様子を例示するための、ＬＥＤデバイスの一部の断面模式図である。基板２上に、赤色ＬＥＤチップ３Ｒ、緑色ＬＥＤチップ３Ｇ、及び青色ＬＥＤチップ３Ｂが配列されているＬＥＤデバイス１において、隔壁４（白色隔壁４）は、図１Ａ、Ｂに示すように、それぞれのＬＥＤチップの周囲を覆うように形成されていてもよく、図２Ａ、Ｂに示すように、３色のＬＥＤチップからなる画素の周囲を覆うように形成されていてもい。また、図１Ａ、Ｂ及び図２Ａ、Ｂには、ＬＥＤチップを封止するための透明封止剤５及びカバーガラス６も示している。 FIGS. 1A, B and 2A, B are schematic cross-sectional views of a part of an LED device for illustrating partition walls formed by the ink of the present invention. In the LED device 1 in which the red LED chip 3R, the green LED chip 3G, and the blue LED chip 3B are arranged on the substrate 2, the partition walls 4 (white partition walls 4) are arranged as shown in FIGS. It may be formed so as to cover the periphery of the LED chip, or as shown in FIGS. 1A, B and 2A, B also show a transparent encapsulant 5 and a cover glass 6 for encapsulating the LED chip.
　隔壁のＬＥＤチップの高さに対する高さは、２５％以上であることを要するが、より混色を防止するためには、５０％以上であることが好ましく、７５％以上であることがより好ましい。また、隔壁が高すぎると輝度を低下させてしまうため、隔壁のＬＥＤチップの高さに対する高さは、２００％以下であることが好ましい。 The height of the partition wall with respect to the height of the LED chip is required to be 25% or more, but in order to further prevent color mixture, it is preferably 50% or more, more preferably 75% or more. Moreover, if the barrier ribs are too high, the luminance is lowered, so the height of the barrier ribs relative to the height of the LED chips is preferably 200% or less.
　図１Ａ、Ｂ及び図２Ａ、Ｂは、ＬＥＤチップの高さに対する高さが約１５０％である隔壁が形成されたＬＥＤデバイスを示しており、図３Ａ、Ｂは、ＬＥＤチップの高さに対する高さが約５０％である隔壁が形成されたＬＥＤデバイスを示している。 FIGS. 1A,B and 2A,B show an LED device formed with a partition having a height relative to the height of the LED chip of about 150%, and FIGS. Figure 3 shows an LED device formed with a barrier rib having a thickness of about 50%.
　図４は、隔壁が形成されていないＬＥＤデバイスを示しており、図５～７は、異なるパターンで隔壁が形成されているＬＥＤデバイスを示している。図４～７は、いずれも、ＬＥＤデバイスの一部を上から見た模式図であり、赤色ＬＥＤチップ３Ｒ、緑色ＬＥＤチップ３Ｇ、及び青色ＬＥＤチップ３Ｂからなるセットを１画素として、４画素分の領域を示している。 FIG. 4 shows an LED device without partitions, and FIGS. 5-7 show LED devices with partitions formed in different patterns. 4 to 7 are all schematic diagrams of a part of the LED device viewed from above, and four pixels are shown, with a set consisting of a red LED chip 3R, a green LED chip 3G, and a blue LED chip 3B as one pixel. area.
　図５は、図１Ａ、Ｂ及び図３Ａ、Ｂを上から見た状態（ＬＥＤチップの数は異なり、透明封止剤５及びカバーガラス６は図示していない。）に相当し、それぞれのＬＥＤチップの周囲を覆うように隔壁４が形成されているパターンを示している。 5 corresponds to the top view of FIGS. 1A, B and FIGS. 3A, B (the number of LED chips is different, and the transparent encapsulant 5 and the cover glass 6 are not shown), and each LED It shows a pattern in which a partition wall 4 is formed so as to cover the periphery of the chip.
　図６は、図２Ａ、Ｂを上から見た状態（透明封止剤５及びカバーガラス６は図示していない。）に相当し、３色のＬＥＤチップからなる画素の周囲を覆うように隔壁４が形成されているパターンを示している。 FIG. 6 corresponds to a state in which FIGS. 2A and 2B are viewed from above (the transparent sealant 5 and the cover glass 6 are not shown), and partition walls are formed so as to cover the pixels composed of LED chips of three colors. 4 shows the pattern in which 4 is formed.
　図７は、図５と同じようにそれぞれのＬＥＤチップの周囲を覆うように隔壁４が形成されているが、隔壁はある幅で形成され、画素間には隔壁が形成されていない領域も存在するパターンを示している。 In FIG. 7, partition walls 4 are formed so as to cover the periphery of each LED chip as in FIG. It shows a pattern that
　なお、図１～７は、実施形態を例示するものであり、本発明のインクによって形成される隔壁のパターンや、本発明のインクが用いられるＬＥＤデバイスにおけるＬＥＤチップの配置を限定するものではない。 1 to 7 illustrate embodiments, and do not limit the pattern of partition walls formed by the ink of the present invention or the arrangement of LED chips in an LED device using the ink of the present invention. .
　隔壁の幅方向の断面形状は、下部と上部の幅が略一定である形状であってもよく、また、下部の幅が広いテーパー型の形状や、上部の幅が広い逆テーパー型の形状であってもよい。隔壁の幅は、特に限定されない。 The cross-sectional shape of the partition wall in the width direction may be a shape in which the widths of the lower part and the upper part are substantially constant, or may be a tapered shape with a wide lower part or a reverse tapered shape with a wide upper part. There may be. The width of the partition is not particularly limited.
　本発明のインクを用いて形成された隔壁の色は、白色又は灰色となるが、本発明以外のインクを更に用いて、２種以上の異なる色の隔壁が重なって構成された隔壁を形成することもできる。例えば、図１Ｂ、図２Ｂ及び図３Ｂに示すように、白色隔壁４Ｗｈと、その上に位置する黒色隔壁４Ｂｌとで構成された隔壁４とすることで、コントラストの向上に寄与する上面は黒色にしつつ、輝度の向上に寄与する側面は部分的に白色にすることができるため、輝度とコントラストを同時に向上させることができる。なお、２種以上の異なる色の隔壁が重なって構成された隔壁の場合、上記の高さや幅等の寸法は、隔壁全体での寸法のことを示す。 The color of the barrier ribs formed using the ink of the present invention is white or gray, but by further using an ink other than the present invention, the barrier ribs are formed by stacking barrier ribs of two or more different colors. can also For example, as shown in FIGS. 1B, 2B, and 3B, the partition walls 4 are made up of a white partition wall 4Wh and a black partition wall 4Bl located thereon, so that the upper surface that contributes to the improvement of the contrast is made black. Meanwhile, since the side surfaces that contribute to the improvement of luminance can be partially made white, luminance and contrast can be improved at the same time. In addition, in the case of a partition made up of overlapping partitions of two or more different colors, the above dimensions such as height and width indicate the dimensions of the partition as a whole.
　本発明において、「白色」とは、マンセル表色系（ＪＩＳ　Ｚ　８７２１）における明度が８．０以上であり、かつ彩度が２．０以下である色のことをいう。また、「黒色」とは、マンセル表色系（ＪＩＳ　Ｚ　８７２１）における明度が２．０以下であり、かつ彩度が２．０以下である色のことをいう。「灰色」とは、白色と黒色の混合色のことをいう。 In the present invention, "white" refers to a color with a brightness of 8.0 or more and a saturation of 2.0 or less in the Munsell color system (JIS Z 8721). In addition, "black" refers to a color having a brightness of 2.0 or less and a saturation of 2.0 or less in the Munsell color system (JIS Z 8721). "Gray" refers to a mixture of white and black.
　本発明のインクは、上記のような隔壁を形成するために用いられるインクである。 The ink of the present invention is an ink used to form the partition walls as described above.
＜１．２　インクの成分＞
　本発明のインクは、光重合性組成物と、白色色材とを含有し、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下であることを特徴とする。以下、成分の詳細を説明する。 <1.2 Ink components>
The ink of the present invention contains a photopolymerizable composition and a white colorant, and is characterized by containing 25% or less of a solvent having a normal boiling point of 250° C. or less. Details of the components are described below.
（光重合性組成物）
　本発明に係る光重合性組成物は、成分として少なくとも重合性化合物を含み、必要に応じて更に光重合開始剤を含むことが好ましい。 (Photopolymerizable composition)
The photopolymerizable composition according to the present invention preferably contains at least a polymerizable compound as a component and, if necessary, a photopolymerization initiator.
　重合性化合物の含有量は、インク全体に対して１～９７質量％の範囲内であることが好ましく、３０～９０質量％の範囲内であることがより好ましい。 The content of the polymerizable compound is preferably within the range of 1 to 97% by mass, more preferably within the range of 30 to 90% by mass, based on the total ink.
　重合性化合物は、特に限定されず、光重合開始剤の共存下又は非存在下において、活性エネルギー線（電子線、紫外線、α線、γ線、及びエックス線等）の照射により重合反応を開始し、重合・架橋により硬化する化合物を用いることができる。なお、重合性化合物は、モノマー、重合性オリゴマー、プレポリマー及びこれらの混合物のいずれであってもよい。 The polymerizable compound is not particularly limited, and in the presence or absence of a photopolymerization initiator, the polymerization reaction is initiated by irradiation with active energy rays (electron beams, ultraviolet rays, α rays, γ rays, X rays, etc.). , a compound that cures by polymerization and cross-linking can be used. The polymerizable compound may be any of monomers, polymerizable oligomers, prepolymers and mixtures thereof.
　重合性化合物としては、例えば、カチオン重合性化合物、ラジカル重合性化合物、又はこれらの混合物が挙げられ、重合速度及び重合度等の観点から、ラジカル重合性化合物であることが好ましく、（メタ）アクリレート化合物であることがより好ましい。 Examples of the polymerizable compound include cationically polymerizable compounds, radically polymerizable compounds, and mixtures thereof. From the viewpoint of polymerization rate and degree of polymerization, radically polymerizable compounds are preferred, and (meth)acrylates are preferred. Compounds are more preferred.
　「ラジカル重合性化合物」とは、分子中にエチレン性不飽和二重結合を有する化合物のことをいう。ラジカル重合性化合物は、単官能又は多官能のどちらの化合物であってもよい。 "Radical polymerizable compound" refers to a compound having an ethylenically unsaturated double bond in the molecule. The radically polymerizable compound may be either monofunctional or polyfunctional.
　ラジカル重合性化合物としては、不飽和カルボン酸エステル化合物である、（メタ）アクリレート化合物が挙げられる。なお、本発明において、「（メタ）アクリレート」は、アクリレート又はメタアクリレートのことをいう。また、本発明において、「（メタ）アクリレート化合物」には、（メタ）アクリロイル基を主鎖に含む化合物、（メタ）アクリロイル基を側鎖として有する化合物、及び（メタ）アクリロイル基を側鎖が有する置換基として含む化合物が含まれる。 Examples of radically polymerizable compounds include (meth)acrylate compounds, which are unsaturated carboxylic acid ester compounds. In the present invention, "(meth)acrylate" refers to acrylate or methacrylate. In the present invention, the "(meth)acrylate compound" includes a compound containing a (meth)acryloyl group in the main chain, a compound having a (meth)acryloyl group as a side chain, and a compound having a (meth)acryloyl group as a side chain. Included are compounds containing as substituents having
　酸性基を有しない（メタ）アクリレート化合物の例には、イソアミル（メタ）アクリレート、ステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、オクチル（メタ）アクリレート、デシル（メタ）アクリレート、イソミルスチル（メタ）アクリレート、イソステアリル（メタ）アクリレート、２-エチルヘキシル－ジグリコール（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシプロピレングリコール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、及びｔ-ブチルシクロヘキシル（メタ）アクリレートなどを含む単官能のアクリレート、並びに、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、１,４－ブタンジオールジ（メタ）アクリレート、１,６－ヘキサンジオールジ（メタ）アクリレート、１,９－ノナンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジメチロール－トリシクロデカンジ（メタ）アクリレート、ビスフェノールＡのＰＯ付加物ジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ポリテトラメチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジアクリレート、トリプロピレングリコールジアクリレート、及びトリシクロデカンジメタノールジアクリレートなどを含む２官能のアクリレート、並びに、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、グリセリンプロポキシトリ（メタ）アクリレート、及びペンタエリスリトールエトキシテトラ（メタ）アクリレートなどの３官能以上のアクリレートを含む多官能のアクリレートなどが含まれる。 Examples of (meth)acrylate compounds without acidic groups include isoamyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isomyrstyl (meth)acrylate , isostearyl (meth)acrylate, 2-ethylhexyl-diglycol (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene monofunctional acrylates, including glycol (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, and t-butylcyclohexyl (meth)acrylate; (meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1, 4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dimethylol-tricyclodecanedi ( meth)acrylate, PO adduct di(meth)acrylate of bisphenol A, neopentyl glycol hydroxypivalate di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, and Bifunctional acrylates including tricyclodecanedimethanol diacrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate , ditrimethylolpropane tetra(meth)acrylate, glycerin propoxy tri(meth)acrylate, and polyfunctional acrylates including tri- or higher functional acrylates such as pentaerythritol ethoxytetra(meth)acrylate.
　カルボキシ基を有する（メタ）アクリレート化合物としては、例えば、ヒドロキシ基を有する（メタ）アクリレート化合物や、これらからなるオリゴマーに酸無水物を付加させた（メタ）アクリレートが挙げられる。この酸無水物としては、例えば、無水フタル酸、イソフタル酸、テレフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、テトラブロモ無水フタル酸、テトラクロル無水フタル酸、無水ハイミック酸、無水マレイン酸、無水トリメリット酸、メチルシクロヘキセントリカルボン酸無水物、及び無水ピロメリット酸が挙げられる。カルボキシ基を有する（メタ）アクリレート化合物の具体的な例としては、２-カルボキシエチルアクリレート、４－（メタ）アクリロイルオキシエトキシカルボニルフタル酸、４－（メタ）アクリロイルオキシブトキシカルボニルフタル酸、４－（メタ）アクリロイルオキシヘキシロキシカルボニルフタル酸、４－（メタ）アクリロイルオキシデシロキシカルボニルフタル酸などの（メタ）アクリロイルオキシアルコキシカルボニルフタル酸類、４－（メタ）アクリロイルオキシエトキシエトキシカルボニルフタル酸などの（メタ）アクリロイルオキシアルコキシアルコキシカルボニルフタル酸類、モノ－２－（アクリロイルオキシ）エチルサクシネート、２，２－ビス（アクリロイルアミド）酢酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシエチル－２－ヒドロキシエチル－フタル酸、及び２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸等が挙げられる。 Examples of (meth)acrylate compounds having a carboxy group include (meth)acrylate compounds having a hydroxy group and (meth)acrylates obtained by adding an acid anhydride to an oligomer composed of these. Examples of the acid anhydride include phthalic anhydride, isophthalic anhydride, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, hymic anhydride, maleic anhydride, and trimellit anhydride. acids, methylcyclohexene tricarboxylic anhydride, and pyromellitic anhydride. Specific examples of (meth)acrylate compounds having a carboxy group include 2-carboxyethyl acrylate, 4-(meth)acryloyloxyethoxycarbonylphthalic acid, 4-(meth)acryloyloxybutoxycarbonylphthalic acid, 4-( meth) acryloyloxyhexyloxycarbonyl phthalic acid, 4-(meth) acryloyloxydecyloxycarbonyl phthalic acid and other (meth) acryloyloxyalkoxycarbonyl phthalates, 4-(meth) acryloyloxyethoxyethoxycarbonyl phthalic acid and other (meth) ) acryloyloxyalkoxyalkoxycarbonyl phthalic acids, mono-2-(acryloyloxy)ethyl succinate, 2,2-bis(acryloylamido)acetic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acrylic royloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalate, and 2-(meth)acryloyloxyethylhexahydrophthalate.
