WO2007046425A1 - Fine particle-containing composition, ink for forming colored film for display, light-blocking film for display, light-blocking material, substrate with light-blocking film, color filter, liquid crystal display element and liquid crystal display - Google Patents

Fine particle-containing composition, ink for forming colored film for display, light-blocking film for display, light-blocking material, substrate with light-blocking film, color filter, liquid crystal display element and liquid crystal display Download PDF

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Publication number
WO2007046425A1
WO2007046425A1 PCT/JP2006/320755 JP2006320755W WO2007046425A1 WO 2007046425 A1 WO2007046425 A1 WO 2007046425A1 JP 2006320755 W JP2006320755 W JP 2006320755W WO 2007046425 A1 WO2007046425 A1 WO 2007046425A1
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Prior art keywords
light
fine particle
group
fine particles
film
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PCT/JP2006/320755
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French (fr)
Japanese (ja)
Inventor
Kousaku Yoshimura
Katsuyuki Takada
Misato Sasada
Kazuhito Miyake
Hideyuki Nakamura
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Fujifilm Corporation
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Application filed by Fujifilm Corporation filed Critical Fujifilm Corporation
Priority to CN2006800390345A priority Critical patent/CN101291989B/en
Publication of WO2007046425A1 publication Critical patent/WO2007046425A1/en
Priority to KR1020087006169A priority patent/KR101217033B1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/38—Esters containing sulfur
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen

Definitions

  • Fine particle-containing composition, colored film forming ink for display device, light shielding film for display device, light shielding material, substrate with light shielding film, color filter, liquid crystal display element, and liquid crystal display device Fine particle-containing composition, colored film forming ink for display device, light shielding film for display device, light shielding material, substrate with light shielding film, color filter, liquid crystal display element, and liquid crystal display device
  • the present invention relates to a fine particle-containing composition suitable for producing a light-shielding film (light-shielding film) provided in a display device such as a plasma display device, an EL display device, and a CRT display device, and
  • a display device such as a plasma display device, an EL display device, and a CRT display device
  • the present invention relates to an ink for forming a colored film for a display device, a light shielding film for a display device, a light shielding material, a substrate with a light shielding film, a color filter, a liquid crystal display element, and a liquid crystal display device.
  • a light-shielding film for a display device is formed inside a device such as a liquid crystal display device, a plasma display display device, an EL display device, and a CRT display device with a black edge, a lattice shape or a stripe shape around a pixel. It is provided as a black edge (V, a so-called black matrix), or a dot-like or linear black pattern for shielding a thin film transistor (TFT).
  • V a so-called black matrix
  • TFT thin film transistor
  • a black matrix is an example of a light shielding film of a liquid crystal display device, and surrounds each of a plurality of colored pixels (red, green, blue) of a color filter provided in the liquid crystal display device. And prevents a decrease in contrast due to light leakage between pixels.
  • the light shielding film there is a light shielding film provided on the TFT in an active matrix liquid crystal display element using TFT in order to prevent deterioration of image quality due to TFT current leakage due to light.
  • These light-shielding films are generally required to have a light-shielding property with an optical density of 2 or more, and the color tone of the light-shielding film is preferably black from the viewpoint of display quality of the display device.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-334182
  • Patent Document 2 JP-A-2-166442
  • Patent Document 3 Japanese Patent Laid-Open No. 4-151140
  • Patent Document 4 US Patent 3615624 Specification
  • the dispersing agent used for dispersing the metal fine particles in the above-described method for producing a light shielding film is generally widely used, and the light shielding film produced by such a method is a light shielding film for a display device. Therefore, satisfactory dispersion of the metal fine particles is not obtained.
  • the film when producing a light-shielding film for a display device, the film is exposed to a high temperature during production (for example, post-development post-beta).
  • a high temperature during production for example, post-development post-beta.
  • the color of a film obtained from a dispersion of metal fine particles containing a widely known dispersing agent changes at high temperatures, and the desired light shielding performance and display contrast cannot be obtained immediately.
