WO2022138185A1 - ホワイトインク組成物、硬化物、光拡散層及びカラーフィルタ - Google Patents

ホワイトインク組成物、硬化物、光拡散層及びカラーフィルタ Download PDF

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WO2022138185A1
WO2022138185A1 PCT/JP2021/045259 JP2021045259W WO2022138185A1 WO 2022138185 A1 WO2022138185 A1 WO 2022138185A1 JP 2021045259 W JP2021045259 W JP 2021045259W WO 2022138185 A1 WO2022138185 A1 WO 2022138185A1
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Prior art keywords
ink composition
mass
white ink
ethylenically unsaturated
light
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PCT/JP2021/045259
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English (en)
French (fr)
Japanese (ja)
Inventor
丈雄 城▲崎▼
駿希 境
真哉 佐々木
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Dic株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising 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
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters

Definitions

  • the present invention relates to a white ink composition, a cured product, a light diffusing layer, and a color filter.
  • color filters constituting an organic EL display have a function of converting blue light from an organic EL into red light and green light, and the blue light uses the light from the organic EL as it is to develop a color.
  • Those having a structure for causing the light are usually used.
  • the blue pixel portion of the color filter is formed as a diffusion layer capable of diffusing blue incident light, and the ink constituting the pixel portion contains a light scattering agent and does not have light emitting nanoparticles. It is configured as a so-called white ink printed matter (for example, Patent Document 1).
  • Examples of the printing method of such a color filter include a photolithography method using a curable resist material containing an alkali-soluble resin and / or an acrylic monomer, and an inkjet method using a UV curable ink.
  • the method for manufacturing a color filter by the photolithography method has a drawback that the resist material other than the pixel portion including the relatively expensive luminescent nanocrystal particles is wasted due to the characteristics of the manufacturing method. Therefore, in order to eliminate the waste of the resist material as described above, it has begun to be studied to form the pixel portion of the optical conversion substrate by the inkjet method (see Patent Document 2).
  • the problem to be solved by the present invention is an active energy ray-curable white ink composition applicable to the inkjet method, in which volatility during printing and curing shrinkage during UV curing are suppressed, and a pixel portion is formed. It is an object of the present invention to provide a white ink composition which suppresses film loss in the above and makes it easy to adjust the transmittance of backlight light to a predetermined value.
  • ethylene in a white ink composition containing light-scattering particles, a polymer dispersant, a photopolymerization initiator, and an ethylenically unsaturated monomer having an ethylenically unsaturated group.
  • An active energy ray-curable ink applicable to the inkjet method by setting the content of each of the bifunctional monomers having two sex unsaturated groups and having a molecular weight of 220 or more and 800 or less within a specific range.
  • a white ink composition that suppresses ink volatility during printing and curing shrinkage during UV curing, suppresses film loss in pixel portions, and makes it easy to adjust the transmittance of backlight light to a predetermined value. was found to be obtained.
  • the present invention contains light-scattering particles, a photopolymerization initiator, and an ethylenically unsaturated monomer, has two ethylenically unsaturated groups in the ethylenically unsaturated monomer, and has a molecular weight.
  • the present invention relates to a white ink composition comprising a bifunctional monomer having a value of 220 or more and 800 or less in a proportion of 65 parts by mass or more with respect to 100 parts by mass of the total amount of ethylenically unsaturated monomers.
  • the lower limit of the molecular weight of the bifunctional monomer in the white ink composition of the present invention is 220 or more, it is possible to suppress the volatility of the white ink composition and satisfactorily suppress the curing shrinkage during curing. can. Since the white ink composition of the present invention contains the above-mentioned bifunctional monomer in a predetermined amount, it is possible to suppress the volatility and curing shrinkage of the white ink composition while reducing the viscosity to a level applicable to inkjet. Become.
  • the content of the monofunctional monomer having one ethylenically unsaturated group is preferably 10 parts by mass or less with respect to 100 parts by mass of the total amount of the ethylenically unsaturated monomer.
  • the solvent content is preferably 1% by mass or less based on the total mass of the white ink composition.
  • the ethylenically unsaturated monomer preferably contains two or more kinds of ethylenically unsaturated monomers.
  • the average number of double bond groups of the ethylenically unsaturated monomer is preferably 1.9 or more.
  • the average boiling point of the ethylenically unsaturated monomer at 1 atm is preferably 310 ° C. or higher.
  • the ethylenically unsaturated monomer preferably has a (meth) acryloyl group.
  • the (meth) acrylic equivalent of the ethylenically unsaturated monomer is preferably 120 to 220 g / mol.
  • the (meth) acrylic equivalent of the ethylenically unsaturated monomer is within the above range, the appropriate viscosity and the balance between volatility and curing shrinkage become even better.
  • the content of methacrylate in the ethylenically unsaturated monomer is preferably 20 parts by mass or less with respect to 100 parts by mass of the total amount of the monomers.
  • the monomer having an ethylenically unsaturated group may contain a dicyclopentenyl group-containing monomer.
  • the monomer having an ethylenically unsaturated group may contain a dendrimer acrylate.
  • the content of the light-scattering particles is preferably 3 to 7 parts by mass with respect to 100 parts by mass of the non-volatile content of the white ink composition.
  • the white ink composition may be used by an inkjet method.
  • the white ink composition may be used for forming a cured film having a thickness of 10 ⁇ m or more.
  • One aspect of the present invention relates to a cured product of the white ink composition described above.
  • One aspect of the present invention includes a plurality of pixel portions and a light-shielding portion provided between the plurality of pixel portions, and the plurality of pixel portions include a luminescent pixel portion containing luminescent nanocrystal particles.
  • the present invention relates to a light diffusing layer having a non-emissive pixel portion containing a cured product of the white ink composition.
  • One aspect of the present invention relates to a color filter provided with the above-mentioned light diffusion layer.
  • the present invention is an active energy ray-curable white ink composition applicable to an inkjet method, in which ink volatility during printing and curing shrinkage during UV curing are suppressed, and film loss in a pixel portion is suppressed. It is possible to provide a white ink composition in which it is easy to adjust the transmittance of the backlight light to a predetermined value.
  • FIG. 1 is a schematic cross-sectional view of a color filter according to an embodiment of the present invention.
  • the term "cured product of a white ink composition” means that a curable component in a white ink composition (or a dried white ink composition when the white ink composition contains a solvent component) is cured. It is something that can be obtained. Therefore, it is preferable that the cured product of the white ink composition does not contain a solvent, but a part of the solvent that has not been completely dried may remain.
  • the “nonvolatile component of the white ink composition” means a component other than the solvent contained in the white ink composition. That is, the "nonvolatile component of the white ink composition” may be paraphrased as a pre-cured component to be contained in the cured product of the white ink composition.
  • the white ink composition of one embodiment contains light scattering particles, a polymer dispersant, a photopolymerization initiator, and an ethylenically unsaturated monomer having an ethylenically unsaturated group.
  • the white ink composition is a composition (non-luminous composition) containing light-scattering particles and substantially free of luminescent nanocrystal particles.
  • the content of the luminescent nanocrystal particles in the white ink composition is preferably 0.1 part by mass or less with respect to 100 parts by mass of the non-volatile content of the white ink composition.
  • the white ink composition of one embodiment does not have to contain luminescent nanocrystal particles.
  • the white ink composition is a composition (inkjet ink) used in an inkjet method.
  • the white ink composition (non-light emitting ink composition) does not substantially contain luminescent nanocrystal particles, the pixel portion (cured product of the non luminescent ink composition) formed by the non luminescent ink composition is formed.
  • the light emitted from the pixel portion when the light is incident on the included pixel portion) has substantially the same wavelength as the incident light. Therefore, the white ink composition is suitably used for forming a pixel portion having the same color as the light from the light source.
  • the pixel portion formed by the white ink composition can be a blue pixel portion.
  • the white ink composition is preferably, for example, a white ink composition used for forming a blue pixel portion included in a color filter or the like.
  • the white ink composition can sufficiently suppress volatility and curing shrinkage, and can form a cured product having an appropriate light transmittance. According to one embodiment of the white ink composition, volatility and curing shrinkage are sufficiently suppressed, so that a cured film having an appropriate light transmittance and a thickness of 10 ⁇ m or more (for example, a thickness of 10 ⁇ m) is formed. Can be suitably used for.
  • the light-scattering particles are, for example, optically inert inorganic particles. According to the pixel portion formed by the white ink composition containing light-scattering particles, the light incident on the pixel portion can be scattered, whereby the light intensity of the light emitted from the pixel portion at the viewing angle. The difference can be reduced.
  • Materials constituting the light-scattering particles include, for example, simple metals such as tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum and gold; silica, barium sulfate, barium carbonate, calcium carbonate, etc.