　リン酸基を有する（メタ）アクリレート化合物としては、例えば、ビス（２－（メタ）アクリロイルオキシエチル）リン酸エステル、２－ヒドロキシエチル（メタ）アクリレートアシッドホスフェート、エチル（メタ）アクリレートアシッドホスフェート、３－クロロ－２－アシッドホスホキシプロピル（メタ）アクリレート、ポリオキシエチレングリコール（メタ）アクリレートアシッドホスフェート、２－（メタ）アクリロイルオキシエチルカプロエートアシッドホスフェート、モノ－２－（メタアクリロイルオキシ）エチルホスフェートが挙げられる。さらに、２－（メタ）アクリロイルオキシエチルリン酸エステル（２－アクリロイルオキシエチルリン酸エステル又は２－メタクリロイルオキシエチルリン酸エステルを意味し、以下この略記法による）、２－（メタ）アクリロイルオキシプロピルリン酸エステル、３－（メタ）アクリロイルオキシプロピルリン酸エステル、４－（メタ）アクリロイルオキシブチルリン酸エステル、６－（メタ）アクリロイルオキシヘキシルリン酸エステル、８－（メタ）アクリロイルオキシオクチルリン酸エステル、１０－（メタ）アクリロイルオキシデシルリン酸エステル、１２－（メタ）アクリロイルオキシラウリルリン酸エステル、１６－（メタ）アクリロイルオキシセチルリン酸エステル、１８－（メタ）アクリロイルオキシステアリルリン酸エステル、２０－（メタ）アクリロイルオキシエイコシルリン酸エステルなどの（メタ）アクリロイルオキシアルキルリン酸エステル類；１，３－ジ（メタ）アクリロイルオキシプロピル－２－リン酸エステルなどのジ（メタ）アクリロイルオキシアルキルリン酸エステル類；２－（メタ）アクリロイルオキシエチルフェニルリン酸エステル、２－（メタ）アクリロイルオキシエチルアニシルリン酸エステル、２－（メタ）アクリロイルオキシエチルトリルリン酸エステルなどの（メタ）アクリロイルオキシアルキルアリールリン酸エステル類；２－（メタ）アクリロイルオキシエチルフェニルホスホン酸などの（メタ）アクリロイルオキシアルキルアリールホスホン酸類；２－（メタ）アクリロイルオキシエチルチオリン酸エステル、２－（メタ）アクリロイルオキシプロピルチオリン酸エステル、３－（メタ）アクリロイルオキシプロピルチオリン酸エステル、４－（メタ）アクリロイルオキシブチルチオリン酸エステル、６－（メタ）アクリロイルオキシヘキシルチオリン酸エステル、８－（メタ）アクリロイルオキシオクチルチオリン酸エステル、１０－（メタ）アクリロイルオキシデシルチオリン酸エステル、１２－（メタ）アクリロイルオキシラウリルチオリン酸エステル、１６－（メタ）アクリロイルオキシセチルチオリン酸エステル、１８－（メタ）アクリロイルオキシステアリルチオリン酸エステル、２０－（メタ）アクリロイルオキシエイコシルチオリン酸エステルなどの（メタ）アクリロイルオキシアルキルチオリン酸エステル類；１，３－ジ（メタ）アクリロイルオキシプロピル－２－チオリン酸エステルなどのジ（メタ）アクリロイルオキシアルキルチオリン酸エステル類；２－（メタ）アクリロイルオキシエチルフェニルチオリン酸エステル、２－（メタ）アクリロイルオキシエチルアニシルチオリン酸エステル、２－（メタ）アクリロイルオキシエチルトリルチオリン酸エステルなどの（メタ）アクリロイルオキシアルキルアリールチオリン酸エステル類；２－（メタ）アクリロイルオキシエチルフェニルチオホスホン酸などの（メタ）アクリロイルオキシアルキルアリールチオホスホン酸類等を挙げることができる。 (Meth)acrylate compounds having a phosphoric acid group include, for example, bis(2-(meth)acryloyloxyethyl) phosphate, 2-hydroxyethyl (meth)acrylate acid phosphate, ethyl (meth)acrylate acid phosphate, 3 -chloro-2-acid phosphooxypropyl (meth)acrylate, polyoxyethylene glycol (meth)acrylate acid phosphate, 2-(meth)acryloyloxyethyl caproate acid phosphate, mono-2-(methacryloyloxy)ethyl phosphate is mentioned. Furthermore, 2-(meth)acryloyloxyethyl phosphate (meaning 2-acryloyloxyethyl phosphate or 2-methacryloyloxyethyl phosphate, hereinafter according to this abbreviation), 2-(meth)acryloyloxypropyl Phosphate, 3-(meth)acryloyloxypropyl phosphate, 4-(meth)acryloyloxybutyl phosphate, 6-(meth)acryloyloxyhexyl phosphate, 8-(meth)acryloyloxyoctyl phosphate ester, 10-(meth)acryloyloxydecyl phosphate, 12-(meth)acryloyloxylauryl phosphate, 16-(meth)acryloyloxycetyl phosphate, 18-(meth)acryloyloxystearyl phosphate, (meth)acryloyloxy alkyl phosphates such as 20-(meth)acryloyloxy eicosyl phosphate; di(meth)acryloyloxy such as 1,3-di(meth)acryloyloxypropyl-2-phosphate Alkyl phosphates; 2-(meth)acryloyloxyethylphenyl phosphate, 2-(meth)acryloyloxyethylanisyl phosphate, 2-(meth)acryloyloxyethyltolyl phosphate, etc. (meth) Acryloyloxyalkylaryl phosphates; (meth)acryloyloxyalkylarylphosphonic acids such as 2-(meth)acryloyloxyethylphenylphosphonic acid; 2-(meth)acryloyloxyethyl thiophosphates, 2-(meth)acryloyl Oxypropylthiophosphate, 3-(meth)acryloyloxypropylthiophosphate, 4-(meth)acryloyloxybutyl thiophosphate, 6-(meth)acryloyloxyhexylthiophosphate, 8-(meth)acryloyloxyoctyl Thiophosphate, 10-(meth)acryloyloxydecylthiophosphate, 12-(meth)acryloyloxylaurylthiophosphate, 16-(meth)acryloyloxycetylthiophosphate, 18-(meth)acryloyloxystearylthiophosphate esters, (meth)acryloyloxyalkylthiophosphates such as 20-(meth)acryloyloxyeicosyl thiophosphate; di(meth)esters such as 1,3-di(meth)acryloyloxypropyl-2-thiophosphate ( meth)acryloyloxyalkylarylthiophosphates; and (meth)acryloyloxyalkylarylthiophosphonic acids such as 2-(meth)acryloyloxyethylphenylthiophosphonic acid.
　スルホン酸基を有する（メタ）アクリレート化合物としては、例えば、メタリルスルホン酸、ビス（３－スルホプロピル）イタコン酸、２－（スルホキシ）エチルメタアクリル酸、２－アクリルアミド－２－メチル－１－プロパンスルホン酸、３－スルホプロピルアクリル酸、３－スルホプロピルメタアクリル酸、及びアクリルアミド－２－メチル－２－プロパンスルホン酸等が挙げられる。 Examples of (meth)acrylate compounds having a sulfonic acid group include methallylsulfonic acid, bis(3-sulfopropyl)itaconic acid, 2-(sulfoxy)ethyl methacrylic acid, 2-acrylamido-2-methyl-1- Propanesulfonic acid, 3-sulfopropylacrylic acid, 3-sulfopropylmethacrylic acid, acrylamido-2-methyl-2-propanesulfonic acid and the like.
　単官能のヒドロキシ基を有する（メタ）アクリレート化合物としては、例えば、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸１－メチル－２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシシクロヘキシル、（メタ）アクリル酸５－ヒドロキシペンチル、（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸４－ヒドロキシメチルシクロヘキシルメチル、（メタ）アクリル酸ｐ－ヒドロキシメチルフェニルメチル、（メタ）アクリル酸２－（ヒドロキシエトキシ）エチル、（メタ）アクリル酸２－（ヒドロキシエトキシエトキシ）エチル、（メタ）アクリル酸２－（ヒドロキシエトキシエトキシエトキシ）エチル、α－ヒドロキシメチルアクリル酸メチル、α－ヒドロキシメチルアクリル酸エチル、ヒドロキシアルキル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２－メタクリロイロキシエチル－２－ヒドロキシプロピルフタレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、及び２－ヒドロキシ－３－フェノキシプロピルアクリレート等が含まれる。 Examples of (meth)acrylate compounds having a monofunctional hydroxy group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 1-methyl-2-hydroxyethyl (meth)acrylate. , 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate , 4-hydroxymethylcyclohexylmethyl (meth)acrylate, p-hydroxymethylphenylmethyl (meth)acrylate, 2-(hydroxyethoxy)ethyl (meth)acrylate, 2-(hydroxyethoxyethoxy) (meth)acrylate Ethyl, 2-(hydroxyethoxyethoxyethoxy)ethyl (meth)acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, hydroxyalkyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2 -methacryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl acrylate, and the like.
　多官能のヒドロキシ基を有する（メタ）アクリレート化合物としては、例えば、２－ヒドロキシ－３－アクリロイロキシプロピルメタクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、エチレンオキサイド付加ペンタエリスリトールテトラ（メタ）アクリレート、トリメチロールプロパンジアクリレート、グリセリンジ（メタ）アクリレート、グリセリンアクリレートメタクリレート、ペンタエリスリトールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、プロピオン酸ジペンタエリスリトールトリ（メタ）アクリレート、ヒドロキシピバルアルデヒド変性ジメチロールプロパントリ（メタ）アクリレート、ソルビトールトリ（メタ）アクリレート、ソルビトールテトラ（メタ）アクリレート、ソルビトールペンタ（メタ）アクリレート、ソルビトールヘキサ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等が含まれる。 Examples of the (meth)acrylate compound having a polyfunctional hydroxy group include 2-hydroxy-3-acryloyloxypropyl methacrylate, dipentaerythritol penta(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, tri Methylolpropane diacrylate, glycerin di(meth)acrylate, glycerin acrylate methacrylate, pentaerythritol di(meth)acrylate, neopentylglycol hydroxypivalate di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol propionate Tri(meth)acrylate, hydroxypivalaldehyde-modified dimethylolpropane tri(meth)acrylate, sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, sorbitol penta(meth)acrylate, sorbitol hexa(meth)acrylate, pentaerythritol Tri(meth)acrylate and the like are included.
　（メタ）アクリレートは、変性物であってもよい。変性物である（メタ）アクリレートの例には、エチレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールテトラアクリレート等を含むエチレンオキサイド変性（メタ）アクリレート、カプロラクトン変性トリメチロールプロパントリ（メタ）アクリレート等を含むカプロラクトン変性（メタ）アクリレート、並びにカプロラクタム変性ジペンタエリスリトールヘキサ（メタ）アクリレート等を含むカプロラクタム変性（メタ）アクリレート等が含まれる。 (Meth)acrylate may be a modified product. Examples of modified (meth)acrylates include ethylene oxide-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetraacrylate, ethylene oxide-modified (meth)acrylates, caprolactone-modified trimethylolpropane tri( Caprolactone-modified (meth)acrylates including meth)acrylates and caprolactam-modified (meth)acrylates including caprolactam-modified dipentaerythritol hexa(meth)acrylates and the like are included.
　（メタ）アクリレートは、重合性オリゴマーであってもよい。重合性オリゴマーである（メタ）アクリレートの例には、エポキシ（メタ）アクリレートオリゴマー、脂肪族ウレタン（メタ）アクリレートオリゴマー、芳香族ウレタン（メタ）アクリレートオリゴマー、ポリエステル（メタ）アクリレートオリゴマー、及び直鎖（メタ）アクリルオリゴマー等が含まれる。 The (meth)acrylate may be a polymerizable oligomer. Examples of (meth)acrylates that are polymerizable oligomers include epoxy (meth)acrylate oligomers, aliphatic urethane (meth)acrylate oligomers, aromatic urethane (meth)acrylate oligomers, polyester (meth)acrylate oligomers, and linear ( meth)acrylic oligomers and the like are included.
　「カチオン重合性化合物」とは、分子中にカチオン重合性基を有する化合物のことをいう。カチオン重合性化合物の例としては、エポキシ化合物、ビニルエーテル化合物及びオキセタン化合物等が挙げられる。 A "cationically polymerizable compound" refers to a compound having a cationically polymerizable group in its molecule. Examples of cationic polymerizable compounds include epoxy compounds, vinyl ether compounds and oxetane compounds.
　エポキシ化合物の例としては、脂環式エポキシ化合物（３，４－エポキシシクロヘキシルメチル－３′，４′－エポキシシクロヘキサンカルボキシレート、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、ビニルシクロヘキセンモノエポキサイド、ε－カプロラクトン変性３，４－エポキシシクロヘキシルメチル３′，４′－エポキシシクロヘキサンカルボキシレート、１－メチル－４－（２－メチルオキシラニル）－７－オキサビシクロ［４，１，０］ヘプタン、２－（３，４－エポキシシクロヘキシル－５，５－スピロ－３，４－エポキシ）シクロヘキサノン－メタ－ジオキサン、及びビス（２，３－エポキシシクロペンチル）エーテル等）、脂肪族エポキシ化合物（１，４－ブタンジオールのジグリシジルエーテル、１，６－ヘキサンジオールのジグリシジルエーテル、グリセリンのトリグリシジルエーテル、トリメチロールプロパンのトリグリシジルエーテル、ポリエチレングリコールのジグリシジルエーテル、プロピレングリコールのジグリシジルエーテル、ポリエーテルポリオールのポリグリシジルエーテル等）、及び芳香族エポキシ化合物（ビスフェノールＡのジグリシジルエーテル、ビスフェノールＡのアルキレンオキサイド付加体のジグリシジルエーテル、水素添加ビスフェノールＡのジグリシジルエーテル、水素添加ビスフェノールＡのアルキレンオキサイド付加体のジグリシジルエーテル、ビスフェノールＡのポリグリシジルエーテル、ビスフェノールＡのアルキレンオキサイド付加体のポリグリシジルエーテル、水素添加ビスフェノールＡのポリグリシジルエーテル、水素添加ビスフェノールＡのアルキレンオキサイド付加体のポリグリシジルエーテル、及びノボラック型エポキシ樹脂等）等が挙げられる。 Examples of epoxy compounds include alicyclic epoxy compounds (3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene monoepoxide, ε -caprolactone-modified 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, 1-methyl-4-(2-methyloxiranyl)-7-oxabicyclo[4,1,0]heptane, 2 -(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexanone-meta-dioxane, and bis(2,3-epoxycyclopentyl) ether), aliphatic epoxy compounds (1,4- diglycidyl ether of butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of propylene glycol, polyether polyol Polyglycidyl ether, etc.), and aromatic epoxy compounds (diglycidyl ether of bisphenol A, diglycidyl ether of alkylene oxide adduct of bisphenol A, diglycidyl ether of hydrogenated bisphenol A, alkylene oxide adduct of hydrogenated bisphenol A Diglycidyl ether, polyglycidyl ether of bisphenol A, polyglycidyl ether of alkylene oxide adduct of bisphenol A, polyglycidyl ether of hydrogenated bisphenol A, polyglycidyl ether of alkylene oxide adduct of hydrogenated bisphenol A, and novolac type epoxy resin, etc.).
　ビニルエーテル化合物の例としては、エチルビニルエーテル、ｎ－ブチルビニルエーテル、イソブチルビニルエーテル、オクタデシルビニルエーテル、シクロヘキシルビニルエーテル、ヒドロキシブチルビニルエーテル、２－エチルヘキシルビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、ｎ－プロピルビニルエーテル、イソプロピルビニルエーテル、イソプロペニルエーテル－ｏ－プロピレンカーボネート、ドデシルビニルエーテル、ジエチレングリコールモノビニルエーテル、オクタデシルビニルエーテル、エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、ブタンジオールジビニルエーテル、ヘキサンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、及びトリメチロールプロパントリビニルエーテル等が挙げられる。 Examples of vinyl ether compounds include ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether. -o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether vinyl ether, cyclohexanedimethanol divinyl ether, trimethylolpropane trivinyl ether, and the like.
　オキセタン化合物の例としては、３－ヒドロキシメチル－３－メチルオキセタン、３－ヒドロキシメチル－３－エチルオキセタン、３－ヒドロキシメチル－３－プロピルオキセタン、３－ヒドロキシメチル－３－ノルマルブチルオキセタン、３－ヒドロキシメチル－３－フェニルオキセタン、３－ヒドロキシメチル－３－ベンジルオキセタン、３－ヒドロキシエチル－３－メチルオキセタン、３－ヒドロキシエチル－３－エチルオキセタン、３－ヒドロキシエチル－３－プロピルオキセタン、３－ヒドロキシエチル－３－フェニルオキセタン、３－ヒドロキシプロピル－３－メチルオキセタン、３－ヒドロキシプロピル－３－エチルオキセタン、３－ヒドロキシプロピル－３－プロピルオキセタン、３－ヒドロキシプロピル－３－フェニルオキセタン、３－ヒドロキシブチル－３－メチルオキセタン、１，４ビス｛［（３－エチル－３－オキセタニル）メトキシ］メチル｝ベンゼン、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタン、及びジ［１－エチル（３－オキセタニル）］メチルエーテル等が挙げられる。 Examples of oxetane compounds include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3-hydroxymethyl-3-n-butyloxetane, 3- Hydroxymethyl-3-phenyloxetane, 3-hydroxymethyl-3-benzyloxetane, 3-hydroxyethyl-3-methyloxetane, 3-hydroxyethyl-3-ethyloxetane, 3-hydroxyethyl-3-propyloxetane, 3- Hydroxyethyl-3-phenyloxetane, 3-hydroxypropyl-3-methyloxetane, 3-hydroxypropyl-3-ethyloxetane, 3-hydroxypropyl-3-propyloxetane, 3-hydroxypropyl-3-phenyloxetane, 3- Hydroxybutyl-3-methyloxetane, 1,4 bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, and di[1- ethyl(3-oxetanyl)]methyl ether and the like.
　本発明に係る光重合性組成物は、必要に応じて、光重合開始剤を含むことが好ましい。 The photopolymerizable composition according to the present invention preferably contains a photopolymerization initiator as necessary.