  • the first aspect of the present invention is a polymer compound having at least metal fine particles and Z or metal compound fine particles and at least one thioether group (hereinafter referred to as "polymer dispersant according to the present invention"). And a fine particle-containing composition comprising a compound that is cured by heat or light.
  • a second aspect of the present invention provides an ink for forming a colored film for a display device comprising the fine particle-containing composition.
  • a third aspect of the present invention is a light-shielding material used for forming a light-shielding film for a display device, and on a support, metal fine particles having an aspect ratio of 2 to: LOO and Z or metal compound fine particles, and at least Provided is a light-shielding material having at least one fine particle-containing layer containing at least a polymer compound having one thioether group and a compound that is cured by heat or light.
  • a fourth aspect of the present invention provides a substrate with a light-shielding film having a light-shielding film formed using the fine particle-containing composition, the colored film forming ink for a display device, or the light-shielding material.
  • a color filter having a plurality of pixels exhibiting different hues and a light-shielded image separating each of the plurality of pixels on a light-transmitting substrate.
  • a color filter which is a light shielding film for the display device.
  • a liquid crystal display device comprising the light-shielding film-coated substrate.
  • a seventh aspect of the present invention provides a liquid crystal display device comprising the liquid crystal display element.
  • the fine particle-containing composition of the present invention will be described in detail, and through the description, the colored film-forming ink for display device, the light-shielding film for display device, the light-shielding material, the substrate with the light-shielding film, the color Details of the filter, the liquid crystal display element, and the liquid crystal display device will also be described in detail.
  • the fine particle-containing composition of the present invention contains at least metal fine particles and Z or metal compound fine particles, a polymer compound having at least one thioether group, and a compound that is cured by heat or light. Depending on the situation, other components may be included.
  • dispersed metal fine particles and Z or metal compound fine particles as a colorant (particularly a black colorant), and a dispersant for dispersing the metal fine particles
  • the use of the polymer dispersant (polymer compound having a thioether group) according to the present invention contributes to the behavior of metal-based fine particles such as aggregation prevention, and even if the film is exposed to high temperature during production, Since the color change associated with the alteration of the oil component and fine particles in the environment is suppressed, the dispersibility of the metallic fine particles described above in the system and the stability of the dispersed fine particles are improved. In addition, good hue and high optical density can be ensured.
  • the metal fine particles and / or the metal compound fine particles are contained in a polymer compound having a thioether group (a polymer dispersant according to the present invention) described later. Preferred to be distributed.
  • the fine particle-containing composition of the present invention contains at least one of metal fine particles and metal compound fine particles as a (particularly black) colorant.
  • metallic fine particles as a colorant, it is possible to form a high-density image with a thin film, and it is particularly effective for forming a black image such as a light-shielded image (including a black matrix).
  • metal in the metal fine particles means “Iwanami Dictionary of Chemical Sciences (5th edition)”
  • metal (page 352) described in 998, published by Iwanami Shoten.
  • the “metal compound” is a compound of a metal and an element other than the metal, and the metal here is also synonymous with the metal in the metal fine particles.
  • the metal fine particles are not particularly limited and may be appropriately selected.
  • the metal fine particles may be selected from a group of metals included in the fourth period, the fifth period, and the sixth period of the long-period periodic table (IUPAC 1991).
  • fine metal particles are metals of the 4th, 5th, or 6th period, and the metals of Group 2, Group 10, Group 11, Group 12, or Group 14 are used. It is more preferable to include it.
  • the shape of the metal fine particles is irregular, rod-shaped (acicular, cylindrical, rectangular parallelepiped, rugby ball, etc.), flat plate (scale, elliptical plate, plate). It may be in the form of a fiber or coil.
  • the shape of the metal fine particles is plate-like particles or rod-like (rod-like).
  • Metals of the fine metal particles are copper, silver, gold, platinum, noradium, nickel, tin, conoleto, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, titanium. Copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, or an alloy thereof, which is preferably at least one selected from bismuth, antimony, lead, and alloys thereof. It is more preferable to be at least one selected from copper, silver, gold, platinum, tin, or alloys thereof. Is preferred.