  • Metal oxides such as talc, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, alumina white, titanium oxide, magnesium oxide, barium oxide, aluminum oxide, bismuth oxide, zirconium oxide, zinc oxide; magnesium carbonate, barium carbonate, Metallic carbonates such as secondary bismuth carbonate and calcium carbonate; Metal hydroxides such as aluminum hydroxide; Composite oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate and strontium titanate, bismuth hyponitrate Such as metal salts and the like.
  • the light-scattering particles are from the group consisting of titanium oxide, alumina, zinc oxide, zinc oxide, calcium carbonate, barium sulfate, barium titanate, and silica from the viewpoint of excellent ejection stability and the effect of improving external quantum efficiency. It is preferable to contain at least one selected, and more preferably to contain at least one selected from the group consisting of titanium oxide, zinc oxide, zinc oxide and barium titanate.
  • the light-scattering particles are preferably those in which at least a part of the surface of the particles is covered with an inorganic substance.
  • the inorganic substance preferably contains an element such as Al or Si. Examples of the inorganic substance include alumina (Al 2 O 3 ) and silica (SiO 2 ).
  • the surface of the light-scattering particles may be covered with alumina and / or silica.
  • the surface of the light-scattering particles may be organically treated. That is, the surface of the light-scattering particles may be covered with an organic substance such as a polyol or a siloxane.
  • light-scattering particles for example, commercially available products such as chlorine oxide titanium oxide (rutile type) manufactured by Ishihara Sangyo Co., Ltd. (for example, "PF-690") and Typure (registered trademark) R-350 manufactured by Chemours are used. It is also possible.
  • the shape of the light-scattering particles is preferably spherical, filamentous, indefinite, or the like.
  • using particles having less directional particle shape for example, particles having a spherical shape, a regular tetrahedron shape, etc.
  • it is more preferable in that it can obtain excellent ejection stability.
  • the average particle size (volume average diameter) of the light-scattering particles in the white ink composition is preferably 50 nm or more, 200 nm or more, or 300 nm or more.
  • the average particle size (volume average diameter) of the light-scattering particles in the white ink composition is preferably 1000 nm or less, 600 nm or less, or 400 nm or less. From the viewpoint that such an average particle diameter (volume average diameter) can be easily obtained, the average particle diameter (volume average diameter) of the light-scattering particles used is preferably 50 nm or more, and preferably 1000 nm or less. ..
  • the average particle diameter (volume average diameter) of the light-scattering particles in the white ink composition is obtained by measuring with a dynamic light-scattering nanotrack particle size distribution meter and calculating the volume average diameter. Be done. Further, the average particle diameter (volume average diameter) of the light-scattering particles to be used can be obtained by measuring the particle diameter of each particle with, for example, a transmission electron microscope or a scanning electron microscope, and calculating the volume average diameter.
  • the content of the light-scattering particles is 0.5 parts by mass or more, 3 parts by mass or more, and 4 parts by mass with respect to 100 parts by mass of the non-volatile content (component of the ink composition excluding the organic solvent) of the white ink composition. It is preferably 7 parts by mass or more, 5 parts by mass or more, or 6 parts by mass or more.
  • the content of the light-scattering particles is preferably 10 parts by mass or less, 9 parts by mass or less, or 8 parts by mass or less with respect to 100 parts by mass of the non-volatile content of the white ink composition.
  • the content of the light-scattering particles is preferably 3 to 7 parts by mass or 3 to 10 parts by mass with respect to 100 parts by mass of the non-volatile content of the white ink composition.
  • the white ink composition contains an ethylenically unsaturated monomer having an ethylenically unsaturated group.
  • the ethylenically unsaturated monomer means a monomer having an ethylenically unsaturated bond (carbon-carbon double bond).
  • Examples of the ethylenically unsaturated monomer include a monomer having one ethylenically unsaturated group (monofunctional monomer) and a monomer having two or more ethylenically unsaturated groups (polyfunctional monomer).
  • the number of ethylenically unsaturated bonds (for example, the number of ethylenically unsaturated groups) in the polyfunctional monomer is preferably 2-3, for example.
  • the ethylenically unsaturated monomer preferably contains one kind or two or more kinds of ethylene unsaturated monomers.
  • the ethylenically unsaturated group is preferably a vinyl group, a vinylene group, a vinylidene group, a (meth) acryloyl group, or the like, and more preferably a (meth) acryloyl group.
  • “(meth) acryloyl group” means “acryloyl group” and the corresponding "methacryloyl group”. The same applies to the expressions "(meth) acrylate” and "(meth) acrylamide”.
  • the content of the monofunctional monomer in the ethylenically unsaturated monomer is preferably 10 parts by mass or less with respect to 100 parts by mass of the ethylenically unsaturated monomer. From the viewpoint of further improving the effect of the present invention, the content of the monofunctional monomer is 9.5 parts by mass or less, 9.0 parts by mass or less, and 8.0 parts by mass or less with respect to 100 parts by mass of the ethylenically unsaturated monomer. , 7.0 parts by mass or less, 6.0 parts by mass or less, 5.0 parts by mass or less, 4.0 parts by mass or less, 3.0 or 2.0 parts by mass or less, more preferably. The content of the monofunctional monomer is preferably 0 to 10 parts by mass or 0 to 9 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer.
  • Examples of the monofunctional monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth).
  • the ethylenically unsaturated monomer contains a bifunctional monomer (first bifunctional monomer) having two ethylenically unsaturated groups and having a molecular weight of 220 or more and 800 or less.
  • the first bifunctional monomer preferably contains a bifunctional monomer having a molecular weight of 225 or more and 335 or less.
  • the first bifunctional monomer may be used alone or in combination of two or more. Since the lower limit of the first bifunctional monomer is 220 or more, the volatility of the white ink composition and the curing shrinkage during curing can be satisfactorily suppressed.
  • the content of the first bifunctional monomer in the ethylenically unsaturated monomer is 65 parts by mass or more with respect to 100 parts by mass of the ethylenically unsaturated monomer.
  • the content of the first bifunctional monomer is preferably 70 parts by mass or more, 75 parts by mass or more, or 80 parts by mass or more, and 99 parts by mass or less, or 99 parts by mass or more, with respect to 100 parts by mass of the ethylenically unsaturated monomer. It is preferably 96 parts by mass or less.
  • the ethylenically unsaturated monomer may contain a bifunctional monomer (second bifunctional monomer) that does not correspond to the first bifunctional monomer.
  • the second bifunctional monomer may be used alone or in combination of two or more.
  • the content of the second bifunctional monomer in the ethylenically unsaturated monomer is preferably 1 part by mass or more, 3 parts by mass or more, or 5 parts by mass or more with respect to 100 parts by mass of the ethylenically unsaturated monomer. , Less than 35 parts by mass, 25 parts by mass or less, 15 parts by mass or less, or 10 parts by mass or less.
  • bifunctional monomer examples include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,5-pentanediol di.
  • the two hydroxyl groups of the di (meth) acrylate in which the two hydroxyl groups of the above are substituted with (meth) acryloyloxy groups, and the two hydroxyl groups of the diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A are (meth).
  • Di (meth) acrylate substituted with an acryloyloxy group The two hydroxyl groups of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane are substituted with a (meth) acryloyloxy group.
  • Di (meth) acrylate di (meth) acrylate in which two hydroxyl groups of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A is replaced with a (meth) acryloyloxy group.
  • di (meth) acrylate in which two hydroxyl groups of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A is replaced with a (meth) acryloyloxy group.
  • the content of the monomer having 3 or more ethylenically unsaturated groups is 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more with respect to 100 parts by mass of the total amount of ethylenically unsaturated monomers. It is preferably 35 parts by mass or less, or 30 parts by mass or less.
  • the content of the monomer having three ethylenically unsaturated groups (trifunctional monomer) is preferably within the above range.
  • trifunctional monomer examples include glycerintri (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropanetri (meth) acrylicate, and EO-modified trimethylolpropanetri (meth) acrylate.
  • the ethylenically unsaturated monomer may contain a dendrimer compound having a (meth) acryloyl group as a polyfunctional monomer other than the above-mentioned bifunctional monomer and trifunctional monomer.
  • the dendrimer compound having a (meth) acryloyl group is preferably a compound having 10 or more (meth) acryloyl groups per molecule. Examples of the dendrimer compound having a (meth) acryloyl group include dendrimer acrylate.
  • the ethylenically unsaturated monomer contains a dendrimer compound having a (meth) acryloyl group (for example, a dendrimer acrylate)
  • the density of the (meth) acryloyl group in the dendrimer molecule tends to increase and the curing rate tends to be further improved.