　光重合開始剤の含有量は、活性エネルギー線の照射によってインクが十分に硬化し、かつ、インクのインクジェット吐出安定性を低下させない範囲において、任意に設定することができる。例えば、光重合開始剤の含有量は、インク全体に対して、０．１～２０質量％の範囲内であることが好ましく、１．０～１２質量％の範囲内であることがより好ましい。 The content of the photopolymerization initiator can be arbitrarily set within a range in which the ink is sufficiently cured by the irradiation of the active energy ray and the inkjet ejection stability of the ink is not lowered. For example, the content of the photopolymerization initiator is preferably within the range of 0.1 to 20% by mass, more preferably within the range of 1.0 to 12% by mass, relative to the total ink.
　光重合開始剤は、上記重合性化合物の重合を開始できるものであればよい。例えば、インクがラジカル重合性化合物を有する場合は、光重合開始剤はラジカル系光重合開始剤とし、インクがカチオン重合性化合物を有する場合は、光重合開始剤はカチオン系光重合開始剤とする。 Any photopolymerization initiator may be used as long as it can initiate the polymerization of the polymerizable compound. For example, when the ink contains a radical polymerizable compound, the photopolymerization initiator is a radical photopolymerization initiator, and when the ink contains a cationically polymerizable compound, the photopolymerization initiator is a cationic photopolymerization initiator. .
　光重合開始剤は、一種類のみを単独で用いてもよく、二種類以上を併用してもよい。また、ラジカル系光重合開始剤及びカチオン系光重合開始剤の両方を組み合わせてもよい。 Only one type of photopolymerization initiator may be used alone, or two or more types may be used in combination. Also, both the radical photopolymerization initiator and the cationic photopolymerization initiator may be combined.
　ラジカル系光重合開始剤としては、分子内結合開裂型と分子内水素引き抜き型とがある。 Radical photopolymerization initiators include an intramolecular bond cleavage type and an intramolecular hydrogen abstraction type.
　分子内結合開裂型のラジカル系光重合開始剤の例としては、アセトフェノン系光重合開始剤（ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、ベンジルジメチルケタール、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、４－（２－ヒドロキシエトキシ）フェニル－（２－ヒドロキシ－２－プロピル）ケトン、１－ヒドロキシシクロヘキシル－フェニルケトン、２－メチル－２－モルホリノ（４－メチルチオフェニル）プロパン－１－オン、及び２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン等）、ベンゾイン系光重合開始剤（ベンゾイン、ベンゾインメチルエーテル、及びベンゾインイソプロピルエーテル等）、アシルフォスフィンオキサイド系光重合開始剤（２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルフォスフィンオキサイド等）、ベンジル、及びメチルフェニルグリオキシエステル等が挙げられる。 Examples of the intramolecular bond cleavage type radical photopolymerization initiator include acetophenone photopolymerization initiators (diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1 -(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino(4-methylthiophenyl)propan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, etc.), benzoin-based photopolymerization initiators (benzoin , benzoin methyl ether, and benzoin isopropyl ether), acylphosphine oxide photopolymerization initiators (2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide), benzyl, and methylphenyl glyoxyester.
　これらの中でも、重合性化合物の硬化性がより向上し、特にＵＶ－ＬＥＤの光による硬化プロセスによる硬化性がより向上する観点から、アシルフォスフィンオキサイド系光重合開始剤であることが好ましい。 Among these, acylphosphine oxide-based photopolymerization initiators are preferable from the viewpoint of further improving the curability of the polymerizable compound, and particularly from the viewpoint of further improving the curability of the curing process by UV-LED light.
　アシルフォスフィンオキサイド系光重合開始剤の市販品としては、例えば、ＩＲＧＡＣＵＲＥ（登録商標）８１９（ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド）、ＩＲＧＡＣＵＲＥ（登録商標）１８００（ビス－（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルフォスフィンオキサイドと、１－ヒドロキシ－シクロヘキシル－フェニルケトンの質量比２５：７５の混合物）、ＩＲＧＡＣＵＲＥ（登録商標）ＴＰＯ（２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド）等が挙げられる。 Commercially available acylphosphine oxide photopolymerization initiators include, for example, IRGACURE (registered trademark) 819 (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), IRGACURE (registered trademark) 1800 (bis -(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 1-hydroxy-cyclohexyl-phenylketone in a mass ratio of 25:75), IRGACURE® TPO (2, 4,6-trimethylbenzoyldiphenylphosphine oxide) and the like.
　分子内水素引き抜き型のラジカル系光重合開始剤の例としては、ベンゾフェノン系光重合開始剤（ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、４，４′－ジクロロベンゾフェノン、ヒドロキシベンゾフェノン、４－ベンゾイル－４′－メチル－ジフェニルサルファイド、アクリル化ベンゾフェノン、３，３′，４，４′－テトラ（ｔ－ブチルペルオキシカルボニル）ベンゾフェノン、及び３，３′－ジメチル－４－メトキシベンゾフェノン等）、チオキサントン系光重合開始剤（２－イソプロピルチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン等）、アミノベンゾフェノン系光重合開始剤（ミヒラーケトン、４，４′－ジエチルアミノベンゾフェノン等）、１０－ブチル－２－クロロアクリドン、２－エチルアンスラキノン、９，１０－フェナンスレンキノン、及びカンファーキノン等が挙げられる。 Examples of intramolecular hydrogen abstraction type radical photopolymerization initiators include benzophenone photopolymerization initiators (benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4 -benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone, etc.), Thioxanthone photoinitiators (2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, etc.), aminobenzophenone photoinitiators (Michler ketone, 4,4'- diethylaminobenzophenone, etc.), 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone.
　カチオン系光重合開始剤の例としては、光酸発生剤が挙げられる。さらに、光酸発生剤の例としては、ジアゾニウム、アンモニウム、ヨードニウム、スルホニウム、及びホスホニウムなどを含む芳香族オニウム化合物のＢ（Ｃ６Ｆ５）４ －、ＰＦ６ －、ＡｓＦ６ －、ＳｂＦ６ －、ＣＦ３ＳＯ３ －塩など、スルホン酸を発生するスルホン化物、ハロゲン化水素を光発生するハロゲン化物、並びに鉄アレン錯体などが含まれる。 Examples of cationic photopolymerization initiators include photoacid generators. Further examples of photoacid generators include aromatic onium compounds B(C 6 F 5 ) 4 − , PF 6 − , AsF 6 − , SbF 6 − including diazonium, ammonium, iodonium, sulfonium, and phosphonium. , CF 3 SO 3 -salts , sulfonates that generate sulfonic acids, halides that photogenerate hydrogen halides, and iron allene complexes.
（白色色材）
　本発明のインクは、白色色材を含有することを特徴とする。白色色材は、顔料であっても染料であってもよい。 (white colorant)
The ink of the present invention is characterized by containing a white colorant. The white colorant may be a pigment or a dye.
　白色白色の含有率は、特に限定されないが、インク全体に対して、２～３０質量％の範囲内であることが好ましく、５～２０質量％の範囲内であることがより好ましく、６～１５質量％の範囲内であることがさらに好ましい。 The white content is not particularly limited, but is preferably in the range of 2 to 30% by mass, more preferably in the range of 5 to 20% by mass, and more preferably in the range of 6 to 15% by mass. It is more preferable to be within the mass % range.
　以下、本発明のインクが含有する白色色材として好適に用いられる白色顔料について、具体的に説明する。 The white pigment suitably used as the white colorant contained in the ink of the present invention will be specifically described below.
　白色顔料の例には、炭酸カルシウム、硫酸バリウム、酸化チタン、酸化亜鉛、硫化亜鉛、酸化アンチモン、酸化ジルコニウム、白色の中空樹脂粒子、及び高分子粒子が含まれる。上記白色顔料の中では、酸化チタン、酸化ジルコニウムが好ましく、酸化チタンがより好ましい。 Examples of white pigments include calcium carbonate, barium sulfate, titanium oxide, zinc oxide, zinc sulfide, antimony oxide, zirconium oxide, white hollow resin particles, and polymer particles. Among the above white pigments, titanium oxide and zirconium oxide are preferred, and titanium oxide is more preferred.
　また、本発明に用いることのできる市販の酸化チタンの例には、ＣＲ－ＥＬ、ＣＲ－５０、ＣＲ－８０、ＣＲ－９０、Ｒ－７８０、Ｒ－９３０（いずれも石原産業社製）、ＴＣＲ－５２、Ｒ－２５、Ｒ－３２、Ｒ－３１０（いずれも堺化学工業社製）、ＫＲ－３１０、ＫＲ－３８０、及びＫＲ－３８０Ｎ（いずれもチタン工業社製）等が含まれる。 Examples of commercially available titanium oxide that can be used in the present invention include CR-EL, CR-50, CR-80, CR-90, R-780, and R-930 (all manufactured by Ishihara Sangyo Co., Ltd.), TCR-52, R-25, R-32, R-310 (all manufactured by Sakai Chemical Industry Co., Ltd.), KR-310, KR-380 and KR-380N (all manufactured by Titan Kogyo Co., Ltd.) and the like are included.
　また、上記白色顔料として使用できる酸化ジルコニウムの例には、市販品のＺｉｒｃｏｎｅｏ（アイテック社製、「Ｚｉｒｃｏｎｅｏ」は同社の登録商標）が含まれる。 Examples of zirconium oxide that can be used as the white pigment include commercially available Zirconeo (manufactured by Aitec, "Zirconeo" is a registered trademark of the company).
　顔料の分散は、例えば、ボールミル、サンドミル、アトライター、ロールミル、アジテータ、ヘンシェルミキサ、コロイドミル、超音波ホモジナイザー、パールミル、湿式ジェットミル、及びペイントシェーカー等により行うことができる。 Dispersion of pigments can be carried out by, for example, ball mills, sand mills, attritors, roll mills, agitators, Henschel mixers, colloid mills, ultrasonic homogenizers, pearl mills, wet jet mills, and paint shakers.
　白色色材として白色顔料を用いる場合、インクジェットヘッドからの吐出性をより高める観点からは、顔料粒子の平均分散粒子径は、５０～１５０ｎｍの範囲内であり、最大粒子径は３００～１０００ｎｍの範囲内であることが好ましい。さらに好ましい平均分散粒子径は８０～１３０ｎｍの範囲内である。 When a white pigment is used as the white colorant, the average dispersed particle diameter of the pigment particles is in the range of 50 to 150 nm, and the maximum particle diameter is in the range of 300 to 1000 nm, from the viewpoint of further improving the ejection property from the inkjet head. preferably within A more preferable average dispersed particle size is in the range of 80 to 130 nm.
　本発明における顔料粒子の平均分散粒子径とは、データサイザーナノＺＳＰ、Ｍａｌｖｅｒｎ社製を使用して動的光散乱法によって求めた値を意味する。なお、色材を含むインクは濃度が高く、この測定機器では光が透過しないので、インクを２００倍で希釈してから測定する。測定温度は常温（２５℃）とする。 The average dispersed particle size of pigment particles in the present invention means a value obtained by a dynamic light scattering method using Datasizer Nano ZSP, manufactured by Malvern. In addition, the ink containing the coloring material has a high density and does not transmit light in this measurement device, so the measurement is performed after diluting the ink by 200 times. The measurement temperature is normal temperature (25°C).
　顔料の分散は、顔料、分散剤、分散媒体、分散条件、及び濾過条件等によって、調整される。 The dispersion of the pigment is adjusted by the pigment, dispersant, dispersion medium, dispersion conditions, filtration conditions, and the like.
　本発明のインクは、色材として顔料を用いる場合、顔料の分散性を高めるために、分散剤をさらに含んでもよい。
　分散剤の例には、ヒドロキシ基を有するカルボン酸エステル、長鎖ポリアミノアマイドと高分子量酸エステルの塩、高分子量ポリカルボン酸の塩、長鎖ポリアミノアマイドと極性酸エステルの塩、高分子量不飽和酸エステル、高分子共重合物、変性ポリウレタン、変性ポリアクリレート、ポリエーテルエステル型アニオン系活性剤、ナフタレンスルホン酸ホルマリン縮合物塩、芳香族スルホン酸ホルマリン縮合物塩、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンノニルフェニルエーテル、及びステアリルアミンアセテート等が含まれる。分散剤の市販品の例には、Ａｖｅｃｉａ社のＳｏｌｓｐｅｒｓｅシリーズ、及び味の素ファインテクノ社製のＰＢシリーズ等が含まれる。 When a pigment is used as the colorant, the ink of the present invention may further contain a dispersant in order to improve the dispersibility of the pigment.
Examples of dispersants include carboxylic acid esters having hydroxy groups, salts of long-chain polyaminoamides and high-molecular-weight acid esters, salts of high-molecular-weight polycarboxylic acids, salts of long-chain polyaminoamides and polar acid esters, high-molecular-weight unsaturated acid esters, polymer copolymers, modified polyurethanes, modified polyacrylates, polyether ester type anionic surfactants, naphthalene sulfonic acid formalin condensate salts, aromatic sulfonic acid formalin condensate salts, polyoxyethylene alkyl phosphate esters, Polyoxyethylene nonylphenyl ether, stearylamine acetate, and the like are included. Examples of commercially available dispersants include Solsperse series from Avecia, PB series from Ajinomoto Fine-Techno Co., Ltd., and the like.
　本発明のインクは、色材として顔料を用いる場合、必要に応じて分散助剤を含有してもよい。分散助剤は、顔料に応じて選択されればよい。 The ink of the present invention may contain a dispersing aid as necessary when using a pigment as a coloring material. A dispersing aid may be selected according to the pigment.
　分散剤及び分散助剤の合計量は、顔料に対して１～５０質量％の範囲内であることが好ましい。 The total amount of the dispersant and dispersing aid is preferably within the range of 1 to 50% by mass based on the pigment.
　本発明のインクは、色材として顔料を用いる場合、必要に応じて顔料を分散させるための分散媒体を含有してもよい。分散媒体としては、溶剤でもよいが、ＬＥＤチップへのダメージを抑制するためには、前述のような重合性化合物（特に粘度の低いモノマー）を分散媒体として用いることが好ましい。 When a pigment is used as a coloring material, the ink of the present invention may contain a dispersion medium for dispersing the pigment, if necessary. A solvent may be used as the dispersing medium, but in order to suppress damage to the LED chip, it is preferable to use a polymerizable compound (especially a monomer having a low viscosity) as the dispersing medium.
（白色色材以外の色材）
　本発明のインクは、本発明の効果が得られる範囲において、白色色材以外の色材を更に含有していてもよい。 (Coloring materials other than white coloring materials)
The ink of the present invention may further contain a colorant other than the white colorant as long as the effects of the present invention can be obtained.
　以下、白色色材以外の色材として好適に用いられる顔料について、具体的に説明する。 Pigments suitably used as colorants other than the white colorant will be specifically described below.
　黒色顔料の例には、Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　７、２８、２６、から選ばれる顔料又はその混合物等が含まれる。 Examples of black pigments include pigments selected from Pigment Black 7, 28, 26, or mixtures thereof.
　黒色顔料の市販品の例には、Ｂｌａｃｋ　Ｐｉｇｍｅｎｔ（Ｍｉｋｕｎｉ社製）、クロモファインブラックＡ－１１０３（大日精化工業社製）、Ｃｏｌｏｒｔｅｘ　Ｂｌａｃｋ　７０２、Ｕ９０５（山陽色素社製）、カーボンブラック＃２６００、＃２４００、＃２３５０、＃２２００、＃１０００、＃９９０、＃９８０、＃９７０、＃９６０、＃９５０、＃８５０、ＭＣＦ８８、＃７５０、＃６５０、ＭＡ６００、ＭＡ７、ＭＡ８、ＭＡ１１、ＭＡ１００、ＭＡ１００Ｒ、ＭＡ７７、＃５２、＃５０、＃４７、＃４５、＃４５Ｌ、＃４０、＃３３、＃３２、＃３０、＃２５、＃２０、＃１０、＃５、＃４４、及びＣＦ９（以上、三菱ケミカル社製）等が含まれる。 Examples of commercially available black pigments include Black Pigment (manufactured by Mikuni), Chromo Fine Black A-1103 (manufactured by Dainichi Seika Kogyo Co., Ltd.), Colortex Black 702, U905 (manufactured by Sanyo Color Co., Ltd.), carbon black #2600, #2400, #2350, #2200, #1000, #990, #980, #970, #960, #950, #850, MCF88, #750, #650, MA600, MA7, MA8, MA11, MA100, MA100R, MA77, #52, #50, #47, #45, #45L, #40, #33, #32, #30, #25, #20, #10, #5, #44, and CF9 (Mitsubishi chemical company) and the like.
　赤色又はマゼンタ顔料の例には、Ｐｉｇｍｅｎｔ　Ｒｅｄ　３、５、１９、２２、３１、３８、４３、４８：１、４８：２、４８：３、４８：４、４８：５、４９：１、５３：１、５７：１、５７：２、５８：４、６３：１、８１、８１：１、８１：２、８１：３、８１：４、８８、１０４、１０８、１１２、１２２、１２３、１４４、１４６、１４９、１６６、１６８、１６９、１７０、１７７、１７８、１７９、１８４、１８５、２０８、２１６、２２６、２５７、Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　３、１９、２３、２９、３０、３７、５０、８８、Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　１３、１６、２０、及び３６から選ばれる顔料又はその混合物等が含まれる。 Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53 : 1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144 , 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Pigments selected from Orange 13, 16, 20, and 36, or mixtures thereof, etc. are included.