  • the metal of the metal fine particles is most preferably silver, more preferably gold, silver, copper, or tin in that fine particles can be easily obtained.
  • the metal fine particles in the present invention may be formed from an alloy of the metal, preferably an alloy of silver and tin, or a metal.
  • the number average particle diameter of the metal fine particles should not exceed the film thickness, but is not particularly limited in other respects.
  • the number average particle size is preferably in the range of 10 to 1000 nm, more preferably in the range of 10 to 500 nm, and even more preferably in the range of 10 to 200 nm.
  • the number average particle size is within the above range, the formation of metal fine particles is easy, and when a color filter is produced using metal fine particles within the range of strength, a good black color is visually observed due to the characteristics. A black image part such as a black matrix that looks like a brownish brown color does not appear, and the stability of the dispersion after dispersion of metal fine particles due to the particle size being too large, or the light shielding property is deteriorated.
  • a black image part such as a black matrix that looks like a brownish brown color does not appear, and the stability of the dispersion after dispersion of metal fine particles due to the particle size being too large, or the light shielding property is deteriorated.
  • particle size refers to the diameter of a circle having the same area as that of the particles, and the number-average particle size is 100 particles. It is obtained by calculating the particle size of the particles and averaging the obtained particle sizes.
  • the particle size distribution is not particularly limited.
  • the metal fine particles may have a uniform composition or a non-uniform composition.
  • Examples of the metal fine particles having a non-uniform composition include particles in which a metal coating layer different from the metal inside the mother particles is provided on the surface of the metal mother particles.
  • the metal compound fine particles are made of a compound of a metal and an element other than the metal.
  • a compound include metal oxides, sulfides, sulfates and carbonates.
  • the metal compound is preferably a sulfate from the viewpoint of color tone and fine particle formation.
  • Specific examples of the metal compound include copper oxide ( ⁇ ), iron sulfide, silver sulfide, copper sulfide (11), titanium black, and the like. From the viewpoint of color tone, fine particle formation, and stability, the metal compound is sulfurated. It ’s even better to be a silver candy.
  • the metal compound fine particles may have a uniform composition, or may have a non-uniform composition.
  • Examples of the metal compound fine particles having a non-uniform composition include particles in which a coating layer having a composition different from the composition inside the mother particle is provided on the surface of the metal compound mother particle.
  • the production method of the metal fine particles and metal compound fine particles in the present invention may be a known method such as a gas phase method or a liquid phase method without particular limitation. A method for producing metal compound fine particles is described in, for example, “Latest Trends in Technology and Application of Ultrafine Particles II” (Sumibe Techno Search Co., Ltd., issued in 2002).
  • the metal fine particles can be prepared by a metal ion chemical reduction method, an electroless plating method, a metal evaporation method, or the like.
  • a silver salt is added to spherical silver fine particles as seed particles.
  • a surfactant such as CTAB (cetyltrimethylammonium bromide)
  • CTAB cetyltrimethylammonium bromide
  • Rod-like particles can be produced by a reduction method in the presence of a surfactant.
  • various rod-shaped particles can be prepared by controlling the type of surfactant, the type of reducing agent, adjusting the amount added, and controlling the pH. Specifically, a surfactant with less interaction with the metal is first added to the system, the metal compound in the system is reduced to grow metal particles, and then a surfactant that interacts greatly with the metal is added. Add to system to prevent further growth of the particles. That is, the shape of the metal particles can be controlled by the type and time of the reducing agent.
  • Metal compound fine particles are prepared by oxidizing or sulfiding rod-shaped particles. Can do.
  • the metal fine particles include composite fine particles of a metal and another metal
  • the metal compound fine particles include a composite fine particle of a metal and a metal compound, a metal compound and another metal compound, and Composite fine particles.
  • the shape of the composite fine particles is not particularly limited. For example, particles having different compositions between the inside and the surface of the particles, particles in which two types of particles are combined, and the like can be mentioned.
  • the composite fine particles can contain one or more kinds of metal compounds and one or more kinds of metals.
  • composite fine particles of metal and metal compound include composite fine particles of silver and silver sulfide, composite fine particles of silver and copper (II) oxide, and the like.