  • the content of the dendrimer compound having a (meth) acryloyl group is, for example, 1 part by mass or more, 2 parts by mass or more, 4 parts by mass or more, or 5 parts by mass or more with respect to 100 parts by mass of the total amount of the ethylenically unsaturated monomer. It is preferably 20 parts by mass or less, 15 parts by mass or less, or 10 parts by mass or less.
  • the average number of double bond groups of the ethylenically unsaturated monomer is preferably 1.5 or more, 1.7 or more, or 1.9 or more.
  • the average number of double bond groups of the ethylenically unsaturated monomer is preferably 2.2 or less or 2.1 or less, for example.
  • the average number of double bond groups of the ethylenically unsaturated monomer is within the above range, the volatility of the ink is further suppressed.
  • the average number of double bond groups of the ethylenically unsaturated monomer is the number of double bond groups per molecule of the ethylenically unsaturated monomer.
  • the average number of double bond groups of the ethylenically unsaturated monomer is the number of ethylenically unsaturated groups of the ethylenically unsaturated monomer in the white ink composition. Is the average value of.
  • the specific method for calculating the average number of double bond groups of the ethylenically unsaturated monomer is as described in Examples described later.
  • the average boiling point of the ethylenically unsaturated monomer at 1 atm (0.1 MPa) is preferably 310 ° C. or higher, 320 ° C. or higher, or 325 ° C. or higher, preferably 380 ° C. or lower, or 370 ° C. from the viewpoint of ink volatility. The following is preferable.
  • the average boiling point of the ethylenically unsaturated monomer at 1 atm (0.1 MPa) is within the above range, the volatility of the white ink composition can be further suppressed.
  • the average boiling point is the boiling point of the ethylenically unsaturated monomer in the white ink composition at 1 atm (0.1 MPa).
  • the average boiling point is the average boiling point of the ethylenically monomers at 1 atm (0.1 MPa).
  • the average boiling point of the ethylenically unsaturated monomer at 1 atm (0.1 MPa) can be determined by the method described in Examples described later.
  • the boiling point of the ethylenically unsaturated monomer at 1 atm is listed in SciFinder (online search service of Chemical Abstracts Service, American Chemical Society).
  • the ethylenically unsaturated monomer is preferably a monomer having a (meth) acryloyl group ((meth) acrylate).
  • the (meth) acrylic equivalent of the ethylenically unsaturated monomer is preferably 110 g / mol or more, 120 g / mol or more, or 125 g / mol or more from the viewpoint of suppressing curing shrinkage.
  • the (meth) acrylic equivalent of the ethylenically unsaturated monomer is preferably 260 g / mol or less, 240 g / mol or more, or 220 g / mol or more from the viewpoint of reducing the ink viscosity.
  • the (meth) acrylic equivalent of the ethylenically unsaturated monomer is preferably 120 g / mol or more and 220 g / mol or less, for example, from the viewpoint of excellent balance between the viscosity of the ink and the suppression of curing shrinkage.
  • the (meth) acrylic equivalent of the ethylenically unsaturated monomer is within the above range, curing shrinkage can be further suppressed.
  • the white ink composition contains two or more kinds of ethylenically unsaturated monomers
  • the (meth) acrylic equivalent of the ethylenically unsaturated monomers is an average value of the (meth) acrylic equivalents of the ethylenically unsaturated monomers.
  • the specific calculation method is as described in Examples described later.
  • the ethylenically unsaturated monomer may or may not contain methacrylate (methacryloyl monomer), which is a monomer having a methacryloyloxy group.
  • methacrylate is preferably the methacrylate exemplified above.
  • the content of methacrylate is preferably 20 parts by mass or less with respect to 100 parts by mass of the total amount of the ethylenically unsaturated monomer from the viewpoint of further suppressing the curing shrinkage.
  • the content of methacrylate is preferably, for example, 0 to 20 parts by mass or 0 to 15 parts by mass with respect to 100 parts by mass of the total amount of the ethylenically unsaturated monomer.
  • the content of methacrylate is the total content of methacrylate with respect to 100 parts by mass of the ethylenically unsaturated monomer in the white ink composition.
  • the ethylenically unsaturated monomer may contain a dicyclopentenyl group-containing monomer from the viewpoint that curing shrinkage is more easily suppressed.
  • the dicyclopentenyl group-containing monomer include dicyclopentenyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate.
  • the content of the dicyclopentenyl group-containing monomer is preferably 5 parts by mass or more, 8 parts by mass or more, or 10 parts by mass or more, and 20 parts by mass or less, based on 100 parts by mass of the total amount of the ethylenically unsaturated monomer. , Or 15 parts by mass or less.
  • the ethylenically unsaturated monomer is preferably alkali-insoluble from the viewpoint that a highly reliable pixel portion (cured product of white ink composition) can be easily obtained.
  • the fact that the ethylenically unsaturated monomer is alkali-insoluble means that the amount of the ethylenically unsaturated monomer dissolved in 1% by mass of potassium hydroxide aqueous solution at 25 ° C. is based on the total mass of the ethylenically unsaturated monomer. It means that it is 30% by mass or less.
  • the dissolved amount of the ethylenically unsaturated monomer is preferably 10% by mass or less, more preferably 3% by mass or less.
  • the content of the ethylenically unsaturated monomer is from the viewpoint that an appropriate viscosity can be easily obtained as an inkjet ink, from the viewpoint of improving the curability of the white ink composition, and the resistance of the pixel portion (cured product of the white ink composition).
  • the amount is preferably 70 parts by mass or more, 80 parts by mass or more, or 85 parts by mass or more with respect to 100 parts by mass of the non-volatile content of the white ink composition.
  • the content of the ethylenically unsaturated monomer is 99 parts by mass or less, 96 parts by mass or less, or 96 parts by mass or less with respect to 100 parts by mass of the non-volatile content of the white ink composition from the viewpoint that an appropriate viscosity can be easily obtained as an inkjet ink. It is preferably 94 parts by mass or less.
  • the ethylenically unsaturated monomer also functions as a dispersion medium, it is possible to disperse light-scattering particles without a solvent. In this case, there is an advantage that the step of removing the solvent by drying when forming the pixel portion becomes unnecessary.
  • the photopolymerization initiator is, for example, a photoradical polymerization initiator or a photocationic polymerization initiator.
  • a photoradical polymerization initiator a molecular cleavage type or hydrogen abstraction type photoradical polymerization initiator is suitable.
  • Examples of the molecular cleavage type photoradical polymerization initiator include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-benzyl-2-dimethylamino-1.
  • -(4-Morphorinophenyl) -butane-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide Etc. are preferably used.
  • molecular cleavage type photoradical polymerization initiators include 1-hydroxycyclohexylphenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4). -Isopropylphenyl) -2-hydroxy-2-methylpropane-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one may be used in combination.
  • Examples of the hydrogen abstraction type photoradical polymerization initiator include benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4'-methyl-diphenylsulfide and the like.
  • a molecular cleavage type photoradical polymerization initiator and a hydrogen abstraction type photoradical polymerization initiator may be used in combination.
  • a commercially available product can also be used as the photocationic polymerization initiator.
  • Commercially available products include sulfonium salt-based photocationic polymerization initiators such as "CPI-100P” manufactured by San-Apro, acylphosphine oxide compounds such as "Lucirin TPO” manufactured by BASF, and "Irgacure 907" manufactured by BASF. Examples thereof include “Irgacure 819", “Irgacure 379EG”, “Irgacure 184" and "Irgacure PAG290".
  • the content of the photopolymerization initiator is 0.1 part by mass or more, 0.5 part by mass or more, and 1 part by mass or more with respect to 100 parts by mass of the ethylenically unsaturated monomer. It is preferably 3 parts by mass or more, or 5 parts by mass or more.
  • the content of the photopolymerization initiator is 40 parts by mass or less, 30 parts by mass or less with respect to 100 parts by mass of the ethylenically unsaturated monomer, from the viewpoint of the stability over time of the pixel portion (cured product of the white ink composition). It is preferably 20 parts by mass or less, or 10 parts by mass or less.
  • the polymer dispersant is a polymer compound having a functional group having an affinity for light-scattering particles.
  • the polymer dispersant has a function of dispersing light-scattering particles.
  • the polymer dispersant is adsorbed on the light-scattering particles via a functional group having an affinity for the light-scattering particles, and the light-scattering particles are generated by electrostatic repulsion and / or steric repulsion between the polymer dispersants. Disperse in the white ink composition.
  • the white ink composition contains a polymer dispersant
  • the content of light-scattering particles is relatively large (for example, when the content is 5% by mass or more with respect to 100 parts by mass of the non-volatile content of the white ink composition).
  • the light-scattering particles can be satisfactorily dispersed.
  • the polymer dispersant may be bonded to the surface of the light-scattering particles and adsorbed on the light-scattering particles.
  • the polymer dispersant preferably has a weight average molecular weight of 750 or more. In the present specification, the weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography).