　青色又はシアン顔料の例には、Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１、１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、１７－１、２２、２７、２８、２９、３６、及び６０から選ばれる顔料又はその混合物等が含まれる。 Examples of blue or cyan pigments include Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36 , and 60, or mixtures thereof, and the like.
　緑色顔料の例には、Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７、２６、３６、及び５０から選ばれる顔料又はその混合物が含まれる。 Examples of green pigments include pigments selected from Pigment Green 7, 26, 36, and 50, or mixtures thereof.
　黄色顔料の例には、Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１、３、１２、１３、１４、１７、３４、３５、３７、５５、７４、８１、８３、９３、９４，９５、９７、１０８、１０９、１１０、１３７、１３８、１３９、１５３、１５４、１５５、１５７、１６６、１６７、１６８、１８０、１８５、及び１９３から選ばれる顔料又はその混合物等が含まれる。 Examples of yellow pigments include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137 , 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, and 193, or mixtures thereof, and the like.
　顔料の市販品の例には、上記挙げたもの以外にも、クロモファインイエロー２０８０、５９００、５９３０、ＡＦ－１３００、２７００Ｌ、クロモファインオレンジ３７００Ｌ、６７３０、クロモファインスカーレット６７５０、クロモファインマゼンタ６８８０、６８８６、６８９１Ｎ、６７９０、６８８７、クロモファインバイオレット　ＲＥ、クロモファインレッド６８２０、６８３０、クロモファインブルーＨＳ－３、５１８７、５１０８、５１９７、５０８５Ｎ、ＳＲ－５０２０、５０２６、５０５０、４９２０、４９２７、４９３７、４８２４、４９３３ＧＮ－ＥＰ、４９４０、４９７３、５２０５、５２０８、５２１４、５２２１、５０００Ｐ、クロモファイングリーン２ＧＮ、２ＧＯ、２Ｇ－５５０Ｄ、５３１０、５３７０、６８３０、セイカファストイエロー１０ＧＨ、Ａ－３、２０３５、２０５４、２２００、２２７０、２３００、２４００（Ｂ）、２５００、２６００、ＺＡＹ－２６０、２７００（Ｂ）、２７７０、セイカファストレッド８０４０、Ｃ４０５（Ｆ）、ＣＡ１２０、ＬＲ－１１６、１５３１Ｂ、８０６０Ｒ、１５４７、ＺＡＷ－２６２、１５３７Ｂ、ＧＹ、４Ｒ－４０１６、３８２０、３８９１、ＺＡ－２１５、セイカファストカーミン６Ｂ１４７６Ｔ－７、１４８３ＬＴ、３８４０、３８７０、セイカファストボルドー１０Ｂ－４３０、セイカライトローズＲ４０、セイカライトバイオレットＢ８００、７８０５、セイカファストマルーン４６０Ｎ、セイカファストオレンジ９００、２９００、セイカライトブルーＣ７１８、Ａ６１２、シアニンブルー４９３３Ｍ、４９３３ＧＮ－ＥＰ、４９４０、４９７３（大日精化工業社製）；　ＫＥＴ　Ｙｅｌｌｏｗ　４０１、４０２、４０３、４０４、４０５、４０６、４１６、４２４、ＫＥＴ　Ｏｒａｎｇｅ　５０１、ＫＥＴ　Ｒｅｄ　３０１、３０２、３０３、３０４、３０５、３０６、３０７、３０８、３０９、３１０、３３６、３３７、３３８、３４６、ＫＥＴ　Ｂｌｕｅ　１０１、１０２、１０３、１０４、１０５、１０６、１１１、１１８、１２４、ＫＥＴ　Ｇｒｅｅｎ　２０１（ＤＩＣ社製）；Ｃｏｌｏｒｔｅｘ　Ｙｅｌｌｏｗ　３０１、３１４、３１５、３１６、Ｐ－６２４、３１４、Ｕ１０ＧＮ、Ｕ３ＧＮ、ＵＮＮ、ＵＡ－４１４、Ｕ２６３、Ｆｉｎｅｃｏｌ　Ｙｅｌｌｏｗ　Ｔ－１３、Ｔ－０５、Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ１７０５、Ｃｏｌｏｒｔｅｘ　Ｏｒａｎｇｅ　２０２、Ｃｏｌｏｒｔｅｘ　Ｒｅｄ１０１、１０３、１１５、１１６、Ｄ３Ｂ、Ｐ－６２５、１０２、Ｈ－１０２４、１０５Ｃ、ＵＦＮ、ＵＣＮ、ＵＢＮ、Ｕ３ＢＮ、ＵＲＮ、ＵＧＮ、ＵＧ２７６、Ｕ４５６、Ｕ４５７、１０５Ｃ、ＵＳＮ、Ｃｏｌｏｒｔｅｘ　Ｍａｒｏｏｎ６０１、Ｃｏｌｏｒｔｅｘ　ＢｒｏｗｎＢ６１０Ｎ、Ｃｏｌｏｒｔｅｘ　Ｖｉｏｌｅｔ６００、Ｐｉｇｍｅｎｔ　Ｒｅｄ　１２２、ＣｏｌｏｒｔｅｘＢｌｕｅ５１６、５１７、５１８、５１９、Ａ８１８、Ｐ－９０８、５１０、Ｃｏｌｏｒｔｅｘ　Ｇｒｅｅｎ４０２、４０３、；Ｌｉｏｎｏｌ　Ｙｅｌｌｏｗ１４０５Ｇ、Ｌｉｏｎｏｌ　Ｂｌｕｅ　ＦＧ７３３０、ＦＧ７３５０、ＦＧ７４００Ｇ、ＦＧ７４０５Ｇ、ＥＳ、ＥＳＰ－Ｓ（東洋インキ社製）、Ｔｏｎｅｒ　Ｍａｇｅｎｔａ　Ｅ０２、Ｐｅｒｍａｎｅｎｔ　ＲｕｂｉｎＦ６Ｂ、Ｔｏｎｅｒ　Ｙｅｌｌｏｗ　ＨＧ、Ｐｅｒｍａｎｅｎｔ　Ｙｅｌｌｏｗ　ＧＧ－０２、Ｈｏｓｔａｐｅａｍ　ＢｌｕｅＢ２Ｇ（ヘキストインダストリー社製）；Ｎｏｖｏｐｅｒｍ　Ｐ－ＨＧ、及びＨｏｓｔａｐｅｒｍ　Ｐｉｎｋ　Ｅ、Ｈｏｓｔａｐｅｒｍ　Ｂｌｕｅ　Ｂ２Ｇ（クラリアント社製）等が挙げられる。 Examples of commercially available pigments include, in addition to those listed above, Chromofine Yellow 2080, 5900, 5930, AF-1300, 2700L, Chromofine Orange 3700L, 6730, Chromofine Scarlet 6750, Chromofine Magenta 6880, 6886 , 6891N, 6790, 6887, Chromofine Violet RE, Chromofine Red 6820, 6830, Chromofine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, 5000P, Chromo Fine Green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400 (B), 2500, 2600, ZAY-260, 2700 (B), 2770, Seika Fast Red 8040, C405 (F), CA120, LR-116, 1531B, 8060R, 1547, ZAW-262, 1537B, GY, 4R-4016, 3820, 3891, ZA-215, Seika Fast Carmin 6B1476T-7, 1483LT, 3840, 3870, Seika Fast Bordeaux 10B-430, Seika Light Rose R40, Seika Light Violet B800, 7805, Seika Fast Maroon 460N, Seika Fast Orange 900, 2900, Seika Light Blue C718, A612, Cyanine Blue 4933M, 4933GN-EP, 4940, 4973 (manufactured by Dainichi Seika Kogyo Co., Ltd.); KET Yellow 401, 402, 403, 404, 405, 406 , 416, 424, KET Orange 501, KET Red 301, 302, 303, 304, 305, 306, 307, 308, 309, 310, 336, 337, 338, 346, KET Blue 101, 102, 103, 104, 105 , 106, 111, 118, 124, KET Green 201 (manufactured by DIC); Colortex Yellow 301, 314, 315, 316, P-624, 314, U10GN, U3GN, UNN, UA-414, U263, Finecol Yellow T- 13, T-05, Pigment Yellow 1705, Colortex Orange 202, Colortex Red 101, 103, 115, 116, D3B, P-625, 102, H-1024, 105C, UFN, UCN, UBN, U3BN, URN, UGN, UG276, U456, U457, 105C, USN, Colortex Maroon 601, Colortex Brown B610N, Colortex Violet 600, Pigment Red 122, Colortex Blue 516, 517, 518, 519, A818, P-908, 510, Colortex　Green 402, 403; Lionol Yellow 1405G, Lionol Blue FG7330, FG7350, FG7400G, FG7405G, ES, ESP-S (manufactured by Toyo Ink), Toner Magenta E02, Permanent Rubin F6B, Toner Yellow HG, Permanent Yellow GG-02, Hostapeam Blue B2G (manufactured by Hoechst Industry); Novoperm P-HG, and Hostaperm Pink E, Hostaperm Blue B2G (manufactured by Clariant) and the like.
（標準沸点が２５０℃以下である溶剤）
　本発明のインクは、標準沸点（１気圧下での沸点）が２５０℃以下である溶剤の含有量が、２５％以下であることを特徴とする。これによって、ＬＥＤチップへのダメージを抑制することができ、また、環境負荷も低減させることができる。標準沸点が２５０℃以下である溶剤の含有量は、１０％以下であることがより好ましく、１％以下であることがさらに好ましい。 (Solvents with a normal boiling point of 250°C or less)
The ink of the present invention is characterized in that the content of a solvent having a normal boiling point (boiling point under 1 atm) of 250° C. or less is 25% or less. As a result, damage to the LED chip can be suppressed, and environmental load can be reduced. The content of the solvent having a normal boiling point of 250° C. or less is more preferably 10% or less, more preferably 1% or less.
　標準沸点が２５０℃以下である溶剤としては、例えば、メチルアルコール、エチルアルコール、Ｎ－プロピルアルコール、及びｉ－プロピルアルコールなどのアルコール系溶媒；メトキシアルコール、及びエトキシアルコールなどのセロソルブ系溶媒；メトキシエトキシエタノール、及びエトキシエトキシエタノールなどのカルビトール系溶媒；酢酸エチル、酢酸ブチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル、及び乳酸エチルなどのエステル系溶媒；アセトン、メチルイソブチルケトン、及びシクロヘキサノンなどのケトン系溶媒；メトキシエチルアセテート、プロピレングリコールモノメチルエーテルアセテート、３－メトキシ－３－メチル－１－ブチルアセテート、３－メトキシブチルアセテート、メトキシブチルアセテート、エトキシエチルアセテート、及びエチルセロソルブアセテートなどのセロソルブアセテート系溶媒；メトキシエトキシエチルアセテート、エトキシエトキシエチルアセテート、及びブチルカルビトールアセテート（ＢＣＡ）などのカルビトールアセテート系溶媒；ジエチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、及びテトラヒドロフランなどのエーテル系溶媒；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、及びＮ－メチルピロリドンなどの非プロトン性アミド溶媒；γ－ブチロラクトンなどのラクトン系溶媒；ベンゼン、トルエン、キシレン、及びナフタレンなどの不飽和炭化水素系溶媒；Ｎ－ヘプタン、Ｎ－ヘキサン、及びＮ－オクタンなどの飽和炭化水素系溶媒などの有機溶媒が挙げられる。 Examples of solvents having a normal boiling point of 250° C. or lower include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol; cellosolve solvents such as methoxy alcohol and ethoxy alcohol; Carbitol solvents such as ethanol and ethoxyethoxyethanol; Ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate; Ketone solvents such as acetone, methyl isobutyl ketone, and cyclohexanone. Solvent; cellosolve acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butyl carbitol acetate (BCA); ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, and tetrahydrofuran; N Aprotic amide solvents such as , N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; Lactone solvents such as γ-butyrolactone; Unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; Solvent; organic solvents such as saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane.
（その他の成分）
　本発明のインクは、本発明の効果が得られる範囲において、重合禁止剤及び界面活性剤を含むその他の成分を更に含有していてもよい。これらの成分は、本発明のインク中に、１種のみが含有されていてもよく、２種類以上が含有されていてもよい。 (other ingredients)
The ink of the present invention may further contain other components including a polymerization inhibitor and a surfactant as long as the effects of the present invention can be obtained. The ink of the present invention may contain only one type of these components, or two or more types thereof.
　重合禁止剤の例には、（アルキル）フェノール、ハイドロキノン、カテコール、レゾルシン、ｐ－メトキシフェノール、ｔ－ブチルカテコール、ｔ－ブチルハイドロキノン、ピロガロール、１，１－ピクリルヒドラジル、フェノチアジン、ｐ－ベンゾキノン、ニトロソベンゼン、２，５－ジ－ｔ－ブチル－ｐ－ベンゾキノン、ジチオベンゾイルジスルフィド、ピクリン酸、クペロン、アルミニウムＮ－ニトロソフェニルヒドロキシアミン、トリ－ｐ－ニトロフェニルメチル、Ｎ－（３－オキシアニリノ－１，３－ジメチルブチリデン）アニリンオキシド、ジブチルクレゾール、シクロヘキサノンオキシムクレゾール、グアヤコール、ｏ－イソプロピルフェノール、ブチラルドキシム、メチルエチルケトキシム及びシクロヘキサノンオキシムが含まれる。 Examples of polymerization inhibitors include (alkyl)phenol, hydroquinone, catechol, resorcinol, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone. , nitrosobenzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cupferron, aluminum N-nitrosophenylhydroxyamine, tri-p-nitrophenylmethyl, N-(3-oxyanilino- 1,3-dimethylbutylidene)aniline oxide, dibutyl cresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime and cyclohexanone oxime.
　重合禁止剤の市販品の例には、Ｉｒｇａｓｔａｂ　ＵＶ１０（ＢＡＳＦ社製）、Ｇｅｎｏｒａｄ　１８（Ｒａｈｎ　Ａ．Ｇ．社製）等が含まれる。 Examples of commercially available polymerization inhibitors include Irgastab UV10 (manufactured by BASF) and Genorad 18 (manufactured by Rahn AG).
　重合禁止剤の量は、本発明の効果が得られる範囲において、任意に設定することができる。重合禁止剤の量は、インク全体に対して、例えば０．００１質量％以上１．０質量％未満とすることができる。 The amount of the polymerization inhibitor can be arbitrarily set within the range where the effects of the present invention can be obtained. The amount of the polymerization inhibitor can be, for example, 0.001% by mass or more and less than 1.0% by mass with respect to the entire ink.
　界面活性剤の例には、ジアルキルスルホコハク酸塩類、アルキルナフタレンスルホン酸塩類及び脂肪酸塩類等のアニオン性界面活性剤、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルアリルエーテル類、アセチレングリコール類及びポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類等のノニオン性界面活性剤、アルキルアミン塩類、及び第四級アンモニウム塩類等のカチオン性界面活性剤、並びにシリコーン系やフッ素系の界面活性剤が含まれる。 Examples of surfactants include anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates and fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols and polyoxy Nonionic surfactants such as ethylene/polyoxypropylene block copolymers, cationic surfactants such as alkylamine salts and quaternary ammonium salts, and silicone-based and fluorine-based surfactants are included.
　シリコーン系の界面活性剤の例には、ポリエーテル変性ポリシロキサン化合物、具体的には、Ｔｅｇｏ　ｒａｄ　２２５０（Ｅｖｏｎｉｋ社製）、ＫＦ－３５１Ａ、ＫＦ－３５２Ａ、ＫＦ－６４２及びＸ－２２－４２７２（以上、信越化学工業社製）、ＢＹＫ３０７、ＢＹＫ３４５、ＢＹＫ３４７及びＢＹＫ３４８（以上、ビッグケミー社製、「ＢＹＫ」は同社の登録商標）、並びにＴＳＦ４４５２（モメンティブ・パフォーマンス・マテリアルズ社製）が含まれる。 Examples of silicone-based surfactants include polyether-modified polysiloxane compounds, specifically Tegorad 2250 (manufactured by Evonik), KF-351A, KF-352A, KF-642 and X-22-4272 ( BYK307, BYK345, BYK347 and BYK348 (manufactured by Big Chemie, "BYK" is a registered trademark of the same company), and TSF4452 (manufactured by Momentive Performance Materials).
　フッ素系の界面活性剤は、通常の界面活性剤の疎水性基の炭素に結合した水素の代わりに、その一部又は全部をフッ素で置換したものを意味する。フッ素系の界面活性剤の例には、Ｍｅｇａｆａｃ　Ｆ（ＤＩＣ社製、「Ｍｅｇａｆａｃ」は同社の登録商標）、Ｓｕｒｆｌｏｎ（ＡＧＣセイケミカル社製、「Ｓｕｒｆｌｏｎ」は同社の登録商標）、Ｆｌｕｏｒａｄ　ＦＣ（３Ｍ社製、「Ｆｌｕｏｒａｄ」は同社の登録商標）、Ｍｏｎｆｌｏｒ（インペリアル・ケミカル・インダストリー社製）、Ｚｏｎｙｌｓ（イー・アイ・デュポン・ネメラス・アンド・カンパニー社製）、Ｌｉｃｏｗｅｔ　ＶＰＦ（ルベベルケ・ヘキスト社製）、及びＦＴＥＲＧＥＮＴ（ネオス社製、「ＦＴＥＲＧＥＮＴ」は同社の登録商標）が含まれる。 　Fluorine-based surfactants mean those in which some or all of the hydrogen atoms in the hydrophobic groups of ordinary surfactants are replaced with fluorine. Examples of fluorine-based surfactants include Megafac F (manufactured by DIC, "Megafac" is a registered trademark of the company), Surflon (manufactured by AGC Seikagaku, "Surflon" is a registered trademark of the company), Fluorad FC (3M company, "Fluorad" is a registered trademark of the company), Monflor (manufactured by Imperial Chemical Industries), Zonyls (manufactured by EI Dupont Nemerus and Company), Licowet VPF (manufactured by Lubewerke Hoechst) , and FTERGENT (manufactured by Neos, "FTERGENT" is a registered trademark of the same company).