  • the metal fine particles and metal compound fine particles in the present invention may be composite particles having a core-shell structure.
  • a composite particle having a core'shell structure has a core material and a shell material that covers the surface of the core material.
  • shell materials include Si, Ge, AlSb, InP, Ga, As, GaP, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, and PbTe.
  • the core material is preferably at least one selected from copper, silver, gold, palladium, nickel, tin, bismuth, ammotine, lead, or alloys thereof.
  • the shell material is also suitably used as a refractive index adjuster for the purpose of reducing the reflectance.
  • the core material of the composite particles having a core 'shell structure for example, at least one metal selected from copper, silver, gold, palladium, or an alloy thereof can be used.
  • a typical method for producing a composite particle having a core-shell structure a typical method without particular limitation is shown below.
  • a method of forming a metal compound shell on the surface of a metal fine particle produced by a known method by oxidation, sulfurization or the like For example, there is a method of adding a sulfide such as sodium sulfate or ammonium sulfate to a dispersion in which metal fine particles are dispersed in a dispersion medium such as water.
  • the metal fine particles to be used can be prepared by a known method such as a gas phase method or a liquid phase method. Latest trends in ultrafine particle technology and applications II ”(Sumibe Techno Research Co., Ltd., published in 2002).
  • the aspect ratio of the metal fine particles and metal compound fine particles described above is 2 in that the absorption spectrum can be controlled and the hue can be made close to black.
  • ⁇ : LOO is preferred.
  • the aspect ratio is preferably 4 to 80, more preferably 10 to 60, and most preferably 15 to 50 in that the absorption spectrum can be controlled and the hue can be made closer to black.
  • the aspect ratio is within the above range, it is relatively easy to obtain black particles, the absorption of visible light is good, and the image quality (resolution) is not lowered.
  • the aspect ratio means a value obtained by dividing a major axis length defined as described later by a minor axis length of metal fine particles or metal compound fine particles, and 100 metal fine particles and Z or metal compound fine particles. It is obtained by measuring the aspect ratio and averaging the measured values.
  • the projected area of the particles can be obtained by measuring the photographic power area of the electron microscope and multiplying the measured area by the photographing magnification.
  • the particle diameter (major axis length, minor axis length) will be described.
  • metal fine particles are used as an example.
  • the following three lengths are used as the particle length of the metal fine particles.
  • a box (a rectangular parallelepiped) in which one metal particle fits tightly is imagined, and the size of this metal particle is defined by the length L, width b, height, or thickness t of this box. There are several methods for assuming such a box. In the present invention, the following method is adopted.
  • metal particles are placed on a virtual plane so that the center of gravity is the lowest and remains stable.
  • the metal particles are sandwiched between two parallel virtual flat plates standing at right angles to the virtual plane so that the distance between the virtual flat plates is the shortest.
  • the distance between the plates at this time is defined as “width.
  • the metal particles are formed by two virtual parallel plates that are perpendicular to the two virtual plates that determine the width b and perpendicular to the virtual plane.
  • the distance between the two plates is “length L”.
  • the virtual top plate is placed parallel to the virtual plane so as to contact the highest position of the metal particles, and the distance between the virtual top plate and the virtual plane is defined as height or thickness t.
  • the short axis length of the metal fine particles or metal compound fine particles is preferably within the range of 4 to 50 nm, more preferably within the range of 15 to 50 nm, and most preferably within the range of 15 to 30 nm.
  • the long axis length (maximum length) of metal fine particles or metal compound fine particles is preferably in the range of 10 to: LOOOnm, more preferably in the range of 100 to 1000 nm, and in the range of 400 to 800 nm. preferable.
  • the shape of the metal fine particles or metal compound fine particles in the present invention is changed to a spherical force, for example, a rod shape, the amount of absorption of visible light is also increased about twice, which is higher than the case of spherical particles. It is possible to increase the transmission density by increasing the absorption coefficient of tall. As a result, the layer of metal fine particles or metal compound fine particles can be thinned while maintaining a high concentration.