  • Examples of the functional group having an affinity for light-scattering particles include an acidic functional group, a basic functional group and a nonionic functional group.
  • the acidic functional group has a dissociative proton and may be neutralized by a base such as an amine or a hydroxide ion, and the basic functional group is neutralized by an acid such as an organic acid or an inorganic acid. May be.
  • the acidic functional groups include a carboxyl group (-COOH), a sulfo group (-SO 3 H), a sulfate group (-OSO 3 H), a phosphonic acid group (-PO (OH) 3 ), and a phosphate group (-OPO (-OPO)).
  • OH) 3 a carboxyl group
  • sulfo group a sulfo group
  • -OSO 3 H a sulfate group
  • -PO (OH) 3 a phosphonic acid group
  • -OPO (-OPO) phosphate group
  • OH) 3 phosphinic acid group (-PO (OH)-), mercapto group (-SH), and the like.
  • Examples of the basic functional group include primary, secondary and tertiary amino groups, ammonium groups, imino groups, and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole, and triazole.
  • Nonionic functional groups include hydroxy group, ether group, thioether group, sulfinyl group (-SO-), sulfonyl group ( -SO2- ), carbonyl group, formyl group, ester group, carbonate ester group, amide group, and the like. Examples thereof include a carbamoyl group, a ureido group, a thioamide group, a thioureido group, a sulfamoyl group, a cyano group, an alkenyl group, an alkynyl group, a phosphine oxide group and a phosphine sulfide group.
  • the polymer dispersant is preferably a polymer of a single monomer (homopolymer) or a copolymer of a plurality of types of monomers (copolymer). Further, the polymer dispersant may be any of a random copolymer, a block copolymer or a graft copolymer. When the polymer dispersant is a graft copolymer, it is preferably a comb-shaped graft copolymer or a star-shaped graft copolymer.
  • polymer dispersant examples include acrylic resin, polyester resin, polyurethane resin, polyamide resin, polyether, phenol resin, silicone resin, polyurea resin, amino resin, epoxy resin, polyamine such as polyethyleneimine and polyallylamine, and polyimide. Can be mentioned.
  • the polymer dispersant is preferably a compound having at least a basic functional group.
  • the amine value of the polymer dispersant is preferably 5 mgKOH / g or more, 10 mgKOH / g or more, 20 mgKOH / g or more, or 30 mgKOH / g or more.
  • the amine value of the polymer dispersant is preferably 120 mgKOH / g or less, 100 mgKOH / g or less, or 90 mgKOH / g or less.
  • polymer dispersant Commercially available products can be used as the polymer dispersant, and the commercially available products include Ajinomoto Fine-Techno Co., Ltd.'s Azispar PB series, BYK's DISPERBYK series, BYK-series, and BASF's Efka series. (For example, PX-4701), "SS71000” manufactured by Lubrizol, or the like can be used.
  • the polymer dispersant is preferably 3 parts by mass or more, or 5 parts by mass or more, and preferably 20 parts by mass or less, or 15 parts by mass or less, with respect to 100 parts by mass of the light-scattering particles.
  • the white ink composition may be substantially free of solvent.
  • the solvent is preferably an organic solvent usually used as a solvent for, for example, a white ink composition.
  • the content of the solvent in the white ink composition is preferably 1% by mass or less based on the total mass of the white ink composition.
  • the content of the solvent in the white ink composition is, for example, 0.0 to 0.8% by mass, 0.0 to 0.6% by mass, 0.0 to 0, based on the total mass of the white ink composition. It is preferably 0.4% by mass, or 0.0 to 0.2% by mass.
  • the solvent is a substance that does not have a polymerizable functional group (for example, an ethylenically unsaturated group) and has a boiling point of 300 ° C. or lower under atmospheric pressure.
  • the white ink composition contains components other than the above-mentioned components (for example, thermosetting resin, curing agent, curing accelerator (curing catalyst), polymerization inhibitor, chain transfer agent, oxidation) as long as the effects of the present invention are not impaired.
  • An inhibitor, etc. may be further contained.
  • the viscosity of the white ink composition described above at the ink temperature during inkjet printing may be, for example, 2 mPa ⁇ s or more, 5 mPa ⁇ s or more, or 7 mPa ⁇ s or more from the viewpoint of ejection stability during inkjet printing. preferable.
  • the viscosity of the white ink composition at the ink temperature during inkjet printing is preferably 20 mPa ⁇ s or less, 15 mPa ⁇ s or less, or 12 mPa ⁇ s or less.
  • the viscosity of the white ink composition is, for example, the viscosity measured by an E-type viscometer, which is measured at 25 ° C.
  • the viscosity of the white ink composition at the ink temperature during inkjet printing is 2 mPa ⁇ s or more, the meniscus shape of the inkjet ink at the tip of the ink ejection hole of the ejection head is stable, so that the ejection control of the inkjet ink (for example, Control of discharge amount and discharge timing) becomes easy.
  • the viscosity of the white ink composition at the ink temperature at the time of inkjet printing is 20 mPa ⁇ s or less, the inkjet ink can be smoothly ejected from the ink ejection holes.
  • the surface tension of the white ink composition is preferably a surface tension suitable for the inkjet method, specifically, preferably in the range of 20 to 40 mN / m, and more preferably 25 to 35 mN / m. preferable.
  • discharge control for example, control of discharge amount and discharge timing
  • the flight bending means that when the white ink composition is ejected from the ink ejection holes, the landing position of the white ink composition deviates from the target position by 30 ⁇ m or more.
  • the surface tension is 40 mN / m or less, the meniscus shape at the tip of the ink ejection hole is stable, so that the ejection control of the white ink composition (for example, control of the ejection amount and the ejection timing) becomes easy.
  • the surface tension is 20 mN / m or more, it is possible to prevent the peripheral portion of the ink ejection hole from being contaminated with the inkjet ink, so that the occurrence of flight bending can be suppressed.
  • a pixel portion may not be accurately filled in the pixel portion forming region to be landed and the white ink composition may not be sufficiently filled, or a pixel portion forming region (or pixel portion) adjacent to the pixel portion forming region to be landed may be generated. ),
  • the white ink composition does not land and the color reproducibility does not deteriorate.
  • the surface tension described in the present specification refers to the surface tension measured at 23 ° C., which is measured by the ring method (also referred to as the ring method).
  • the white ink composition of the present embodiment When used as a white ink composition for an inkjet method, it may be applied to a piezojet type inkjet recording device using a mechanical ejection mechanism using a piezoelectric element.
  • the inkjet white ink composition of the above-described embodiment can be used, for example, by a photolithography method in addition to the inkjet method.
  • the white ink composition contains an alkali-soluble resin as a binder polymer.
  • the white ink composition When the white ink composition is used by the photolithography method, first, the white ink composition is applied on a substrate, and then the white ink composition is dried to form a coating film.
  • the coating film thus obtained is soluble in an alkaline developer and is patterned by being treated with an alkaline developer.
  • the alkaline developer is mostly an aqueous solution from the viewpoint of ease of waste liquid treatment of the developer, the coating film of the white ink composition is treated with the aqueous solution.
  • the coating film of the white ink composition is preferably alkali-insoluble. That is, the white ink composition of the present embodiment is preferably a white ink composition capable of forming an alkali-insoluble coating film.
  • Such a white ink composition can be obtained by using a curable component capable of forming an alkali-insoluble cured product.
  • the fact that the coating film of the ink composition is alkaline insoluble means that the amount of the coating film of the white ink composition dissolved at 25 ° C. in a 1% by mass potassium hydroxide aqueous solution is based on the total mass of the coating film of the white ink composition. It means that it is 30% by mass or less.
  • the dissolved amount of the coating film of the white ink composition is preferably 10% by mass or less, more preferably 3% by mass or less.
  • the white ink composition is a white ink composition capable of forming an alkali-insoluble coating film, which is obtained by applying the white ink composition on a substrate and then drying it at 80 ° C. for 3 minutes. It can be confirmed by measuring the above-mentioned dissolution amount of the coating film having a thickness of 1 ⁇ m.
  • Another embodiment of the present invention is a cured product (cured film) of the white ink composition, and it can be said that the cured product (cured film) of the white ink composition is alkali-insoluble. As a result, it becomes easy to obtain a pixel portion having excellent reliability.
  • the fact that the cured product of the white ink composition is alkaline insoluble means that the amount of the cured product of the white ink composition dissolved at 25 ° C. in 1% by mass of a potassium hydroxide aqueous solution is the curing amount of the white ink composition, as described above. It means that it is 30% by mass or less based on the total mass of the object.
  • the dissolved amount of the cured product of the white ink composition is preferably 10% by mass or less, more preferably 3% by mass or less.
  • the cured product (cured film) of the white ink composition has an appropriate light transmittance.