　界面活性剤の量は、本発明の効果が得られる範囲において、任意に設定することができる。界面活性剤の量は、インク全体に対して、例えば０．００１質量％以上１．０質量％未満とすることができる。 The amount of surfactant can be arbitrarily set within the range where the effects of the present invention can be obtained. The amount of surfactant can be, for example, 0.001% by mass or more and less than 1.0% by mass with respect to the entire ink.
＜１．３　インクの色＞
　本発明のインクの色は、白色又は灰色であることが好ましく、白色であることが特に好ましい。インクの色は、各色の色材の含有量により調整することができる。 <1.3 Ink Color>
The color of the ink of the present invention is preferably white or gray, particularly preferably white. The color of the ink can be adjusted by the content of the colorant of each color.
＜１．４　インクの調製方法＞
　本発明のインクは、前述の光重合性組成物、及び顔料等を、加熱しながら公知の方法で混合することによって、調製することができる。 <1.4 Ink preparation method>
The ink of the present invention can be prepared by mixing the above-mentioned photopolymerizable composition, pigment, etc. while heating by a known method.
＜１．５　隔壁形成用インクジェットインクセット＞
　本発明の隔壁形成用インクジェットインクセット（以下、単に「インクセット」ともいう。）は、ＬＥＤデバイスのＬＥＤチップ間に隔壁を形成するための隔壁形成用インクジェットインクセットであって、第１の隔壁形成用インクジェットインクと、第２の隔壁形成用インクジェットインクとを有し、前記第１の隔壁形成用インクジェットインクが、光重合性組成物と、白色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下であり、前記第２の隔壁形成用インクジェットインクが、光重合性組成物と、黒色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下であることを特徴とする。 <1.5 Inkjet ink set for forming partition walls>
The inkjet ink set for forming partitions of the present invention (hereinafter also referred to simply as "ink set") is an inkjet ink set for forming partitions for forming partitions between LED chips of an LED device. It has a forming inkjet ink and a second partition-forming inkjet ink, wherein the first partition-forming inkjet ink contains a photopolymerizable composition and a white colorant, and has a normal boiling point of The content of the solvent having a temperature of 250° C. or less is 25% or less, the second inkjet ink for forming partition walls contains a photopolymerizable composition and a black colorant, and has a normal boiling point of 250° C. The content of the following solvent is 25% or less.
　第１の隔壁形成用インクジェットインクが含有する各成分等については上述のとおりである。また、第２の隔壁形成用インクジェットインクは、黒色色材を含有することを特徴とする。 The components and the like contained in the first inkjet ink for forming partition walls are as described above. In addition, the second inkjet ink for forming partition walls is characterized by containing a black colorant.
　第１の隔壁形成用インクジェットインクの色は、白色又は灰色であることが好ましく、白色であることが特に好ましい。また、第２の隔壁形成用インクジェットインクの色は、黒色であることが好ましい。このようなインクセットを用いることで、後述する白色隔壁又は灰色隔壁と黒色隔壁とで構成される隔壁を形成することができる。インクの色は、各色の色材の含有量により調整することができる。 The color of the first inkjet ink for forming partition walls is preferably white or gray, and particularly preferably white. Further, the color of the second inkjet ink for forming partition walls is preferably black. By using such an ink set, it is possible to form white partition walls or partition walls composed of gray partition walls and black partition walls, which will be described later. The color of the ink can be adjusted by the content of the colorant of each color.
　第２の隔壁形成用インクジェットインクにおける黒色色材の含有率は、インク全体に対して、１～２０質量％の範囲内であることが好ましく、１．５～１５質量％の範囲内であることがより好ましく、２～１０質量％の範囲内であることがさらに好ましい。 The content of the black colorant in the second ink-jet ink for forming partition walls is preferably in the range of 1 to 20% by mass, more preferably in the range of 1.5 to 15% by mass, based on the total ink. is more preferable, and more preferably within the range of 2 to 10% by mass.
　黒色色材は、顔料であっても染料であってもよい。また、黒色色材としては、単独で黒色を有する色材を用いてもよく、または、赤、緑、及び青等の色材の混合により黒色色材としてもよい。 The black colorant may be either a pigment or a dye. As the black colorant, a black colorant may be used alone, or a black colorant may be obtained by mixing colorants such as red, green, and blue.
　また、第２の隔壁形成用インクジェットインクは、本発明の効果が得られる範囲において、白色色材以外の色材や、その他成分を更に含有していてもよい。 In addition, the second inkjet ink for forming partition walls may further contain a coloring material other than the white coloring material and other components as long as the effects of the present invention can be obtained.
＜２　ＬＥＤデバイスの製造方法＞
　本発明のＬＥＤデバイスの製造方法は、一の実施形態として、ＬＥＤチップ間に隔壁を有するＬＥＤデバイスの製造方法であって、インクジェット法によって前記隔壁のパターニングを行う隔壁形成工程を有し、前記隔壁形成工程が、少なくとも、白色隔壁形成工程を有し、前記白色隔壁形成工程において、光重合性組成物と、白色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下である隔壁形成用インクジェットインクを用いることを特徴とする。 <2 Manufacturing method of LED device>
A method for manufacturing an LED device of the present invention, as an embodiment, is a method for manufacturing an LED device having partitions between LED chips, comprising a partition forming step of patterning the partitions by an inkjet method, wherein the partitions The forming step has at least a white partition forming step, and in the white partition forming step, the content of a solvent containing a photopolymerizable composition and a white coloring material and having a normal boiling point of 250° C. or lower is 25% or less.
　また、本発明のＬＥＤデバイスの製造方法は、一の実施形態として、ＬＥＤチップ間に隔壁を有するＬＥＤデバイスの製造方法であって、インクジェット法によって前記隔壁のパターニングを行う隔壁形成工程を有し、前記隔壁形成工程が、少なくとも、灰色隔壁形成工程を有し、前記灰色隔壁形成工程において、光重合性組成物と、白色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下である隔壁形成用インクジェットインクを用いることを特徴とする。 Further, a method for manufacturing an LED device of the present invention, as an embodiment, is a method for manufacturing an LED device having partitions between LED chips, comprising a partition forming step of patterning the partitions by an inkjet method, The partition wall forming step has at least a gray partition wall forming step, and in the gray partition wall forming step, a solvent containing a photopolymerizable composition and a white colorant and having a normal boiling point of 250 ° C. or less It is characterized by using an ink-jet ink for forming partition walls having a content of 25% or less.
　当該ＬＥＤデバイスの製造方法で用いる隔壁形成用インクジェットインクは上述のとおりである。 The ink-jet ink for partition formation used in the manufacturing method of the LED device is as described above.
　隔壁形成工程では、インクジェット法によって隔壁のパターニングを行う。具体的には、インクジェットヘッドからインクの液滴を吐出して、基板上の隔壁を形成する位置に着弾させて、パターニングする。着弾したインクに活性エネルギー線を照射してインクを硬化させ、隔壁を形成する。インクジェット法によって隔壁のパターニングを行うことによって、フォトリソグラフィ法のようにＬＥＤチップにダメージを与えることがなく、またスクリーン印刷法や塗布法では困難な微細な形状の隔壁の形成が可能となる。 In the partition formation process, the partition is patterned by the inkjet method. Specifically, droplets of ink are ejected from an inkjet head and landed on positions where partition walls are to be formed on the substrate for patterning. The landed ink is irradiated with an active energy ray to cure the ink and form partition walls. By patterning the barrier ribs by the inkjet method, unlike the photolithographic method, the LED chips are not damaged, and fine barrier ribs can be formed, which is difficult with the screen printing method or the coating method.
　インクジェットヘッドからの吐出方式は、オンデマンド方式とコンティニュアス方式のいずれでもよい。オンデマンド方式のインクジェットヘッドは、シングルキャビティー型、ダブルキャビティー型、ベンダー型、ピストン型、シェアーモード型及びシェアードウォール型等の電気－機械変換方式、並びにサーマルインクジェット型及びバブルジェット（バブルジェットはキヤノン社の登録商標）型等の電気－熱変換方式等のいずれでもよい。 The ejection method from the inkjet head may be either an on-demand method or a continuous method. On-demand inkjet heads include electro-mechanical conversion methods such as single-cavity, double-cavity, bender, piston, shear mode and shared wall types, as well as thermal inkjet and bubble jet (bubble jet is A registered trademark of Canon Inc.) may be used.
　インクの液滴を、加熱した状態でインクジェットヘッドから吐出することで、吐出安定性を高めることができる。吐出される際のインクの温度は、４０～１００℃の範囲内であることが好ましく、吐出安定性をより高めるためには、４０～９０℃の範囲内であることがより好ましい。特には、インクの粘度が７～１５ｍＰａ・ｓの範囲内、より好ましくは８～１３ｍＰａ・ｓの範囲内となるようなインクの温度において吐出することが好ましい。 Ejection stability can be improved by ejecting the ink droplets from the inkjet head in a heated state. The temperature of the ink when ejected is preferably in the range of 40 to 100° C., and more preferably in the range of 40 to 90° C. in order to further improve the ejection stability. In particular, it is preferable to eject the ink at a temperature such that the viscosity of the ink is within the range of 7 to 15 mPa·s, more preferably within the range of 8 to 13 mPa·s.
　インクの加熱方法は、特に制限されない。例えば、ヘッドキャリッジを構成するインクタンク、供給パイプ及びヘッド直前の前室インクタンク等のインク供給系、フィルター付き配管並びにピエゾヘッド等の少なくともいずれかをパネルヒーター、リボンヒーター又は保温水等によって加熱することができる。 The method of heating the ink is not particularly limited. For example, at least one of an ink tank constituting the head carriage, an ink supply system such as a supply pipe and an ink tank in the front chamber immediately before the head, a pipe with a filter, a piezo head, etc. is heated by a panel heater, a ribbon heater, or thermal water. be able to.
　吐出される際のインクの液滴量は、２～２０ｐＬの範囲内であることが好ましい。 The amount of ink droplets to be ejected is preferably within the range of 2 to 20 pL.
　活性エネルギー線は、例えば電子線、紫外線、α線、γ線、及びエックス線等から選択することができるが、好ましくは紫外線である。 The active energy ray can be selected from, for example, electron beams, ultraviolet rays, α rays, γ rays, and X rays, but ultraviolet rays are preferred.
　活性エネルギー線の照射によるインクの硬化は、隔壁の形成に必要なインクを全て着弾させた後にまとめて行ってもよく、インクの吐出と活性エネルギー線の照射を繰り返すことで複数回に分けて行ってもよい。高い隔壁を形成する場合や、高精細な隔壁を形成する場合は、複数回に分けて行うことが好ましい。 Curing of the ink by irradiation with active energy rays may be performed collectively after all the ink necessary for forming the partition walls has landed, or may be performed in multiple steps by repeating ejection of the ink and irradiation with the active energy rays. may When forming high partition walls or when forming high-precision partition walls, it is preferable to perform the step in multiple steps.
　活性エネルギー線として紫外線を照射する場合は、例えばＰｈｏｓｅｏｎ　Ｔｅｃｈｎｏｌｏｇｙ社製の水冷ＬＥＤを用いて、波長３９５ｎｍの条件下で行うことができる。ＬＥＤを光源とすることで、光源の輻射熱によってインクが溶けることによるインクの硬化不良を抑制することができる。 When irradiating ultraviolet rays as active energy rays, for example, a water-cooled LED manufactured by Phoseon Technology can be used under the condition of a wavelength of 395 nm. By using an LED as a light source, it is possible to suppress poor curing of the ink due to melting of the ink by the radiant heat of the light source.
　活性エネルギー線として紫外線を照射する場合のピーク照度は、硬化させるインクの材料や量によって適宜調整し得るが、例えば０．１～４．０Ｗ／ｃｍ２の範囲内とすることができる。 The peak illumination intensity in the case of irradiating ultraviolet rays as active energy rays can be appropriately adjusted depending on the material and amount of the ink to be cured, and can be, for example, within the range of 0.1 to 4.0 W/cm 2 .
　活性エネルギー線として紫外線を照射する場合の光量は、硬化させるインクの材料や量によって適宜調整し得るが、例えば１００～５０００ｍＪ／ｃｍ２範囲内とすることができる。 The amount of light when irradiating ultraviolet rays as active energy rays can be appropriately adjusted depending on the material and amount of the ink to be cured, and can be, for example, within the range of 100 to 5000 mJ/cm 2 .
　本発明のＬＥＤデバイスの製造方法は、隔壁形成工程が、少なくとも、白色隔壁形成工程を有することによって、輝度を向上させるための白色隔壁を形成することができる。また、隔壁形成工程が、少なくとも、灰色隔壁形成工程を有することによって、反射率とコントラストを制御できる灰色隔壁を形成することができる。 In the manufacturing method of the LED device of the present invention, the partition forming step includes at least the white partition forming step, so that white partitions for improving luminance can be formed. In addition, the gray partition wall formation step includes at least the gray partition wall formation step, so that the gray partition wall can be formed in which the reflectance and the contrast can be controlled.
　また、一の実施形態として、隔壁形成工程が、少なくとも、白色隔壁形成工程と、白色隔壁形成工程で形成した白色隔壁の上に黒色隔壁を形成する黒色隔壁形成工程とを有することによって、コントラストの向上に寄与する上面は黒色であり、輝度の向上に寄与する側面は部分的に白色である隔壁を形成することができる。この場合、活性エネルギー線の照射は、白色隔壁形成工程と黒色隔壁形成工程のそれぞれで行ってもよく、黒色隔壁形成工程の後でまとめて行ってもよい。さらに、当該実施形態において、白色隔壁工程と黒色隔壁形成工程の間に灰色隔壁形成工程を追加したり、白色隔壁形成工程の代わりに灰色隔壁形成工程を行うこともできる。 Further, as one embodiment, the partition forming step includes at least a white partition forming step and a black partition forming step of forming black partitions on the white partitions formed in the white partition forming step. The barrier ribs may be formed such that the upper surface that contributes to the improvement is black and the side surface that contributes to the improvement of luminance is partially white. In this case, the irradiation with the active energy ray may be performed in each of the white barrier rib formation process and the black barrier rib formation process, or may be collectively performed after the black barrier rib formation process. Furthermore, in this embodiment, a gray barrier rib formation process may be added between the white barrier rib formation process and the black barrier rib formation process, or a gray barrier rib formation process may be performed instead of the white barrier rib formation process.
　ＬＥＤデバイスの製造において、ＬＥＤチップは、公知のものを用いることができ、ミニＬＥＤチップやマイクロＬＥＤチップを用いることもできる。また、ＬＥＤチップの水分による劣化を防止するために、ＬＥＤチップ上に透明封止剤を充填することが好ましい。透明封止剤としては、ポリビニルカルバゾールや、エポキシ樹脂等の樹脂を用いることができる。ＬＥＤデバイスが備え得る基板、カバーガラス、電極、回路、配線、その他の部材は、特に限定されず、公知の部材を用いることができる。さらに、必要に応じて、波長変換層やカラーフィルタを備える構成とすることもできる。 In the manufacture of LED devices, known LED chips can be used, and mini LED chips and micro LED chips can also be used. Moreover, in order to prevent deterioration of the LED chip due to moisture, it is preferable to fill the LED chip with a transparent sealant. Polyvinylcarbazole and resin such as epoxy resin can be used as the transparent sealant. Substrates, cover glasses, electrodes, circuits, wirings, and other members that the LED device may have are not particularly limited, and known members can be used. Furthermore, a configuration including a wavelength conversion layer and a color filter can be used as necessary.
　なお、基板の色は、隔壁等が形成されていない領域はコントラストに影響し得るため、黒色であることが好ましい。特に図７のように、画素間に隔壁が形成されていない領域も存在するパターンで隔壁が形成される場合は、基板が黒色であることによって、コントラストをより向上させることができる。黒色である基板としては、例えば、黒色の材料を用いて形成された基板や、スパッタリング等により黒化処理された基板を用いることができる。 It should be noted that the color of the substrate is preferably black because areas where partition walls and the like are not formed may affect the contrast. In particular, as shown in FIG. 7, when the partitions are formed in a pattern in which there are areas where the partitions are not formed between the pixels, the black substrate can further improve the contrast. As the black substrate, for example, a substrate formed using a black material or a substrate blackened by sputtering or the like can be used.
　以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例において「部」又は「％」の表示を用いるが、特に断りがない限り「質量部」又は「質量％」を表す。 The present invention will be specifically described below with reference to examples, but the present invention is not limited to these. In the examples, "parts" or "%" are used, but "mass parts" or "mass%" are indicated unless otherwise specified.