  • the desired content of metal fine particles and Z or metal compound fine particles in the fine particle-containing composition varies depending on the type and properties of the fine particles, the metal fine particles and Z or metal compound fine particles in the total solid content of the composition
  • the content of is preferably 10 to 98% by mass, more preferably 20 to 95% by mass, and most preferably 30 to 93% by mass.
  • a high concentration can be obtained even if the layer of metal fine particles or metal compound fine particles is a thin film, and development performance is not hindered.
  • the fine particle-containing composition of the present invention contains at least one polymer compound having at least one thioether group (polymer dispersant according to the present invention) as a dispersant for the metal fine particles and Z or metal compound fine particles. . Since the polymer compound having a thioether group is used as the dispersant, the dispersibility of the metal fine particles described above in the system and the stability of the dispersed fine particles are improved, and the hue (particularly the black phase) is improved. ) Is good, and high optical density image formation is possible.
  • the polymer dispersant according to the present invention is a polymer compound that can be selected from polymer compounds having at least one thioether group in the molecule, and having a thioether group in the side chain portion. Is preferred.
  • the polymer dispersant according to the present invention includes, as a polymer structural unit, an ethylenically unsaturated monomer force-induced repeating unit containing at least one thioether structure in the side chain in the molecule. It is more preferable that the polymer compound has at least one kind of repeating unit represented by the following general formula (1).
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms in total.
  • alkyl group having 1 to 4 carbon atoms examples include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a sec butyl group, an isobutyl group, and a tert-butyl group.
  • a methyl group is preferred.
  • R 2 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 16 carbon atoms.
  • Each of the alkyl group, aryl group, and aralkyl group may be unsubstituted or may have one or more substituents, and may form a saturated or unsaturated cyclic structure. Moyo.
  • the alkyl group having 1 to 18 carbon atoms represented by R 2 may be unsubstituted or substituted.
  • a substituent when R 2 is a substituted alkyl group a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, or a sulfonyl group is preferable.
  • R 2 is an alkyl group
  • the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group having 1 to 8 carbon atoms. And more preferably an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, or a tert-butyl group.
  • the aryl group having 6 to 14 carbon atoms in total represented by R 2 may be unsubstituted or substituted.
  • a phenyl group, a tolyl group, a xylyl group, A naphthyl group and an anthracyl group are mentioned.
  • the substituent when R 2 is a substituted aryl group include a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, or a sulfonyl group. Is preferred.
  • R 2 is an aryl group
  • the aryl group is preferably an aryl group having a total carbon number of 6 to LO and more preferably a phenol group.
  • the aralkyl group having 7 to 16 total carbon atoms represented by R 2 may be unsubstituted or may have a substituent.
  • a benzyl group, a phenethyl group, a naphthylmethyl group, an anthracene group may be substituted.
  • -Rumethyl group As the substituent when R 2 is a substituted aralkyl group, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, or a sulfonyl group is preferable.
  • R 2 is an aralkyl group
  • the aralkyl group is more preferably a benzyl group, preferably an aralkyl group having a total carbon number of 7 to: L 1.
  • Z represents O or NH.
  • Y represents a divalent linking group having 1 to 8 carbon atoms in total.
  • the divalent linking group having a total carbon number of 1 to 8 represented by Y is an alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, pentylene group), alkene group (eg, etylene).
  • R represents a hydrogen atom, an alkyl group, or an aryl group, or a combination thereof (for example, NHCH CH NH—
  • the alkylene group, alkylene group, alkylene group, arylene group, or divalent heterocyclic group represented by Y, and the alkyl group or aryl group represented by R are one or more. It may have a substituent. Examples of the substituent are the same as the examples of the substituent of the aryl group represented by R 2 .
  • the alkyl group and aryl group represented by R are synonymous with the alkyl group and aryl group represented by R 2 described above.