  • the transmittance of blue light of the cured product of the white ink composition is preferably 61 to 63%, for example.
  • the transmittance of blue light is measured by the method described in Examples described later.
  • the white ink composition of the above-described embodiment includes, for example, a step of mixing light scattering particles, a photopolymerization initiator and an ethylenically unsaturated monomer, and if necessary, other components (for example, a polymer dispersant). It can be manufactured by the method.
  • a dispersion treatment may be carried out in addition to the mixing.
  • the mixing and dispersion treatment may be performed using a dispersion device such as a bead mill, a paint conditioner, a planetary stirrer, or a jet mill. It is preferable to use a bead mill or a paint conditioner from the viewpoint that the dispersibility of the light-scattering particles is good and the average particle size of the light-scattering particles can be easily adjusted to a desired range.
  • the ink composition set of one embodiment includes the white ink composition of the above-described embodiment.
  • the ink composition set may include an ink composition (light emitting ink composition) containing luminescent nanocrystal particles in addition to the white ink composition (non-light emitting ink composition) of the above-described embodiment. ..
  • the luminescent ink composition is, for example, a curable ink composition.
  • a conventionally known ink composition can be used.
  • an ink composition containing luminescent nanocrystal particles can also be used.
  • the luminescent nanocrystal particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, and for example, the maximum particle size measured by a transmission electron microscope or a scanning electron microscope is 100 nm or less. It is a crystal.
  • the luminescent nanocrystal particles can emit light (fluorescence or phosphorescence) having a wavelength different from the absorbed wavelength, for example, by absorbing light having a predetermined wavelength.
  • the luminescent nanocrystal particles are red luminescent nanocrystal particles (red luminescent nanocrystal particles) that emit light (red light) having an emission peak wavelength in the range of 605 to 665 nm, and emission peak wavelengths in the range of 500 to 560 nm.
  • Green-emitting nano-crystal particles green-emitting nano-crystal particles that emit light (green light), or blue-emitting nano that emits light (blue light) having an emission peak wavelength in the range of 420 to 480 nm.
  • the ink preferably contains at least one of these luminescent nanocrystal particles.
  • the light absorbed by the luminescent nanocrystal particles is, for example, light having a wavelength in the range of 400 nm or more and less than 500 nm (particularly, light having a wavelength in the range of 420 to 480 nm) (blue light) or light in the range of 200 nm to 400 nm. It is preferable that the light has a wavelength of (ultraviolet light).
  • the emission peak wavelength of the luminescent nanocrystal particles can be confirmed, for example, in the fluorescence spectrum or the phosphorescence spectrum measured by using a spectrofluorometer.
  • the red-emitting nanocrystal particles are 665 nm or less, 663 nm or less, 660 nm or less, 658 nm or less, 655 nm or less, 653 nm or less, 651 nm or less, 650 nm or less, 647 nm or less, 645 nm or less, 643 nm or less, 640 nm or less, 637 nm or less, 635 nm or less.
  • an emission peak wavelength of 632 nm or less or 630 nm or less it is preferable to have an emission peak wavelength of 628 nm or more, 625 nm or more, 623 nm or more, 620 nm or more, 615 nm or more, 610 nm or more, 607 nm or more or 605 nm or more.
  • These upper limit values and lower limit values can be arbitrarily combined. In the same description below, the upper limit value and the lower limit value described individually can be arbitrarily combined.
  • Green luminescent nanocrystal particles have emission peak wavelengths of 560 nm or less, 557 nm or less, 555 nm or less, 550 nm or less, 547 nm or less, 545 nm or less, 543 nm or less, 540 nm or less, 537 nm or less, 535 nm or less, 532 nm or less, or 530 nm or less.
  • an emission peak wavelength of 528 nm or more, 525 nm or more, 523 nm or more, 520 nm or more, 515 nm or more, 510 nm or more, 507 nm or more, 505 nm or more, 503 nm or more, or 500 nm or more.
  • Blue luminescent nanocrystal particles have emission peak wavelengths of 480 nm or less, 477 nm or less, 475 nm or less, 470 nm or less, 467 nm or less, 465 nm or less, 463 nm or less, 460 nm or less, 457 nm or less, 455 nm or less, 452 nm or less, or 450 nm or less.
  • an emission peak wavelength at 450 nm or more, 445 nm or more, 440 nm or more, 435 nm or more, 430 nm or more, 428 nm or more, 425 nm or more, 422 nm or more, or 420 nm or more.
  • the wavelength of light emitted by luminescent nanocrystal particles depends on the size of the luminescent nanocrystal particles (for example, particle size) according to the solution of the Schrodinger wave equation of the well-type potential model, but the luminescent nanocrystal particles. It also depends on the energy gap of the crystal particles. Therefore, the emission color can be selected by changing the constituent material and size of the luminescent nanocrystal particles to be used.
  • the luminescent nanocrystal particles are preferably luminescent nanocrystal particles (luminescent semiconductor nanocrystal particles) containing a semiconductor material.
  • Examples of the luminescent semiconductor nanocrystal particles include quantum dots and quantum rods. Among these, quantum dots are preferable from the viewpoint of easy control of the emission spectrum.
  • the luminescent semiconductor nanocrystal particles may consist only of a core containing the first semiconductor material, and include a core containing the first semiconductor material and a second semiconductor material different from the first semiconductor material, as described above. It may have a shell that covers at least a portion of the core.
  • the structure of the luminescent semiconductor nanocrystal particles is preferably a structure consisting of only a core (core structure) or a structure consisting of a core and a shell (core / shell structure).
  • the luminescent semiconductor nanocrystal particles include a third semiconductor material different from the first and second semiconductor materials in addition to the shell (first shell) containing the second semiconductor material, and the above-mentioned core.
  • the structure of the luminescent semiconductor nanocrystal particles is preferably a structure including a core, a first shell, and a second shell (core / shell / shell structure).
  • Each of the core and the shell is preferably a mixed crystal (for example, CdSe + CdS, CIS + ZnS, etc.) containing two or more kinds of semiconductor materials.
  • the luminescent nanocrystal particles are selected as the semiconductor material from the group consisting of II-VI group semiconductors, III-V group semiconductors, I-III-VI group semiconductors, IV group semiconductors and I-II-IV-VI group semiconductors. It is preferable to contain at least one semiconductor material.
  • Specific semiconductor materials include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeDZn.
  • red-emitting semiconductor nanocrystal particles examples include CdSe nanocrystal particles and nanocrystal particles having a core / shell structure, wherein the shell portion is CdS and the inner core portion is CdSe.
  • the shell part is a mixed crystal of ZnS and ZnSe and the inner core part is InP nanocrystal particles, the mixed crystal nanocrystal particles of CdSe and CdS, the mixed crystal nanocrystal particles of ZnSe and CdS, and the core.
  • Nanocrystal particles with a / shell / shell structure the first shell portion is ZnSe, the second shell portion is ZnS, and the inner core portion is InP.
  • Nanocrystal particles with a shell structure the first shell portion is a mixed crystal of ZnS and ZnSe, the second shell portion is ZnS, and the inner core portion is InP. And so on.
  • green-emitting semiconductor nanocrystal particles examples include CdSe nanocrystal particles, mixed-crystal nanocrystal particles of CdSe and ZnS, and nanocrystal particles having a core / shell structure, wherein the shell portion is ZnS.
  • Nanocrystal particles whose inner core is InP nanocrystal particles having a core / shell structure, whose shell is a mixed crystal of ZnS and ZnSe, and whose inner core is InP.
  • Nanocrystal particles with a core / shell / shell structure the first shell portion is a mixed crystal of ZnS and ZnSe, the second shell portion is ZnS, and the inner core portion is InP. Examples include certain nanocrystal particles.
  • the blue light emitting semiconductor nanocrystal particles include, for example, ZnSe nanocrystal particles, ZnS nanocrystal particles, and nanocrystal particles having a core / shell structure, and the shell portion is ZnSe and the inner core portion.
  • the nano-crystal particles have a core / shell / shell structure.
  • the first shell portion is ZnSe
  • the second shell portion is ZnS
  • the inner core portion is InP
  • the nanocrystal particles have a core / shell / shell structure. Examples thereof include nano-crystal particles in which the first shell portion is a mixed crystal of ZnS and ZnSe, the second shell portion is ZnS, and the inner core portion is InP.
  • Semiconductor nanocrystal particles have the same chemical composition, and by changing the average particle size of the particles themselves, the color to be emitted from the particles can be changed to red or green. Further, it is preferable to use semiconductor nanocrystal particles as such, which have as little adverse effect on the human body as possible.