＜顔料分散液の調製＞
　下記の手順で、黒色顔料分散液、白色顔料分散液Ａ、及び白色顔料分散液Ｂを調製した。 <Preparation of pigment dispersion>
A black pigment dispersion, a white pigment dispersion A, and a white pigment dispersion B were prepared by the following procedure.
（白色顔料分散液Ａの調製）
　７０．７質量部のトリプロピレングリコールジアクリレート（Ｍｉｒａｍｅｒ　Ｍ２００　Ｍｉｗｏｎ社製、「Ｍｉｒａｍｅｒ」は同社の登録商標）と、８質量部の分散剤（ＢＹＫＪＥＴ－９１５１、ＢＹＫ社製、「ＢＹＫＪＥＴ」は同社の登録商標）とを、ステンレス鋼製のビーカーに入れ、６５℃のホットプレート上で加熱しながら１時間撹拌して分散剤を溶解させた。得られた液体を室温まで冷却した後、白色顔料として２１．３質量部の酸化チタン（ＴＣＲ－５２、堺化学工業社製）を加えて、混合液を得た。得られた混合液を、ジルコニアビーズ２２０ｇ（直径：０.５ｍｍ）と共にガラス瓶に入れて密栓し、ペイントシェーカーにて５時間分散処理した。その後、混合液からジルコニアビーズを除去して、白色顔料分散液Ａを得た。 (Preparation of white pigment dispersion liquid A)
70.7 parts by mass of tripropylene glycol diacrylate (Miramer M200 manufactured by Miwon, "Miramer" is a registered trademark of the company) and 8 parts by mass of a dispersant (BYKJET-9151, manufactured by BYK, "BYKJET" is the company's registered trademark) was placed in a stainless steel beaker and stirred for 1 hour while being heated on a hot plate at 65° C. to dissolve the dispersant. After cooling the resulting liquid to room temperature, 21.3 parts by mass of titanium oxide (TCR-52, manufactured by Sakai Chemical Industry Co., Ltd.) was added as a white pigment to obtain a mixed liquid. The resulting mixed solution was placed in a glass bottle together with 220 g of zirconia beads (diameter: 0.5 mm), sealed, and subjected to dispersion treatment in a paint shaker for 5 hours. After that, the zirconia beads were removed from the mixture to obtain a white pigment dispersion A.
（白色顔料分散液Ｂの調製）
　７０．７質量部のトリプロピレングリコールジアクリレート（Ｍｉｒａｍｅｒ　Ｍ２００　Ｍｉｗｏｎ社製、「Ｍｉｒａｍｅｒ」は同社の登録商標）と、８質量部の分散剤（ＢＹＫＪＥＴ－９１５１、ＢＹＫ社製、「ＢＹＫＪＥＴ」は同社の登録商標）とを、ステンレス鋼製のビーカーに入れ、６５℃のホットプレート上で加熱しながら１時間撹拌して分散剤を溶解させた。得られた液体を室温まで冷却した後、白色顔料として２１．３質量部の酸化ジルコニウム（Ｚｉｒｃｏｎｅｏ、アイテック社製）を加えて、混合液を得た。得られた混合液を、ジルコニアビーズ２２０ｇ（直径：０.５ｍｍ）と共にガラス瓶に入れて密栓し、ペイントシェーカーにて５時間分散処理した。その後、混合液からジルコニアビーズを除去して、白色顔料分散液Ｂを得た。 (Preparation of white pigment dispersion B)
70.7 parts by mass of tripropylene glycol diacrylate (Miramer M200 manufactured by Miwon, "Miramer" is a registered trademark of the company) and 8 parts by mass of a dispersant (BYKJET-9151, manufactured by BYK, "BYKJET" is the company's registered trademark) was placed in a stainless steel beaker and stirred for 1 hour while being heated on a hot plate at 65° C. to dissolve the dispersant. After cooling the resulting liquid to room temperature, 21.3 parts by mass of zirconium oxide (Zirconeo, manufactured by ITEC Co., Ltd.) was added as a white pigment to obtain a mixed liquid. The resulting mixed solution was placed in a glass bottle together with 220 g of zirconia beads (diameter: 0.5 mm), sealed, and subjected to dispersion treatment in a paint shaker for 5 hours. After that, the zirconia beads were removed from the mixture to obtain a white pigment dispersion B.
（黒色顔料分散液の調製）
　７１．０質量部のジプロピレングリコールジアクリレートと、９．０質量部の分散剤（味の素ファインテクノ社製、アジスパーＰＢ８２４）とを、ステンレス鋼製のビーカーに入れ、６５℃のホットプレート上で加熱しながら１時間撹拌して分散剤を溶解させた。得られた液体を室温まで冷却した後、黒色顔料として２０．０質量部のｐｉｇｉｍｅｎｔ　Ｂｌａｃｋ　７（三菱化学社製、ＭＡ７７）を加えて、混合液を得た。得られた混合液を、２００ｇのジルコニアビーズ（直径：０.５ｍｍ）と共にガラス瓶に入れて密栓し、ペイントシェーカーにて５時間分散処理した。その後、混合液からジルコニアビーズを除去して、黒色顔料分散液を得た。 (Preparation of black pigment dispersion)
71.0 parts by mass of dipropylene glycol diacrylate and 9.0 parts by mass of a dispersing agent (Ajinomoto Fine-Techno Co., Inc., Ajisper PB824) are placed in a stainless steel beaker and heated on a hot plate at 65°C. While stirring for 1 hour, the dispersant was dissolved. After cooling the resulting liquid to room temperature, 20.0 parts by mass of pigment Black 7 (manufactured by Mitsubishi Chemical Corporation, MA77) was added as a black pigment to obtain a mixed liquid. The resulting mixed solution was placed in a glass bottle together with 200 g of zirconia beads (diameter: 0.5 mm), sealed, and subjected to dispersion treatment in a paint shaker for 5 hours. After that, the zirconia beads were removed from the mixture to obtain a black pigment dispersion.
＜インクの調製＞
　下記の手順で、黒色顔料インク及び白色顔料インクを調製した。 <Ink preparation>
A black pigment ink and a white pigment ink were prepared by the following procedures.
（白色顔料インク１～７の調製）
　表Ｉに示す材料をステンレスビーカーに入れ、ホットプレートで８０℃に加熱しながら１時間撹拌した。得られた溶液を加熱しながら、ＡＤＶＡＴＥＣ社製テフロン（登録商標）３μｍメンブランフィルターで濾過することにより、白色顔料インク１～７を得た。 (Preparation of white pigment inks 1 to 7)
The materials shown in Table I were placed in a stainless steel beaker and stirred for 1 hour while being heated to 80° C. with a hot plate. White pigment inks 1 to 7 were obtained by filtering the resulting solution through a Teflon (registered trademark) 3 μm membrane filter manufactured by ADVATEC while heating.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表Ｉに示す材料の詳細は以下のとおりである。
　６ＥＯ－ＴＭＰＴＡ：６ＥＯ変性トリメチロールプロパントリアクリレート
　４ＥＯ－ＨＤＤＡ：４ＥＯ変性ヘキサンジオールジアクリレート
　ＴＰＧＤＡ：トリプロピレングリコールジアクリレート
　ＤＡＲＯＣＵＲＥ　ＴＰＯ：２，４，６－トリメチルベンゾインジフェニルフォスフィンオキサイド、ＢＡＳＦ社製
　Ｉｒｇａｃｕｒｅ　８１９：ＢＡＳＦ社製
　Ｉｒｇａｓｔａｂ　ＵＶ－１０：ＢＡＳＦ社製
　ＫＦ－３５２：信越化学工業社製
　白色顔料分散液Ａ：上記調製した白色顔料分散液Ａ
　白色顔料分散液Ｂ：上記調製した白色顔料分散液Ｂ
　ブチルカルビトールアセテート：標準沸点２４７℃である溶剤 Details of the materials shown in Table I are as follows.
6EO-TMPTA: 6EO-modified trimethylolpropane triacrylate 4EO-HDDA: 4EO-modified hexanediol diacrylate TPGDA: tripropylene glycol diacrylate DAROCURE TPO: 2,4,6-trimethylbenzoindiphenylphosphine oxide, manufactured by BASF Irgacure 819: Irgastab UV-10 manufactured by BASF: KF-352 manufactured by BASF: White pigment dispersion A manufactured by Shin-Etsu Chemical Co.: White pigment dispersion A prepared above
White pigment dispersion B: White pigment dispersion B prepared above
Butyl carbitol acetate: a solvent with a normal boiling point of 247°C
（黒色顔料インク１～７の調製）
　表IIに示す材料をステンレスビーカーに入れ、ホットプレート上で８０℃に加熱しながら１時間撹拌した。得られた溶液を加熱しながら、ＡＤＶＡＴＥＣ社製テフロン（登録商標）３μｍメンブランフィルターで濾過することにより、黒色顔料インク１～７を得た。 (Preparation of black pigment inks 1 to 7)
The materials shown in Table II were placed in a stainless steel beaker and stirred for 1 hour while being heated to 80° C. on a hot plate. Black pigment inks 1 to 7 were obtained by filtering the resulting solution through a Teflon (registered trademark) 3 μm membrane filter manufactured by ADVATEC while heating.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表IIに示す材料の詳細は以下のとおりである。
　ＤＰＧＤＡ：ジプロピレングリコールジアクリレート
　ＨＤＤＡ：１，６－ヘキサンジオールジアクリレート
　３ＰＯ－ＴＭＰＴＡ：３ＰＯ変性トリメチロールプロパントリアクリレート
　９ＥＯ－ＴＭＰＴＡ：９ＥＯ変性トリメチロールプロパントリアクリレート
　ＰＥＧＤＡ（６００）：ポリエチレングリコール＃６００ジアクリレート
　４ＥＯ－ＰＥＴＡ：４ＥＯ変性ペンタエリスリトールテトラアクリレート
　ＤＡＲＯＣＵＲＥ　ＴＰＯ：２，４，６－トリメチルベンゾインジフェニルフォスフィンオキサイド、ＢＡＳＦ社製
　Ｓｐｅｅｄｃｕｒｅ　ＩＴＸ：２－イソプロピルチオキサントン、Ｌａｍｂｓｏｎ社製
　Ｉｒｇａｓｔａｂ　ＵＶ－１０：ＢＡＳＦ社製
　黒色顔料分散液：上記調製した黒色顔料分散液
　ブチルカルビトールアセテート：標準沸点２４７℃である溶剤 Details of the materials shown in Table II are as follows.
DPGDA: dipropylene glycol diacrylate HDDA: 1,6-hexanediol diacrylate 3PO-TMPTA: 3PO-modified trimethylolpropane triacrylate 9EO-TMPTA: 9EO-modified trimethylolpropane triacrylate PEGDA (600): polyethylene glycol #600 diacrylate 4EO-PETA: 4EO-modified pentaerythritol tetraacrylate DAROCURE TPO: 2,4,6-trimethylbenzoindiphenylphosphine oxide, BASF Speedcure ITX: 2-isopropylthioxanthone, Lambson Irgastab UV-10: BASF black pigment Dispersion: the black pigment dispersion prepared above Butyl carbitol acetate: a solvent with a normal boiling point of 247°C
＜比較例用レジスト組成物の調製＞
　特開２０２０－２０５４１７号公報を参考に、以下の手順で、比較例用の白色顔料含有レジスト組成物（以下、「白色顔料レジスト」と略す。）及び黒色顔料含有レジスト組成物（以下、「黒色顔料レジスト」と略す。）を調製した。 <Preparation of Comparative Resist Composition>
With reference to JP-A-2020-205417, a white pigment-containing resist composition (hereinafter abbreviated as "white pigment resist") and a black pigment-containing resist composition (hereinafter, "black abbreviated as "pigment resist") was prepared.
（白色顔料レジストの調製）
　１０００ｍＬの三口フラスコに、トリフルオロプロピルトリメトキシシランを１４７．３２ｇ（０．６７５ｍｏｌ）、３－メタクリロキシプロピルメチルジメトキシシランを４０．６６ｇ（０．１７５ｍｏｌ）、３－トリメトキシシリルプロピルコハク酸無水物を２６．２３ｇ（０．１０ｍｏｌ）、３－（３，４－エポキシシクロヘキシル）プロピルトリメトキシシランを１２．３２ｇ（０．０５ｍｏｌ）、ＢＨＴ（ジブチルヒドロキシトルエン）を０．８０８ｇ、ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）を１７１．６２ｇ仕込み、室温で撹拌しながら水５２．６５ｇにリン酸２．２６５ｇ（仕込みモノマーに対して１．０重量％）を溶かしたリン酸水溶液を３０分間かけて添加した。その後、フラスコを７０℃のオイルバスに浸けて９０分間撹拌した後、オイルバスを３０分間かけて１１５℃まで昇温した。昇温開始１時間後に溶液温度（内温）が１００℃に到達し、そこから２時間加熱撹拌し（内温は１００～１１０℃）、ポリシロキサン溶液を得た。なお昇温及び加熱撹拌中、窒素９５体積％、酸素５体積％の混合気体を０．０５Ｌ／分で流した。反応中に副生成物であるメタノール、水が合計１３１．３５ｇ留出した。得られたポリシロキサン溶液に、固形分濃度が４０重量％となるようにＰＧＭＥＡを追加し、ポリシロキサン溶液を得た。 (Preparation of white pigment resist)
147.32 g (0.675 mol) of trifluoropropyltrimethoxysilane, 40.66 g (0.175 mol) of 3-methacryloxypropylmethyldimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride were placed in a 1000 mL three-necked flask. 26.23 g (0.10 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane 12.32 g (0.05 mol) BHT (dibutylhydroxytoluene) 0.808 g PGMEA (propylene glycol monomethyl 171.62 g of ether acetate) was charged, and an aqueous phosphoric acid solution prepared by dissolving 2.265 g of phosphoric acid (1.0% by weight relative to the charged monomers) in 52.65 g of water was added over 30 minutes while stirring at room temperature. After that, the flask was immersed in an oil bath at 70° C. and stirred for 90 minutes, and then the oil bath was heated to 115° C. over 30 minutes. After 1 hour from the start of heating, the temperature of the solution (internal temperature) reached 100° C., and the solution was heated and stirred for 2 hours (internal temperature: 100 to 110° C.) to obtain a polysiloxane solution. A mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 L/min during the temperature rise and heating and stirring. A total of 131.35 g of methanol and water, which are by-products, were distilled during the reaction. PGMEA was added to the obtained polysiloxane solution so that the solid content concentration was 40% by weight to obtain a polysiloxane solution.
　白色顔料として、二酸化チタン顔料（Ｒ－９６０、ＢＡＳＦジャパン社製）５．００ｇに、樹脂としてポリシロキサン溶液５．００ｇを混合し、ジルコニアビーズが充填されたミル型分散機を用いて分散し、顔料分散液を得た。 As a white pigment, 5.00 g of a titanium dioxide pigment (R-960, manufactured by BASF Japan) is mixed with 5.00 g of a polysiloxane solution as a resin, and dispersed using a mill-type disperser filled with zirconia beads, A pigment dispersion was obtained.
　次に、顔料分散液９．９８ｇ、ＤＡＡ（ジアセトンアルコール）０．７１ｇ、ポリシロキサン溶液１．５７ｇ、光重合開始剤として、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（ｏ－アセチルオキシム）（ＢＡＳＦジャパン社製）０．０５０ｇ、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（ＢＡＳＦジャパン社製）０．４００ｇ、光塩基発生剤として、２－（３－ベンゾイルフェニル）プロピオン酸１，２－ジイソプロピル－３－［ビス（ジメチルアミノ）メチレン］グアニジニウム（富士フイルム和光純薬社製）０．１００ｇ、光重合性化合物として、ジペンタエリスリトールヘキサアクリレート（新日本薬業社製）１．２０ｇ、撥液化合物として、光重合性フッ素含有化合物（“メガファック”（登録商標）ＲＳ－７６－Ｅ、ＤＩＣ社製）の４０重量％ＰＧＭＥＡ希釈溶液１．００ｇ、３′，４′－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート（ダイセル社製）０．１００ｇ、エチレンビス（オキシエチレン）ビス［３－（５－ｔｅｒｔ－ブチル－４－ヒドロキシ－ｍ－トリル）プロピオネート］（ＢＡＳＦジャパン社製）０．０３０ｇ、アクリル系界面活性剤（“ＢＹＫ”（登録商標）３５２、ビックケミージャパン社製）のＰＧＭＥＡ１０重量％希釈溶液０．１００ｇ（濃度５００ｐｐｍに相当）を、溶媒ＰＧＭＥＡ４．７６ｇに溶解させ、撹拌した。 Next, 9.98 g of pigment dispersion liquid, 0.71 g of DAA (diacetone alcohol), 1.57 g of polysiloxane solution, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl) as a photopolymerization initiator -9H-carbazol-3-yl]-,1-(o-acetyloxime) (manufactured by BASF Japan) 0.050 g, bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF Japan) ) 0.400 g, and 0.100 g of 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium 2-(3-benzoylphenyl)propionate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a photobase generator. , as a photopolymerizable compound, dipentaerythritol hexaacrylate (manufactured by Shinnihon Yakugyo Co., Ltd.) 1.20 g, as a liquid-repellent compound, a photopolymerizable fluorine-containing compound (“Megafac” (registered trademark) RS-76-E, 1.00 g of a 40% by weight PGMEA diluted solution of DIC Corporation), 0.100 g of 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (manufactured by Daicel Corporation), ethylene bis(oxyethylene) bis[ 3-(5-tert-butyl-4-hydroxy-m-tolyl) propionate] (manufactured by BASF Japan) 0.030 g, acrylic surfactant (“BYK” (registered trademark) 352, manufactured by BYK Chemie Japan) was dissolved in 4.76 g of solvent PGMEA and stirred.