  • the divalent linking group having 1 to 8 carbon atoms in total represented by Y is preferably an ethylene group, propylene group, or butylene group having 1 to 6 carbon atoms in total. , Hexylene group, CH-C
  • the polymer dispersant according to the present invention may contain only one type of repeating unit represented by the general formula (1), and may copolymerize a monomer containing two or more types of repeating units. It may be a polymer compound obtained in this way. Further, the thioether structure constituting the side chain may have only one sulfur atom, or two or more sulfur atoms can be used by using a group having a sulfur atom as Z and R 2. It can also be a side chain having
  • the polymer dispersant according to the present invention introduces a thioether structure into a desired polymer compound (preferably as a side chain) or a thioether group (preferably into a side chain).
  • a copolymer of a monomer having a thioether group (preferably in the side chain) with another monomer.
  • it can be obtained by homopolymerization of an ethylenically unsaturated monomer having a thioether structure in the side chain, or by copolymerization of an ethylenically unsaturated monomer having a thioether structure in the side chain with another copolymerization component. it can.
  • a R 1 is a hydrogen atom or a methyl group
  • R 2 is a methyl group
  • Echiru group n-propyl group, n-butyl group, tert- butyl group, or a phenyl group Z is -
  • Preferred is a repeating unit O—, where Y is an ethylene group.
  • the polymer dispersant according to the present invention has a repeating unit represented by the general formula (1). It may be a copolymer of a monomer and one or more other bull monomers.
  • bur monomers include aromatic bur compounds (eg, styrene, OC-methyl styrene, p-hydroxy styrene, chloromethyl styrene, and butyltoluene), cyanide bur (eg, (meth) acrylonitrile, and acrylonitrile acrylonitrile), Carboxylate butyl esters (eg, vinyl acetate, vinyl benzoate, and vinyl formate), aliphatic conjugates (eg, 1,3-butadiene and isoprene), (meth) acrylic acid alkyl esters (eg, methyl (meta ) Atarylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 2-ethyl hexyl (meth) acrylate), (meth) acrylate alkyl ester , Benzyl (meth) acrylate),
  • the polymerization ratio of the repeating unit represented by the general formula (1) in the polymer compound having at least one thioether group is 1 to 100% force in mass fraction. S, preferably 5 to 80%, more preferably 10 to 50%. When the polymerization ratio is within the above range, it is effective to improve the dispersibility of the metallic fine particles in the system and the stability, hue and optical density in the dispersed fine particles.
  • the polymer dispersant of the present invention is preferably a polymer compound having an acid group in the molecule from the viewpoint that alkali developability can be imparted if necessary.
  • the acid group a group such as a carboxylic acid group, a sulfonic acid, a phosphoric acid, a boronic acid, phenols, and a sulfoamide is preferable.
  • the polymer dispersant of the present invention is more preferably a polymer compound having at least one carboxylic acid group.
  • the acid value of the polymer dispersant of the present invention is preferably 20 to 250 mgK OHZg, more preferably 50 to 200 mgKOHZg, and 70 to 180 mgKOHZg. Most preferred.
  • the acid value is within the above range, the dispersibility of the metal-based fine particles in the system and the stability of the dispersed fine particles in the system are good, and the alkali developability of the fine particle-containing composition is also good. is there.
  • the weight average molecular weight of the polymer dispersant according to the present invention is preferably 2,000 to 1,000,000, preferably S, more preferably 3,000 to 200,000, more preferably S. Most preferably, it is between 000 and 100,000.
  • a polymer dispersant having a weight average molecular weight within the above range is effective for improving dispersibility of metal-based fine particles in the system, can provide good film strength, and does not interfere with developability. ,.
  • the content of the polymer compound having at least one thioether group with respect to the aforementioned metal fine particles and Z or metal compound fine particles is preferably 1 to 40% by mass, more preferably 3 to 30% by mass. It is more preferably 5 to 20% by mass.
  • the polymer compound is sufficiently adsorbed on the fine particles to improve the dispersibility of the fine particles, and it is effective in improving the hue and optical density by suppressing the hue change due to heat. Also, it does not interfere with developability.
  • the fine particle-containing composition of the present invention contains at least one compound that is cured by heat or light.
  • a polyfunctional monomer can be used as the compound that is cured by heat or light.