  • semiconductor nanocrystal particles containing cadmium, selenium, etc. are used as luminescent nanocrystal particles
  • semiconductor nanocrystal particles containing the above elements (cadmium, selenium, etc.) as little as possible are selected and used alone, or the above elements. It is preferable to use it in combination with other luminescent nanocrystal particles so that the amount is as small as possible.
  • the shape of the luminescent nanocrystal particles is not particularly limited, and examples of the shape of the luminescent nanocrystal particles include an arbitrary geometric shape or an arbitrary irregular shape. Examples of the shape of the luminescent nanocrystal particles include a spherical shape, an ellipsoidal shape, a pyramidal shape, a disc shape, a branch shape, a net shape, a rod shape, and the like. As the luminescent nanocrystal particles, it is preferable to use particles having less directional particle shape (for example, particles having a spherical shape, a regular tetrahedron shape, or the like) in that the uniformity and fluidity of the ink can be further improved.
  • the average particle size (volume average diameter) of the luminescent nanocrystal particles is 1 nm or more, 1.5 nm or more, or 2 nm from the viewpoint of easily obtaining light emission of a desired wavelength and excellent dispersibility and storage stability.
  • the above is preferable, and from the viewpoint that a desired emission wavelength can be easily obtained, it is preferably 40 nm or less, 30 nm or less, or 20 nm or less.
  • the average particle diameter (volume average diameter) of the luminescent nanocrystal particles is obtained by measuring with a transmission electron microscope or a scanning electron microscope and calculating the volume average diameter.
  • the luminescent nanocrystal particles preferably have an organic ligand on the surface thereof.
  • the surface of the luminescent nanocrystal particles may be passivated by an organic ligand.
  • the organic ligand may be coordinate-bonded to the surface of the luminescent nanocrystal particles. Details of the organic ligand will be described later.
  • the luminescent nanocrystal particles may have a polymer dispersant on the surface thereof.
  • the polymer dispersant may be bound to the surface of the luminescent nanocrystal particles by exchanging the organic ligand that binds to the surface of the luminescent nanocrystal particles with the polymer dispersant.
  • the polymer dispersant is blended with the luminescent nanocrystal particles in which the organic ligand is coordinated. Details of the polymer dispersant will be described later.
  • the luminescent nanocrystal particles those dispersed in a colloidal form in a solvent, an ethylenically unsaturated monomer, or the like can be used.
  • the surface of the luminescent nanocrystal particles in a dispersed state is preferably passivated by an organic ligand.
  • the solvent include cyclohexane, hexane, heptane, chloroform, toluene, octane, chlorobenzene, tetralin, diphenyl ether, propylene glycol monomethyl ether acetate, butyl carbitol acetate, or a mixture thereof.
  • luminescent nanocrystal particles examples include indium phosphide / zinc sulfide, D-dot, CuInS / ZnS from NN-Labs, and InP / ZnS from Aldrich.
  • the content of the luminescent nanocrystal particles is, for example, 20 to 80% by mass, 22 to 70% by mass, and 24 to 60% by mass based on the total mass of the ink from the viewpoint of further improving the external quantum efficiency of the pixel portion. , 24-50% by mass or 26-40% by mass.
  • the content of the luminescent nanocrystal particles does not include the amount of the organic ligand bound to the luminescent nanocrystal particles.
  • the "total mass of the ink" can be rephrased as a component to be contained in the cured product of the ink. That is, when the ink contains a solvent, it means a component other than the solvent contained in the ink, and the amount of the solvent is not included in the total mass of the ink unless otherwise specified.
  • the ink may contain two or more of the red luminescent nanocrystal particles, the green luminescent nanocrystal particles, and the blue luminescent nanocrystal particles as the luminescent nanocrystal particles, but these particles are preferable. Includes only one of them.
  • the content of the green luminescent nanocrystal particles and the content of the blue luminescent nanocrystal particles are preferably 10% by mass based on the total mass of the luminescent nanocrystal particles. The following is more preferable, and it is 0% by mass.
  • the content of the red luminescent nanocrystal particles and the content of the blue luminescent nanocrystal particles are preferably 10% by mass based on the total mass of the luminescent nanocrystal particles. The following is more preferable, and it is 0% by mass.
  • the organic ligand exists near the surface of the luminescent nanocrystal particles and has a function of dispersing the luminescent nanocrystal particles.
  • the organic ligand is, for example, a functional group for ensuring affinity with an ethylenically unsaturated monomer, a solvent, etc. (hereinafter, also simply referred to as “affinity group”) and a functional group capable of binding to luminescent nanocrystal particles. It has a group (a functional group for ensuring the adsorptivity to luminescent nanoparticles) and is coordinated to the surface of the luminescent nanoparticles so as to be in the vicinity of the surface of the luminescent nanoparticles. exist.
  • organic ligand examples include TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), oleic acid, linoleic acid, linolenic acid, lysynolic acid, gluconic acid, 16-hydroxyhexadecanoic acid, 12-hydroxystearic acid, N.
  • the content of the organic ligand is, for example, preferably 10 to 50 parts by mass or 10 to 15 parts by mass with respect to 100 parts by mass of the luminescent nanocrystal particles.
  • FIG. 1 is a schematic cross-sectional view of the color filter of one embodiment.
  • the color filter 100 includes a base material 40 and a light diffusion layer 30 provided on the base material 40.
  • the light diffusion layer 30 includes a plurality of pixel portions 10 and a light-shielding portion 20.
  • the light diffusion layer 30 has a first pixel unit 10a, a second pixel unit 10b, and a third pixel unit 10c as the pixel unit 10.
  • the first pixel portion 10a, the second pixel portion 10b, and the third pixel portion 10c are arranged in a grid pattern so as to repeat in this order.
  • the light-shielding portion 20 is located between adjacent pixel portions, that is, between the first pixel portion 10a and the second pixel portion 10b, between the second pixel portion 10b and the third pixel portion 10c, and the third. It is provided between the pixel portion 10c of the above and the first pixel portion 10a. In other words, these adjacent pixel portions are separated from each other by the light-shielding portion 20.
  • the first pixel portion 10a and the second pixel portion 10b are luminescent pixel portions (light emitting pixel portions) containing the cured product of the above-mentioned luminescent ink composition, respectively.
  • the cured product shown in FIG. 1 contains luminescent nanocrystal particles, a cured component, and light-scattering particles.
  • the first pixel portion 10a includes a first curing component 13a, a first luminescent nanocrystal particle 11a and a first light scattering particle 12a dispersed in the first curing component 13a, respectively.
  • the second pixel portion 10b includes the second curing component 13b and the second luminescent nanocrystal particles 11b and the second light scattering particles 12b dispersed in the second curing component 13b, respectively.
  • the curing component is a component obtained by polymerizing a polymerizable compound, and includes a polymer of the polymerizable compound.
  • the curing component may contain components other than the organic solvent contained in the ink composition (polymer dispersant, unreacted polymerizable compound, etc.).
  • the first curing component 13a and the second curing component 13b may be the same or different, and the first light scattering particles 12a and the second It may be the same as or different from the light scattering particles 12b.
  • the first luminescent nanocrystal particles 11a are red luminescent nanocrystal particles that absorb light having a wavelength in the range of 420 to 480 nm and emit light having a emission peak wavelength in the range of 605 to 665 nm. That is, the first pixel portion 10a may be paraphrased as a red pixel portion for converting blue light into red light.
  • the second luminescent nanocrystal particle 11b is a green luminescent nanocrystal particle that absorbs light having a wavelength in the range of 420 to 480 nm and emits light having a emission peak wavelength in the range of 500 to 560 nm. That is, the second pixel portion 10b may be paraphrased as a green pixel portion for converting blue light into green light.
  • the content of the luminescent nanocrystal particles in the luminescent pixel portion is based on the total mass of the cured product of the luminescent ink composition from the viewpoint of being superior in the effect of improving the external quantum efficiency and obtaining excellent emission intensity. It is preferably 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, or 30% by mass or more.
  • the content of the luminescent nanocrystal particles is 80% by mass or less, 75, based on the total mass of the cured product of the luminescent ink composition, from the viewpoint of excellent reliability of the pixel portion and excellent emission intensity. It is preferably 1% by mass or less, 70% by mass or less, or 60% by mass or less.
  • the content of the light-scattering particles in the luminescent pixel portion is 0.1% by mass or more and 1% by mass based on the total mass of the cured product of the luminescent ink composition from the viewpoint of being more excellent in the effect of improving the external quantum efficiency. It is preferably more than or equal to 3% by mass or more.
  • the content of the light-scattering particles is 60% by mass or less, 50, based on the total mass of the cured product of the luminescent ink composition, from the viewpoint of improving the effect of improving the external quantum efficiency and the reliability of the pixel portion. It is preferably 7% by mass or less, 40% by mass or less, 30% by mass or less, 25 parts by mass or less, 20 parts by mass or less, or 15% by mass or less.