　次いで、５．０μｍのフィルターでろ過を行い、白色顔料レジストを得た。 Then, filtration was performed with a 5.0 μm filter to obtain a white pigment resist.
（黒色顔料レジストの調製）
　特許第３１２０４７６号公報の実施例１の記載の方法により、メチルメタクリレート／メタクリル酸／スチレン共重合体（質量比３０／４０／３０）を合成後、グリシジルメタクリレート４０質量部を付加させ、精製水で再沈、濾過、乾燥することにより、アクリルポリマー粉末を得た。 (Preparation of black pigment resist)
After synthesizing a methyl methacrylate/methacrylic acid/styrene copolymer (mass ratio 30/40/30) by the method described in Example 1 of Japanese Patent No. 3120476, 40 parts by mass of glycidyl methacrylate was added, followed by adding purified water. Acrylic polymer powder was obtained by reprecipitation, filtration and drying.
　黒色顔料として窒化チタン粒子（日清エンジニアリング社製）を２００ｇ、アクリルポリマーのＰＧＭＥＡ３５質量％溶液を１１４ｇ、高分子分散剤として３級アミノ基と４級アンモニウム塩を有するディスパービックＬＰＮ－２１１１６を２５ｇ及びＰＧＭＥＡ６６１ｇをタンクに仕込み、ホモミキサーで２０分間撹拌し、予備分散液を得た。その後、０．０５ｍｍφジルコニアビーズを７５％充填した遠心分離セパレーターを具備したウルトラアペックスミル（寿工業製）に予備分散液を供給し、回転速度８ｍ／ｓで３時間分散を行い、固形分濃度２５質量％、黒色顔料／樹脂（質量比）＝８０／２０の黒色顔料分散液を得た。 200 g of titanium nitride particles (manufactured by Nisshin Engineering Co., Ltd.) as a black pigment, 114 g of a 35% by mass acrylic polymer PGMEA solution, 25 g of Disperbyk LPN-21116 having a tertiary amino group and a quaternary ammonium salt as a polymer dispersant, and 661 g of PGMEA was charged into a tank and stirred with a homomixer for 20 minutes to obtain a preliminary dispersion. After that, the preliminary dispersion was supplied to an Ultra Apex mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 0.05 mmφ zirconia beads at 75%, and dispersed at a rotation speed of 8 m/s for 3 hours to obtain a solid content concentration of 25. A black pigment dispersion of black pigment/resin (mass ratio)=80/20 was obtained.
　ＰＧＭＥＡ３２．７８ｇに、光重合開始剤としてＮＣＩ－８３１（ＡＤＥＫＡ社製）を０．３５ｇ添加し、固形分が溶解するまで撹拌した。さらに、アクリルポリマーのＰＧＭＥＡ３５質量％溶液を４．８６ｇ、多官能モノマーとしてジペンタエリスリトールヘキサアクリレート（日本化薬社製）を２．４６ｇ、密着改良剤としてＫＢＭ５１０３（信越化学社製）を０．６０ｇ、界面活性剤としてシリコーン系界面活性剤ＢＹＫ３３３のＰＧＭＥＡ１０質量％溶液を０．４０ｇ、撥液化合物として、光重合性フッ素含有化合物（“メガファック”（登録商標）ＲＳ－７６－Ｅ、ＤＩＣ社製）の４０重量％ＰＧＭＥＡ希釈溶液１．４７ｇを添加し、室温にて１時間撹拌し、感光性レジストを得た。 To 32.78 g of PGMEA, 0.35 g of NCI-831 (manufactured by ADEKA) was added as a photopolymerization initiator, and stirred until the solid content was dissolved. Furthermore, 4.86 g of a 35% by mass solution of acrylic polymer PGMEA, 2.46 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, and 0.60 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver. , 0.40 g of a PGMEA 10% by mass solution of silicone surfactant BYK333 as a surfactant, and a photopolymerizable fluorine-containing compound (“Megafac” (registered trademark) RS-76-E, manufactured by DIC Corporation as a liquid-repellent compound. ) was added and stirred at room temperature for 1 hour to obtain a photosensitive resist.
　この感光性レジストに黒色顔料分散液を５６．９８ｇ添加することで全固形分濃度２０％、黒色顔料／樹脂（質量比）＝５８／４２、の黒色顔料レジストを調製した。 A black pigment resist having a total solid concentration of 20% and a black pigment/resin (mass ratio) of 58/42 was prepared by adding 56.98 g of a black pigment dispersion to this photosensitive resist.
＜ＬＥＤデバイスの作製＞
　以下の手順で、ＬＥＤデバイスを作製した。 <Production of LED device>
An LED device was produced by the following procedure.
（ＬＥＤデバイス１～７の作製）
　特開２０２１－１１０８７５号公報の明細書段落［００９１］～［０１０６］に記載の方法を参考に、下記の手順で、基板上に赤色、緑色、及び青色のＬＥＤチップを配置し、隔壁未形成ＬＥＤデバイスを形成した。 (Production of LED devices 1 to 7)
With reference to the method described in paragraphs [0091] to [0106] of JP-A-2021-110875, red, green, and blue LED chips are arranged on the substrate in the following procedure, and no partition is formed. An LED device was formed.
　ＬＥＤチップは、大きさが１００μｍ×１００μｍ×１００μｍのマイクロＬＥＤチップを用いた。３色のマイクロＬＥＤチップからなる画素の数は、８０×８０とし、合計８０×８０×３個のマイクロＬＥＤチップを用いた。画素内におけるマイクロＬＥＤチップの配置は、図４や図７に示すような、３色のマイクロＬＥＤチップが横並びとなる配置とした。同一画素内における隣接するマイクロＬＥＤチップの間隔は、２５０μｍとした。また、画素ピッチは１３００μｍとした。 A micro LED chip with a size of 100 μm × 100 μm × 100 μm was used as the LED chip. The number of pixels composed of micro LED chips of three colors was 80×80, and a total of 80×80×3 micro LED chips were used. The arrangement of the micro LED chips in the pixel is such that three color micro LED chips are arranged side by side as shown in FIGS. 4 and 7 . The interval between adjacent micro LED chips in the same pixel was set to 250 μm. Also, the pixel pitch was set to 1300 μm.
　駆動基板には、大きさが２００ｍｍ×２００ｍｍである無アルカリガラス基板に、ＴＦＴ（thin film transistor）、配線、及びマイクロＬＥＤチップ数に応じた数のＣｕの電極パッドが形成されているものを用いた。駆動基板のマイクロＬＥＤチップとの接合部位以外は、スパッタリングにより黒化処理を行った。 The driving substrate used is a non-alkali glass substrate with a size of 200 mm × 200 mm, on which TFTs (thin film transistors), wiring, and Cu electrode pads corresponding to the number of micro LED chips are formed. board. A blackening treatment was performed by sputtering except for the bonding portion of the driving substrate with the micro LED chip.
　中継基板は、駆動基板と同じサイズで、厚み０．７ｍｍの無アルカリガラス基板を用いた。中継基板上には、ＰＤＭＳ（dimethylpolysiloxane）樹脂を１０μｍの厚みで形成した。 A non-alkali glass substrate with a thickness of 0.7 mm and the same size as the drive substrate was used for the relay substrate. PDMS (dimethylpolysiloxane) resin was formed with a thickness of 10 μm on the relay substrate.
　ＰＤＭＳ樹脂の形成は、ラミネート塗布で基板表面にＰＤＭＳ樹脂を均一な膜厚で塗布し、１００℃のオーブンで１時間加熱してＰＤＭＳ樹脂を熱架橋させた。ＰＤＭＳ樹脂は、信越化学工業社製、信越シリコーンＳＩＭ３６０及びＣＡＴ３６０を配合して、出来上がりの硬度を調整した。出来上がり（熱架橋後）の硬度は、ゴム硬度ショアＡ６０であった。 To form the PDMS resin, the PDMS resin was applied to the surface of the substrate in a uniform film thickness by lamination and heated in an oven at 100°C for 1 hour to thermally crosslink the PDMS resin. As the PDMS resin, Shin-Etsu Silicone SIM360 and CAT360 manufactured by Shin-Etsu Chemical Co., Ltd. were blended to adjust the finished hardness. The hardness of the finished product (after thermal crosslinking) was a rubber hardness Shore A60.
　マイクロＬＥＤチップは、半導体層が形成されたサファイア基板からダイシングされて、保持基板への移載したのち、さらに中継基板に移載した。また、マイクロＬＥＤチップに、チップ側電極を形成し、そのチップ側電極上に、高さ５μｍのはんだによるマイクロバンプを形成した。はんだはＳＡＣ（ＳｎＡｇＣｕ）を用いた。 The micro LED chip was diced from the sapphire substrate on which the semiconductor layer was formed, transferred to the holding substrate, and then transferred to the relay substrate. A chip-side electrode was formed on the micro LED chip, and a micro-bump with a height of 5 μm was formed on the chip-side electrode by solder. SAC (SnAgCu) was used as solder.
　中継基板への移載では、スタンプを用いて、マイクロＬＥＤチップを中継基板上に配列させた。 When transferring to the relay board, a stamp was used to arrange the micro LED chips on the relay board.
　次に、中継基板上のマイクロＬＥＤチップ及びチップ側電極上などに残った樹脂残渣を酸素アッシャーで除去した後、Ａｒプラズマ処理のトリートメントを行った。 Next, after removing the resin residue remaining on the micro LED chip and the chip-side electrode on the relay board with an oxygen asher, Ar plasma treatment was performed.
　次に、駆動基板と中継基板をアライメント後、それぞれの電極が重なる位置ではんだ溶融温度以下の温度で一括ボンディングした。これにより、チップ側電極と駆動基板側電極を、はんだを介して仮接合した。 Next, after aligning the driving substrate and the relay substrate, they were collectively bonded at a temperature below the melting temperature of the solder at the positions where the respective electrodes overlap. As a result, the chip-side electrodes and the driving substrate-side electrodes were temporarily joined with solder.
　次に、中継基板を剥離して除去した。 Next, the relay board was peeled off and removed.
　次に、駆動基板上のマイクロＬＥＤチップが仮接合された面に、フラックスを塗布して、リフロー炉内ではんだ溶融温度以上の加熱処理を行った。このリフローにより、マイクロＬＥＤチップを実装した。 Next, flux was applied to the surface of the driving substrate on which the micro LED chip was temporarily bonded, and heat treatment was performed in a reflow furnace at a temperature higher than the melting temperature of the solder. A micro LED chip was mounted by this reflow.
　上記手順により、基板上に赤色、緑色、及び青色のマイクロＬＥＤチップを配置し、隔壁未形成ＬＥＤデバイスを形成した。 According to the above procedure, red, green, and blue micro LED chips were arranged on the substrate to form an LED device without partition walls.
　次いで、上記調製した白色顔料インク１を用いて、図７に示すパターンで、上記形成した隔壁未形成ＬＥＤデバイスの各マイクロＬＥＤチップの周囲を覆うように、幅２００μｍ、合計高さ１００μｍの隔壁を形成した。具体的な手順は以下のとおりである。 Next, using the white pigment ink 1 prepared above, barrier ribs having a width of 200 μm and a total height of 100 μm were formed in the pattern shown in FIG. formed. The specific procedure is as follows.
　インクジェット装置を用いて白色顔料インク１の液滴を吐出し、パターニングしながら、硬化後の高さが２０μｍとなる未硬化隔壁を形成した。吐出される際のインクの温度は、８０℃に調製した。また、吐出される際のインクの液滴量は、５ｐＬとした。当該未硬化隔壁に、光量１０００ｍＪ／ｃｍ２で紫外線を照射して、高さ２０μｍの隔壁を形成した。 Droplets of the white pigment ink 1 were ejected using an inkjet device, and uncured barrier ribs having a height of 20 μm after curing were formed while patterning. The temperature of the ink during ejection was adjusted to 80°C. In addition, the amount of ink droplets to be ejected was set to 5 pL. The uncured barrier ribs were irradiated with ultraviolet rays at a light amount of 1000 mJ/cm 2 to form barrier ribs with a height of 20 μm.
　次いで、上記形成した隔壁の上に、上記と同様に白色顔料インク１の液滴を吐出し、硬化後の高さが２０μｍとなる未硬化隔壁を形成した。当該未硬化隔壁に、光量１０００ｍＪ／ｃｍ２で紫外線を照射して、隔壁の高さを４０μｍとした。 Subsequently, droplets of the white pigment ink 1 were ejected on the barrier ribs thus formed in the same manner as described above to form uncured barrier ribs having a height of 20 μm after curing. The uncured barrier ribs were irradiated with ultraviolet rays at a light intensity of 1000 mJ/cm 2 to make the height of the barrier ribs 40 µm.
　上記工程を繰り返し、幅２００μｍ、合計高さ１００μｍの隔壁を形成した。 The above steps were repeated to form barrier ribs with a width of 200 μm and a total height of 100 μm.
　以上の手順により、インクジェット法によって隔壁のパターニングを行う隔壁形成工程を行なった。 According to the above procedure, the partition forming step of patterning the partition by the inkjet method was performed.
　次いで、ＬＥＤチップ上に、ディスペンサーを用いて、透明封止剤としてポリビニルカルバゾールを充填し、カバーガラスと張り合わせた。 Next, the LED chip was filled with polyvinyl carbazole as a transparent sealant using a dispenser, and laminated with a cover glass.
　以上の手順により、ＬＥＤデバイス１を作製した。 The LED device 1 was produced according to the above procedure.
　上記ＬＥＤデバイス１の作製において、インクを表IIIに示すとおり変更して、ＬＥＤデバイス２～７を作製した。 In the production of LED device 1 above, LED devices 2 to 7 were produced by changing the ink as shown in Table III.
（ＬＥＤデバイス８～１０の作製）
　上記と同様の方法で、基板上に赤色、緑色、及び青色のマイクロＬＥＤチップを配置し、隔壁未形成ＬＥＤデバイスを形成した。 (Production of LED devices 8 to 10)
Red, green, and blue micro LED chips were arranged on a substrate in the same manner as above to form an LED device without partition walls.
　次いで、上記形成した隔壁未形成ＬＥＤデバイスに、白色顔料レジストをスピンコーターで塗布し、９０℃で１０分間プリベークを行った。この塗布膜にマスクアライナーＰＥＭ－６Ｍ（ユニオン光学社製）を用い、フォトマスクを介して紫外線を１００ｍＪ／ｃｍ２（ｉ線露光量換算：全波長露光）の露光量で露光した。次に、テトラメチルアンモニウムヒドロキシドの０．５質量％水溶液のアルカリ現像液で現像し、続いて純水洗浄を行った。 Next, a white pigment resist was applied to the thus-formed LED device without partition walls using a spin coater, and pre-baked at 90° C. for 10 minutes. Using a mask aligner PEM-6M (manufactured by Union Optical Co., Ltd.), this coating film was exposed to ultraviolet rays at an exposure amount of 100 mJ/cm 2 (i-line exposure amount conversion: full wavelength exposure) through a photomask. Next, it was developed with an alkaline developer of 0.5 mass % aqueous solution of tetramethylammonium hydroxide, and then washed with pure water.
　次いで、熱風オーブン中２３０℃で３０分保持しキュアを行なうことで、赤色、緑色、及び青色のマイクロＬＥＤチップ間に、高さ１００μｍ、幅２００μｍの白色隔壁を形成した。 Then, it was cured in a hot air oven at 230°C for 30 minutes to form white barrier ribs with a height of 100 µm and a width of 200 µm between the red, green, and blue micro LED chips.
　次いで、ＬＥＤチップ上に、ディスペンサーを用いて、透明封止剤としてポリビニルカルバゾールを充填し、カバーガラスと張り合わせた。 Next, the LED chip was filled with polyvinylcarbazole as a transparent sealant using a dispenser, and laminated with a cover glass.
　以上の手順により、ＬＥＤデバイス８を作製した。 The LED device 8 was produced by the above procedure.
　上記ＬＥＤデバイス８の作製において、キュア温度を表IIIに示すとおり変更して、ＬＥＤデバイス９及び１０を作製した。 In the production of LED device 8 above, LED devices 9 and 10 were produced by changing the curing temperature as shown in Table III.
（ＬＥＤデバイス１１～１７の作製）
　上記と同様の方法で、基板上に赤色、緑色、及び青色のマイクロＬＥＤチップを配置し、隔壁未形成ＬＥＤデバイスを形成した。 (Production of LED devices 11 to 17)
Red, green, and blue micro LED chips were arranged on a substrate in the same manner as above to form an LED device without partition walls.