  • the polyfunctional monomer is polymerized to form a polymer, and this polymer functions as a binder. Since the fine particle-containing composition of the present invention contains the polyfunctional monomer, the strength of the film formed using the fine particle-containing composition of the present invention is high.
  • a photopolymerizable monomer is preferred, and more preferred is a polymer having thermal polymerizability. When the polyfunctional monomer has thermal polymerizability, the degree of cure can be further increased by heat-treating the polymer obtained by photopolymerization of the polyfunctional monomer.
  • the polyfunctional monomer may be a compound having a boiling point of 100 ° C or higher at normal pressure.
  • examples of such compounds include ethylene glycol di (meth) acrylate and triethyleneglycol.
  • the polyfunctional monomer trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or dipentaerythritol penta (meth) ) It is preferable to use a polyfunctional acrylic monomer such as acrylate.
  • a polyfunctional monomer When a polyfunctional monomer is used, it is generally 5 to 50% by mass with respect to the total solid content of the composition, with no particular limitation on the amount of polyfunctional monomer added in the fine particle-containing composition. Yes, 10 to 40% by mass is preferable. When the addition amount is within the above range, the photosensitivity and the strength of the film constituting the image are good, and the adhesiveness of the film when the film is formed does not become excessive.
  • the polyfunctional monomer is a compound that can be polymerized using light or heat.
  • the fine particle-containing composition in which it is preferable to use a polymerization initiator in combination with the polyfunctional monomer contains a photopolymerization initiator and is photocurable. More preferably. Furthermore, the fine particle-containing yarn composition may contain an oligomer in addition to the polyfunctional monomer.
  • photopolymerization initiator examples include compounds described in paragraph No. [0024] of JP-A No. 2004-347831. Furthermore, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.
  • a photopolymerization initiator based on trino and romethyloxadiazole and trino and romethyl —S Combinations with triazine-based photopolymerization initiators, including 2-trichloromethyl-5- (p-styrylmethyl) 1, 3, 4 oxaziazole and 2,4 bis (trichloromethyl) — 6— [ 4 '— (N, N bisethoxycarboromethylamino) —3′—promophor] s
  • a combination with triazine is preferred.
  • the ratio when the photopolymerization initiator is combined as described above is 95Z5 to 20Z80. 90/10 to 30/70 force S is more preferable, and most preferable is ⁇ 80/20 to 40/60.
  • photopolymerization initiator For details of the photopolymerization initiator, the descriptions in JP-A-1-152449, JP-A-1-254918, and JP-A-2-153353 can be referred to.
  • suitable photopolymerization initiators include benzophenone photopolymerization initiators.
  • Examples of the coumarin compounds include 7- [2- [4 (3-hydroxymethylbiperidino) 6
  • the ratio of the photopolymerization initiator to the coumarin compound is preferably 20-80 to 80-20. 0 to 70 Z30 force is more preferable, and 40 to 60 to 40 is most preferable.
  • the photopolymerization initiator that can be used in the present invention is not limited to the above-described polymerization initiators, and can be appropriately selected from other known ones.
  • the fine particle-containing composition may contain one kind of photopolymerization initiator alone or two or more kinds, but preferably contains two or more kinds.
  • the content of the photopolymerization initiator in the total solid content in the fine particle-containing composition is generally 0.1 to 20% by mass.
  • the fine particle-containing composition of the present invention preferably contains a compound curable by heat or light in the form of a photosensitive resin composition.
  • photosensitive resin composition examples include a photosensitive resin composition containing the polyfunctional monomer and resin or oligomer described above and a photopolymerization initiator, and paragraph numbers [0016] to JP-A-10-160926. [0022] and [0029] are preferred. Furthermore, other photopolymerizable monomers may be used in combination with the polyfunctional monomer.
  • an aqueous one is useful as the photosensitive resin composition.
  • the aqueous photosensitive resin composition include those described in paragraphs [0015] to [0023] of JP-A-8-271727, and commercially available products such as “SPP” manufactured by Toyo Gosei Co., Ltd. — ⁇ 20
  • the fine particle-containing composition of the present invention can be used in combination with at least one kind of the following known pigment, at least one surfactant, and a polymer compound having a thioether group, if necessary.