  • the third pixel portion 10c is a non-light emitting pixel portion (non-light emitting pixel portion) containing a cured product of the above-mentioned non-light emitting ink composition.
  • the cured product does not contain luminescent nanocrystal particles, but contains light-scattering particles and a cured component. That is, the third pixel portion 10c includes a third curing component 13c and a third light scattering particle 12c dispersed in the third curing component 13c.
  • the third cured component 13c is, for example, a component obtained by polymerizing an ethylenically unsaturated monomer and contains a polymer of an ethylenically unsaturated monomer.
  • the third light-scattering particle 12c may be the same as or different from the first light-scattering particle 12a and the second light-scattering particle 12b.
  • the third pixel portion 10c has a transmittance of 30% or more with respect to light having a wavelength in the range of, for example, 420 to 480 nm. Therefore, the third pixel unit 10c functions as a blue pixel unit when a light source that emits light having a wavelength in the range of 420 to 480 nm is used.
  • the transmittance of the third pixel unit 10c can be measured by a microspectroscopy device.
  • the content of the light-scattering particles in the non-emissive pixel portion is 1% by mass based on the total mass of the cured product of the non-emission ink composition from the viewpoint that the difference in light intensity at the viewing angle can be further reduced. It is preferably more than or equal to 3% by mass or more.
  • the content of the light-scattering particles is 7% by mass or less, 6% by mass or less, or 5% by mass based on the total mass of the cured product of the non-emissive ink composition from the viewpoint of further reducing light reflection. % Or less is preferable.
  • the thickness of the pixel portion is preferably, for example, 1 ⁇ m or more, 5 ⁇ m or more, or 10 ⁇ m or more.
  • the thickness of the pixel portion is preferably, for example, 30 ⁇ m or less, 20 ⁇ m or less, or 15 ⁇ m or less.
  • the light-shielding portion 20 is a so-called black matrix provided for the purpose of separating adjacent pixel portions to prevent color mixing and for the purpose of preventing light leakage from a light source.
  • the material constituting the light-shielding portion 20 is not particularly limited, and the curing of the resin composition containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in the binder polymer in addition to a metal such as chromium. Objects and the like can be used.
  • the binder polymer used here includes one or a mixture of resins such as polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, and cellulose, photosensitive resin, and O / W.
  • the thickness of the light-shielding portion 20 is preferably, for example, 1 ⁇ m or more, 5 ⁇ m or more, or 10 ⁇ m or more.
  • the thickness of the light-shielding portion 20 is preferably, for example, 30 ⁇ m or less, 20 ⁇ m or less, or 15 ⁇ m or less.
  • the base material 40 is a transparent base material having light transmission, and is, for example, a transparent glass substrate such as quartz glass, Pylex (registered trademark) glass, a synthetic quartz plate, a transparent resin film, an optical resin film, or the like.
  • a flexible base material or the like can be used.
  • a glass substrate made of non-alkali glass that does not contain an alkaline component in the glass.
  • "7059 glass”, “1737 glass”, “Eagle 200” and “Eagle XG” manufactured by Corning Inc., "AN100” manufactured by Asahi Glass Co., Ltd., "OA-10G” and “OA-10G” manufactured by Nippon Electric Glass Co., Ltd. OA-11 ” is suitable. These are materials with a small thermal expansion rate and are excellent in dimensional stability and workability in high temperature heat treatment.
  • the color filter 100 provided with the above light diffusion layer 30 is suitably used when a light source that emits light having a wavelength in the range of 420 to 480 nm is used.
  • the color filter 100 can be manufactured, for example, by forming the light-shielding portion 20 in a pattern on the base material 40 and then forming the pixel portion 10 in the pixel portion-forming region partitioned by the light-shielding portion 20 on the base material 40. ..
  • the pixel portion 10 includes a step of selectively adhering a light emitting or non-light emitting ink composition (inkjet ink) to a pixel portion forming region on the base material 40 by an inkjet method, and an active energy ray for the ink composition. It can be formed by a method comprising a step of irradiating (for example, ultraviolet rays) and curing the inkjet ink to obtain a light emitting pixel portion.
  • a light emitting pixel portion can be obtained by using the above-mentioned light emitting ink composition as the inkjet ink, and a non-light emitting pixel portion can be obtained by using the non-light emitting ink composition.
  • the method of forming the light-shielding portion 20 is to form a metal thin film such as chromium or a thin film of a resin composition containing light-shielding particles in a region serving as a boundary between a plurality of pixel portions on one surface side of the base material 40.
  • a method of patterning this thin film and the like can be mentioned.
  • the metal thin film can be formed by, for example, a sputtering method, a vacuum vapor deposition method, or the like, and the thin film of the resin composition containing the light-shielding particles can be formed, for example, by a method such as coating or printing. Examples of the method for patterning include a photolithography method.
  • Examples of the inkjet method include a bubble jet (registered trademark) method using an electric heat converter as an energy generating element, a piezo jet method using a piezoelectric element, and the like.
  • a mercury lamp, a metal halide lamp, a xenon lamp, an LED or the like may be used for curing the ink composition.
  • the wavelength of the light to be irradiated is, for example, preferably 200 nm or more, and preferably 440 nm or less.
  • the exposure amount is, for example, preferably 10 mJ / cm 2 or more, and preferably 12000 mJ / cm 2 or less.
  • the present invention is not limited to the above embodiment.
  • the light diffusion layer may include, in addition to the third pixel portion 10c, a pixel portion (blue pixel portion) containing a cured product of a luminescent ink composition containing blue luminescent nanocrystal particles. .. Further, even if the light diffusion layer includes a pixel portion (for example, a yellow pixel portion) containing a cured product of a luminescent ink composition containing nanocrystal particles that emit light of colors other than red, green, and blue. good. In these cases, it is preferable that each of the luminescent nanocrystal particles contained in each pixel portion of the light diffusion layer has an absorption maximum wavelength in the same wavelength range.
  • a part of the pixel portion of the light diffusion layer can contain a cured product of a composition containing a pigment other than the luminescent nanocrystal particles.
  • the color filter may be provided with an ink-repellent layer made of a material having an ink-repellent property narrower than that of the light-shielding portion on the pattern of the light-shielding portion.
  • an ink-repellent layer instead of providing an ink-repellent layer, a photocatalyst-containing layer as a wettability variable layer is formed in a solid coating shape in a region including a pixel portion forming region, and then light is applied to the photocatalyst-containing layer via a photomask. Irradiation and exposure may be performed to selectively increase the parental ink property of the pixel portion forming region.
  • the photocatalyst include titanium oxide and zinc oxide.
  • the color filter may be provided with an ink receiving layer containing hydroxypropyl cellulose, polyvinyl alcohol, gelatin, etc. between the base material and the pixel portion.
  • the color filter may be provided with a protective layer on the pixel portion.
  • This protective layer flattens the color filter and prevents the components contained in the pixel portion, or the components contained in the pixel portion and the components contained in the photocatalyst-containing layer from elution into the liquid crystal layer. It is provided.
  • a material used as a known protective layer for a color filter can be used.
  • the pixel portion may be formed by a photolithography method instead of the inkjet method.
  • the ink composition (light emitting ink composition or non-light emitting ink composition) is coated on the base material in a layered manner to form an ink composition layer.
  • the ink composition layer is exposed in a pattern and then developed using a developing solution. In this way, a pixel portion made of a cured product of the ink composition is formed.
  • the developer is usually alkaline, an alkali-soluble material is used as the material of the ink composition.
  • the inkjet method is superior to the photolithography method.
  • the photolithography method removes about two-thirds or more of the material, which wastes the material. Therefore, in the present embodiment, it is preferable to use an inkjet ink and form a pixel portion by an inkjet method.
  • the pixel portion of the light diffusion layer may further contain a pigment having substantially the same color as the luminescent color of the luminescent nanocrystal particles.
  • the pigment may be contained in the ink composition.
  • one or two types of luminescent pixel portions do not contain luminescent nanocrystal particles. It may be a pixel portion containing a coloring material.
  • a known color material can be used.
  • a diketopyrrolopyrrole pigment and / or an anionic red organic dye is used. Can be mentioned.
  • Examples of the coloring material used for the green pixel portion (G) include at least one selected from the group consisting of a halogenated copper phthalocyanine pigment, a phthalocyanine-based green dye, and a mixture of a phthalocyanine-based blue dye and an azo-based yellow organic dye.
  • Examples of the coloring material used for the blue pixel portion (B) include an ⁇ -type copper phthalocyanine pigment and / or a cationic blue organic dye.
  • the amount of these coloring materials used is 1 to 5 based on the total mass of the pixel portion (cured product of the ink composition) from the viewpoint of preventing a decrease in light transmittance when contained in the light diffusion layer. It is preferably by mass%.