　次いで、上記調製した白色顔料インク１及び黒色顔料インク１を用いて、図７に示すパターンで、上記形成した隔壁未形成ＬＥＤデバイスの各マイクロＬＥＤチップの周囲を覆うように、幅２００μｍ、合計高さ１００μｍの隔壁を形成した。具体的な手順は以下のとおりである。 Next, using the white pigment ink 1 and the black pigment ink 1 prepared above, in the pattern shown in FIG. Partition walls with a thickness of 100 μm were formed. The specific procedure is as follows.
　インクジェット装置を用いて白色顔料インク１の液滴を吐出し、パターニングしながら、硬化後の高さが２０μｍとなる未硬化隔壁を形成した。吐出される際のインクの温度は、８０℃に調製した。また、吐出される際のインクの液滴量は、５ｐＬとした。当該未硬化隔壁に、光量１０００ｍＪ／ｃｍ２で紫外線を照射して、高さ２０μｍの隔壁を形成した。 Droplets of the white pigment ink 1 were ejected using an inkjet device, and uncured barrier ribs having a height of 20 μm after curing were formed while patterning. The temperature of the ink during ejection was adjusted to 80°C. In addition, the amount of ink droplets to be ejected was set to 5 pL. The uncured barrier ribs were irradiated with ultraviolet rays at a light amount of 1000 mJ/cm 2 to form barrier ribs with a height of 20 μm.
　次いで、上記形成した隔壁の上に、上記と同様に白色顔料インク１の液滴を吐出し、硬化後の高さが２０μｍとなる未硬化隔壁を形成した。当該未硬化隔壁に、光量１０００ｍＪ／ｃｍ２で紫外線を照射して、隔壁の高さを４０μｍとした。 Subsequently, droplets of the white pigment ink 1 were ejected on the barrier ribs thus formed in the same manner as described above to form uncured barrier ribs having a height of 20 μm after curing. The uncured barrier ribs were irradiated with ultraviolet rays at a light intensity of 1000 mJ/cm 2 to make the height of the barrier ribs 40 μm.
　上記工程を繰り返し、幅２００μｍ、合計高さ８０μｍの白色隔壁を形成した。 The above steps were repeated to form white barrier ribs with a width of 200 μm and a total height of 80 μm.
　次いで、上記形成した白色隔壁の上に、黒色顔料インク１の液滴を吐出し、硬化後の高さが２０μｍとなる未硬化隔壁を形成した。当該未硬化隔壁に、光量１０００ｍＪ／ｃｍ２で紫外線を照射して、高さ２０μｍの黒色隔壁を形成した。これにより、幅２００μｍ、合計高さ１００μｍの隔壁を形成した。 Next, droplets of the black pigment ink 1 were ejected onto the white barrier ribs thus formed to form uncured barrier ribs having a height of 20 μm after curing. The uncured barrier ribs were irradiated with ultraviolet rays at a light intensity of 1000 mJ/cm 2 to form black barrier ribs with a height of 20 µm. Thus, barrier ribs having a width of 200 μm and a total height of 100 μm were formed.
　以上の手順により、白色隔壁形成工程と、白色隔壁形成工程で形成した白色隔壁の上に黒色隔壁を形成する黒色隔壁形成工程とを有する隔壁形成工程を行なった。 According to the above procedure, a partition forming step including a white partition forming step and a black partition forming step of forming a black partition on the white partition formed in the white partition forming step was performed.
　次いで、ＬＥＤチップ上に、ディスペンサーを用いて、透明封止剤としてポリビニルカルバゾールを充填し、カバーガラスと張り合わせた。 Next, the LED chip was filled with polyvinyl carbazole as a transparent sealant using a dispenser, and laminated with a cover glass.
　以上の手順により、ＬＥＤデバイス１１を作製した。 The LED device 11 was produced by the above procedure.
　上記ＬＥＤデバイス１１の作製において、インクを表IIIに示すとおり変更して、ＬＥＤデバイス１２～１７を作製した。 In the production of LED device 11, LED devices 12 to 17 were produced by changing the ink as shown in Table III.
（ＬＥＤデバイス１８～２０の作製）
　上記と同様の方法で、基板上に赤色、緑色、及び青色のマイクロＬＥＤチップを配置し、隔壁未形成ＬＥＤデバイスを形成した。 (Production of LED devices 18 to 20)
Red, green, and blue micro LED chips were arranged on a substrate in the same manner as above to form an LED device without partition walls.
　次いで、上記形成した隔壁未形成ＬＥＤデバイスに、白色顔料レジストをスピンコーターで塗布し、９０℃で１０分間プリベークを行った。この塗布膜にマスクアライナーＰＥＭ－６Ｍ（ユニオン光学社製）を用い、フォトマスクを介して紫外線を１００ｍＪ／ｃｍ２（ｉ線露光量換算：全波長露光）の露光量で露光した。次に、テトラメチルアンモニウムヒドロキシドの０．５質量％水溶液のアルカリ現像液で現像し、続いて純水洗浄を行った。 Next, a white pigment resist was applied to the thus-formed LED device without partition walls using a spin coater, and pre-baked at 90° C. for 10 minutes. Using a mask aligner PEM-6M (manufactured by Union Optical Co., Ltd.), this coating film was exposed to ultraviolet rays at an exposure amount of 100 mJ/cm 2 (i-line exposure amount conversion: full wavelength exposure) through a photomask. Next, it was developed with an alkaline developer of 0.5 mass % aqueous solution of tetramethylammonium hydroxide, and then washed with pure water.
　次いで、熱風オーブン中２３０℃で３０分保持しキュアを行なうことで、基板に配置された赤色、緑色、及び青色のマイクロＬＥＤチップ間に、高さ８０μｍ、幅２００μｍの白色隔壁を形成した。 Then, it was held in a hot air oven at 230°C for 30 minutes and cured to form white partition walls with a height of 80 µm and a width of 200 µm between the red, green, and blue micro LED chips arranged on the substrate.
　次いで、白色隔壁を形成した基板上に、黒色顔料レジストをスピンコーターで塗布し、９０℃で１０分間プリベークを行った。この塗布膜にマスクアライナーＰＥＭ－６Ｍ（ユニオン光学社製）を用い、フォトマスクを介して紫外線を１００ｍＪ／ｃｍ２（ｉ線露光量換算：全波長露光）の露光量で露光した。次に、テトラメチルアンモニウムヒドロキシドの０．５質量％水溶液のアルカリ現像液で現像し、続いて純水洗浄を行った。 Next, a black pigment resist was applied by a spin coater onto the substrate on which the white barrier ribs were formed, and prebaked at 90° C. for 10 minutes. Using a mask aligner PEM-6M (manufactured by Union Optical Co., Ltd.), this coating film was exposed to ultraviolet rays at an exposure amount of 100 mJ/cm 2 (i-line exposure amount conversion: full wavelength exposure) through a photomask. Next, it was developed with an alkaline developer of 0.5 mass % aqueous solution of tetramethylammonium hydroxide, and then washed with pure water.
　次いで、熱風オーブン中２３０℃で３０分保持しキュアを行なうことで、黒色隔壁を、高さ２０μｍ、幅２００μｍで、白色隔壁の上に形成した。これにより、合計高さ１００μｍ、幅２００μｍの隔壁を形成した。 Then, it was cured in a hot air oven at 230° C. for 30 minutes to form black partition walls having a height of 20 μm and a width of 200 μm on the white partition walls. Thus, barrier ribs having a total height of 100 μm and a width of 200 μm were formed.
　次いで、ＬＥＤチップ上に、ディスペンサーを用いて、透明封止剤としてポリビニルカルバゾールを充填し、カバーガラスと張り合わせた。 Next, the LED chip was filled with polyvinyl carbazole as a transparent sealant using a dispenser, and laminated with a cover glass.
　以上の手順により、ＬＥＤデバイス１８を作製した。 The LED device 18 was produced by the above procedure.
　上記ＬＥＤデバイス１８の作製において、キュア温度を表IIIに示すとおり変更して、ＬＥＤデバイス１９及び２０を作製した。 In the fabrication of LED device 18, LED devices 19 and 20 were fabricated by changing the curing temperature as shown in Table III.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表III中、「ＩＪ」はインクジェット法を示し、「ＰＬ」はフォトリソグラフィ法を示す。 In Table III, "IJ" indicates the inkjet method, and "PL" indicates the photolithography method.
＜評価＞
　上記作製したＬＥＤデバイスを用いて、下記のとおり評価を行った。 <Evaluation>
Using the LED device produced above, evaluation was performed as follows.
（輝度）
　ＬＥＤデバイスを点灯させ、輝度を測定した。ＬＥＤデバイス１～１０は、ＬＥＤデバイス１の輝度を１００とし、それと比較した輝度の相対値を算出し、相対輝度とした。同様に、ＬＥＤデバイス１１～２０は、ＬＥＤデバイス１１の輝度を１００として、相対輝度を算出した。 (Luminance)
The LED device was turned on and the brightness was measured. For the LED devices 1 to 10, the luminance of the LED device 1 was taken as 100, and the relative luminance values were calculated and used as the relative luminance. Similarly, for the LED devices 11 to 20, the relative luminance was calculated with the luminance of the LED device 11 set to 100.
　算出した相対輝度から、下記の評価基準で輝度を評価した。評価結果は表IIIに示すとおりである。
　◎：相対輝度が９０以上
　○：相対輝度が８０以上９０未満
　×：相対輝度が８０未満 Based on the calculated relative brightness, brightness was evaluated according to the following evaluation criteria. The evaluation results are shown in Table III.
◎: Relative brightness is 90 or more ○: Relative brightness is 80 or more and less than 90 ×: Relative brightness is less than 80
（高温耐久性）
　温度８５℃、相対湿度８５％のサーモ機に、ＬＥＤデバイスを投入し、１０００時間保存した。１０００時間保存前の輝度と保存後の輝度から、下記式により、輝度維持率［％］を算出した。
　輝度維持率［％］＝保存後の輝度／保存前の輝度×１００ (high temperature durability)
The LED device was placed in a thermostat with a temperature of 85° C. and a relative humidity of 85%, and stored for 1000 hours. From the luminance before storage for 1000 hours and the luminance after storage, the luminance maintenance rate [%] was calculated by the following formula.
Luminance maintenance rate [%]=Luminance after storage/Luminance before storage×100
　算出した輝度維持率［％］から、下記の評価基準で高温耐久性を評価した。評価結果は表IIIに示すとおりである。
　◎：輝度維持率が９０％以上
　○：輝度維持率が８０％以上９０％未満
　△：輝度維持率が７０％以上８０％未満
　×：輝度維持率が７０％未満 From the calculated luminance retention rate [%], high-temperature durability was evaluated according to the following evaluation criteria. The evaluation results are shown in Table III.
◎: luminance maintenance rate of 90% or more ○: luminance maintenance rate of 80% or more and less than 90% △: luminance maintenance rate of 70% or more and less than 80% ×: luminance maintenance rate of less than 70%
（歩留まり）
　各構成のＬＥＤデバイスを１０個ずつ作製し、各構成において、十分な輝度が得られたＬＥＤデバイスの個数を求めた。 (Yield)
Ten LED devices with each configuration were produced, and the number of LED devices that provided sufficient brightness in each configuration was determined.
　十分な輝度が得られたＬＥＤデバイスの個数から、下記の評価基準で歩留まりを評価した。評価結果は表IIIに示すとおりである。
　◎：十分な輝度が得られたＬＥＤデバイスの個数が９個又は１０個
　○：十分な輝度が得られたＬＥＤデバイスの個数が７個又は８個
　△：十分な輝度が得られたＬＥＤデバイスの個数が５個又は６個
　×：十分な輝度が得られたＬＥＤデバイスの個数が４個以下 Based on the number of LED devices with sufficient brightness, the yield was evaluated according to the following evaluation criteria. The evaluation results are shown in Table III.
◎: 9 or 10 LED devices with sufficient brightness ○: 7 or 8 LED devices with sufficient brightness △: Number of LED devices with sufficient brightness The number is 5 or 6 ×: The number of LED devices with sufficient brightness is 4 or less
　これらの結果から、本発明の隔壁形成用インクジェットインクを用いることによって、輝度を低下させない隔壁を形成する際のＬＥＤデバイスへのダメージを抑えることができ、ＬＥＤデバイスの高温耐久性や歩留まりを向上させることが可能であることが確認できた。 From these results, by using the ink-jet ink for forming barrier ribs of the present invention, it is possible to suppress damage to LED devices when forming barrier ribs that do not reduce luminance, and to improve high-temperature durability and yield of LED devices. It was confirmed that it is possible.
　本発明は、輝度を低下させない隔壁をＬＥＤチップ間に低ダメージで形成することができる隔壁形成用インクジェットインク、隔壁形成用インクジェットインクセット、及びそれを用いたＬＥＤデバイスの製造方法に利用することができる。 INDUSTRIAL APPLICABILITY The present invention can be applied to an ink jet ink for forming a partition wall, an inkjet ink set for forming a partition wall, and a method for manufacturing an LED device using the same, which can form a partition wall between LED chips with low damage without reducing luminance. can.
１　　　ＬＥＤデバイス
２　　　基板
３Ｒ　　赤色ＬＥＤチップ
３Ｇ　　緑色ＬＥＤチップ
３Ｂ　　青色ＬＥＤチップ
４　　　隔壁
４Ｗｈ　白色隔壁
４Ｂｌ　黒色隔壁
５　　　透明封止剤
６　　　カバーガラス 1 LED device 2 substrate 3R red LED chip 3G green LED chip 3B blue LED chip 4 partition 4Wh white partition 4Bl black partition 5 transparent sealant 6 cover glass

Claims (5)

  1. 　ＬＥＤデバイスのＬＥＤチップ間に隔壁を形成するための隔壁形成用インクジェットインクであって、
    　光重合性組成物と、白色色材とを含有し、
    　標準沸点が２５０℃以下である溶剤の含有量が、２５％以下である
    　ことを特徴とする隔壁形成用インクジェットインク。     An inkjet ink for forming partitions for forming partitions between LED chips of an LED device,
    Containing a photopolymerizable composition and a white colorant,
    An inkjet ink for forming partition walls, wherein the content of a solvent having a normal boiling point of 250° C. or less is 25% or less.
  2. 　前記光重合性組成物の成分として、（メタ）アクリレート化合物を含有する
    　ことを特徴とする請求項１に記載の隔壁形成用インクジェットインク。     The inkjet ink for forming partition walls according to claim 1, wherein the photopolymerizable composition contains a (meth)acrylate compound.
  3. 　ＬＥＤデバイスのＬＥＤチップ間に隔壁を形成するための隔壁形成用インクジェットインクセットであって、
    　第１の隔壁形成用インクジェットインクと、第２の隔壁形成用インクジェットインクとを有し、
    　前記第１の隔壁形成用インクジェットインクが、光重合性組成物と、白色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下であり、
    　前記第２の隔壁形成用インクジェットインクが、光重合性組成物と、黒色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下である
    　ことを特徴とする隔壁形成用インクジェットインクセット。     An inkjet ink set for forming partitions for forming partitions between LED chips of an LED device,
    having a first partition-forming inkjet ink and a second partition-forming inkjet ink,
    The first inkjet ink for forming partition walls contains a photopolymerizable composition and a white colorant, and the content of a solvent having a normal boiling point of 250° C. or less is 25% or less,
    The second inkjet ink for forming partition walls contains a photopolymerizable composition and a black colorant, and the content of a solvent having a normal boiling point of 250° C. or less is 25% or less. An inkjet ink set for forming partition walls.
  4. 　ＬＥＤチップ間に隔壁を有するＬＥＤデバイスの製造方法であって、
    　インクジェット法によって前記隔壁のパターニングを行う隔壁形成工程を有し、
    　前記隔壁形成工程が、少なくとも、白色隔壁形成工程を有し、
    　前記白色隔壁形成工程において、光重合性組成物と、白色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下である隔壁形成用インクジェットインクを用いる
    　ことを特徴とするＬＥＤデバイスの製造方法。     A method of manufacturing an LED device having partitions between LED chips, comprising:
    A partition forming step of patterning the partition by an inkjet method,
    The partition forming step has at least a white partition forming step,
    In the step of forming white barrier ribs, an inkjet ink for forming barrier ribs containing a photopolymerizable composition and a white colorant and having a normal boiling point of 250° C. or less and a solvent content of 25% or less is used. A method for manufacturing an LED device, characterized by:
  5. 　前記隔壁形成工程が、少なくとも、前記白色隔壁形成工程と、前記白色隔壁形成工程で形成した白色隔壁の上に黒色隔壁を形成する黒色隔壁形成工程とを有し、
    　前記黒色隔壁形成工程において、光重合性組成物と、黒色色材とを含有し、かつ、標準沸点が２５０℃以下である溶剤の含有量が、２５％以下である隔壁形成用インクジェットインクを用いる
    　ことを特徴とする請求項４に記載のＬＥＤデバイスの製造方法。     The partition wall forming step includes at least the white partition wall forming step and a black partition wall forming step of forming a black partition wall on the white partition wall formed in the white partition wall forming step,
    In the step of forming black partition walls, a partition-forming inkjet ink containing a photopolymerizable composition and a black colorant and containing 25% or less of a solvent having a normal boiling point of 250° C. or lower is used. 5. The manufacturing method of the LED device according to claim 4, characterized in that:
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