  • a monomer having one ethylenically unsaturated group is referred to as a monofunctional monomer
  • a monomer having two ethylenically unsaturated groups is referred to as a bifunctional monomer
  • a monomer having three ethylenically unsaturated groups is referred to as a trifunctional monomer.
  • Light-scattering particles A titanium oxide, product name: PF-690, manufactured by Ishihara Sangyo Co., Ltd.
  • Light-scattering particles B titanium oxide, product name: R-350, manufactured by The Chemours
  • Polymer dispersant A (PX-4701, manufactured by BASF, amine value: 69-86 mgKOH / g)
  • Polymer dispersant B (SS71000, manufactured by Lubrizol, amine value: 40 mgKOH / g)
  • Photopolymerization initiator > Photopolymerization Initiator A (Omnirad TPO-H, manufactured by IGM resin) Photopolymerization Initiator B (Omnirad 819, manufactured by IGM resin) TPO-H: 2,4,6-trimethylbenzoyl-diphenyl-phosphine phosphine oxide 819: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
  • ⁇ Light scattering particle dispersion A> In the container, 24.0 g of light-scattering particles A, 2.4 g of polymer dispersant A, and 33.6 g of PhEA were mixed, and then zirconia beads (diameter: 1.25 mm) were added to the obtained mixture. In addition, the mixture was dispersed by shaking with a paint conditioner for 2 hours, and the zirconia beads were removed from the mixture with a polyester mesh filter to obtain a light scattering particle dispersion A.
  • ⁇ Light scattering particle dispersion B> In the container, 33.0 g of light-scattering particles A, 1.65 g of polymer dispersant B, and 25.35 g of HDDMA were mixed, and then zirconia beads (diameter: 1.25 mm) were added to the obtained mixture. Was added, and the mixture was shaken for 2 hours using a paint conditioner to disperse the mixture, and the zirconia beads were removed from the mixture with a polyester mesh filter to obtain a light-scattering particle dispersion B.
  • ⁇ Light scattering particle dispersion C> In the container, 33.0 g of light-scattering particles B, 1.65 g of polymer dispersant B, and 25.35 g of 4-HBA were mixed, and then zirconia beads (diameter: 1.) were added to the obtained mixture. 25 mm) was added, and the mixture was shaken for 2 hours using a paint conditioner to disperse the mixture, and the zirconia beads were removed with a polyester mesh filter to obtain a light-scattering particle dispersion C.
  • Example 1 15.0 g of the light-scattering particle dispersion A, 0.1 g of the polymerization inhibitor (polymerization inhibitor) A, 2.7 g of the photopolymerization initiator A, and 0.5 g of the photopolymerization initiator B.
  • a white ink composition was obtained by uniformly mixing 20.4 g of TMP (EO) 3TA and 61.3 g of HDDA in a container, and then filtering the mixture with a filter having a pore size of 5 ⁇ m.
  • the average boiling point of the ethylenically unsaturated monomer at 1 atm was calculated based on the boiling point of each of the following monomers at 1 atm (monomer boiling point), the molar ratio of each monomer, and the mole fraction (%) of each monomer.
  • the (meth) acrylic equivalent was calculated based on the (meth) acrylic equivalent of each monomer (molecular weight per (meth) acryloyl group) and the mass ratio of each monomer.
  • Examples 2 to 7, Comparative Examples 1 to 3 White inks of Examples 2 to 7 and Comparative Examples 1 to 3 in the same manner as in Example 1 except that a light-scattering particle dispersion, a polymerization inhibitor, a photopolymerization initiator and a monomer shown in the table below were used. The composition was obtained. The average number of double bond groups, the average boiling point, and the (meth) acrylic equivalent of the mixed monomer were calculated in the same manner as in Example 1.
  • the table below shows the content (unit: parts by mass) of each component (light scattering particles, polymer dispersant, photopolymerization initiator, polymerization inhibitor and monomer) with respect to 100 parts by mass of the non-volatile content of the white ink composition. Also shown.
  • Volatility / 30 minutes Film thickness ( ⁇ m)
  • an inkjet printer manufactured by Fujifilm Dimatics, trade name "DMP-2831" was used.
  • DMP-2831 a layer made of the white ink composition
  • the thickness of the light diffusing layer was measured after 30 minutes in an environment of 23 ° C. and 50% RH, and evaluated by the rate of change.
  • the rate of change was calculated from the thickness of the light diffusing layer after 30 minutes / the thickness of the light diffusing layer immediately after printing (12.5 ⁇ m).
  • the thickness of the light diffusion layer was measured using a scanning white interference microscope manufactured by Hitachi High-Tech Science. Volatility was evaluated according to the following criteria. ⁇ : The rate of change of the light diffusing layer is less than 5% ⁇ : The rate of change of the light diffusing layer is 5% or more
  • UV-LED curing shrinkage film thickness ( ⁇ m)
  • An inkjet printer manufactured by Fujifilm Dimatix, trade name "DMP-2831" was used for the evaluation of the UV-LED curing shrinkage of the white ink composition.
  • DMP-2831 By inkjet printing, a white ink composition was filled in a bank on a glass substrate with a bank to form a light diffusing layer (a layer made of the white ink composition) before curing.
  • the thickness of the light diffusing layer immediately after printing was measured using a scanning white interference microscope manufactured by Hitachi High-Tech Science.
  • the glass substrate with a bank filled with the white ink composition was cured by irradiating it with UV so that the integrated light amount was 12 J / cm 2 with a UV irradiation device using an LED lamp having a main wavelength of 395 nm under a nitrogen atmosphere.
  • the thickness of the light diffusing layer (the layer made of the cured product of the white ink composition) after curing was measured and evaluated by the rate of change. The rate of change was calculated from the thickness of the light diffusing layer before curing / the thickness of the light diffusing layer after curing.
  • UV-LED curing shrinkage was evaluated according to the following criteria. ⁇ : The rate of change of the light diffusing layer is less than 16% ⁇ : The rate of change of the light diffusing layer is 16% or more
  • a blue LED peak emission wavelength: 450 nm
  • CCS Co., Ltd. a blue LED (peak emission wavelength: 450 nm) manufactured by CCS Co., Ltd.
  • an integrating sphere was connected to a radiation spectrophotometer (product name "MCPD-9800") manufactured by Otsuka Electronics Co., Ltd., and the integrating sphere was installed above the blue LED.
  • the prepared evaluation sample was inserted between the blue LED and the integrating sphere, and the blue LED was turned on to measure the observed light transmittance.
  • the optical characteristics (light transmittance) were evaluated according to the following criteria. ⁇ : Within 62 ⁇ 1% ⁇ : 62 ⁇ 1% or more
  • the white ink composition of the example is an active energy ray-curable white ink composition applicable to an inkjet method, in which ink volatility during printing and curing shrinkage during UV curing are suppressed, and film reduction in a pixel portion is achieved. It was confirmed that the white ink composition was easy to adjust the transmittance of the backlight light to a predetermined value (comparison between Examples 1 to 7 and Comparative Examples 1 to 3).

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PCT/JP2021/045259 2020-12-25 2021-12-09 ホワイトインク組成物、硬化物、光拡散層及びカラーフィルタ WO2022138185A1 (ja)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016091687A (ja) * 2014-10-31 2016-05-23 積水化学工業株式会社 積層型電池の製造方法
JP2020015894A (ja) * 2018-07-13 2020-01-30 Dic株式会社 インク組成物、光変換層及びカラーフィルタ
WO2020137988A1 (ja) * 2018-12-26 2020-07-02 Dic株式会社 インク組成物、光変換層、及びカラーフィルタ
JP2020129034A (ja) * 2019-02-07 2020-08-27 Dic株式会社 カラーフィルタ用インクジェットインク、光変換層及びカラーフィルタ
JP2021127458A (ja) * 2020-02-13 2021-09-02 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. 光散乱インク組成物、これを用いて製造された画素、前記画素を含むカラーフィルタおよび前記カラーフィルタを備える画像表示装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016091687A (ja) * 2014-10-31 2016-05-23 積水化学工業株式会社 積層型電池の製造方法
JP2020015894A (ja) * 2018-07-13 2020-01-30 Dic株式会社 インク組成物、光変換層及びカラーフィルタ
WO2020137988A1 (ja) * 2018-12-26 2020-07-02 Dic株式会社 インク組成物、光変換層、及びカラーフィルタ
JP2020129034A (ja) * 2019-02-07 2020-08-27 Dic株式会社 カラーフィルタ用インクジェットインク、光変換層及びカラーフィルタ
JP2021127458A (ja) * 2020-02-13 2021-09-02 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. 光散乱インク組成物、これを用いて製造された画素、前記画素を含むカラーフィルタおよび前記カラーフィルタを備える画像表示装置

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