  • Other components such as a polymer, at least one dispersant, and Z or at least one dispersion stabilizer can be included.
  • a black pigment such as carbon black can be used.
  • the addition rate of the pigment is 50% of the metal fine particles and Z or metal compound fine particles described above. Less than 30% by mass is more preferable. When the pigment addition rate exceeds 50% by mass, the thickness of the light shielding film necessary to obtain a desired optical density increases, and the quality of red, blue, and green pixels formed on the light shielding film decreases. Sometimes.
  • the fine particle-containing composition of the present invention may contain blue and other pigments in addition to black.
  • the content of the pigment is preferably 40% by mass or less, preferably 20% by mass with respect to the above-described metal fine particles and Z or metal compound fine particles. The following is more preferable.
  • the content exceeds 40% by mass, the color of the formed film may be deteriorated.
  • the fine particle-containing composition of the present invention can contain at least one surfactant for the purpose of improving coating properties and dispersion stability of fine particles.
  • a non-one, ar-on, or cationic surfactant can be used without particular limitation.
  • the surfactant is preferably ionic. Also preferred are fluorosurfactants.
  • Examples of commercially available products include F110, F113, F120, F150, F176PF, F177, and F780 (all manufactured by Dainippon Ink and Chemicals, Inc., oligomer type fluorosurfactants).
  • the fine particle-containing composition of the present invention is used as a binder having alkali developability, or in order to further improve the dispersion stability of the metal fine particles and Z or metal compound fine particles described above, Polymers other than “having a polymer compound” can be included. There is no restriction
  • the fine particle-containing composition of the present invention can contain a dispersion stabilizer.
  • a dispersion stabilizer for example, those described in “Pigment Dispersion Technology” (Technical Information Association, Inc., issued in 1999) can be used.
  • the fine particle-containing composition of the present invention comprises metal fine particles and Z or metal compound fine particles, a polymer compound having a polyether group, a compound curable by heat or light, and other components as necessary (preferably a solvent).
  • it can be prepared by mixing and stirring.
  • metal fine particles and Z or metal compound fine particles are preliminarily dispersed in a solvent together with a polymer compound having a thioether group to prepare a fine particle dispersion, and the fine particle dispersion is cured with heat or light. It can be prepared by adding and mixing other ingredients.
  • the type of solvent used for the preparation is not particularly limited, but it is particularly preferable that the SP value is 9.0 or more.
  • the solvent has an SP value of 9.0 or more, for example, the dispersibility of metal fine particles and Z or metal compound fine particles becomes good, and a sufficient optical density can be achieved even with a thin film.
  • the SP value is both a solubility parameter and is expressed by the square root of the cohesive energy density.
  • the “adhesion handbook” (edited by the Adhesion Society of Japan, published by Nikkan Kogyo Shimbun, 1971) Means the one described on page 838 of the first edition).
  • the SP value of the solvent for example, the SP value of n-hexane is 7.3, the SP value of toluene is 8.9, the SP value of ethyl acetate is 9.1, and the SP value of methyl ethyl ketone 9.3, SP value of acetone ⁇ 10.0, SP value of ethinorea nore cornore ⁇ ma 12.7, SP value of methino leno eno konole ⁇ ma 15.5, SP value of water 23 4 is.
  • the unit of SP value is “(cal / cm 3 ) 1/2 ”.
  • the fine particle-containing composition of the present invention comprises an ultrasonic disperser prepared by mixing a mixed liquid obtained by mixing metal fine particles and / or metal compound fine particles together with at least a “polymer compound having a thioether group” (and preferably a solvent). It can be prepared by stirring using a known disperser such as a paint shaker, ball mill, Eiger mill or the like. Among these, an ultrasonic disperser is preferable as the disperser.
  • the fine particle-containing composition of the present invention is used for applications containing dispersed metal fine particles and Z or metal compound fine particles, for example, (preferably black) colored film forming ink, light-shielding film, color filter, and the like. It can be suitably used for a black image of a filter (including a black matrix).
  • the ink for forming a colored film for a display device of the present invention is prepared using the fine particle-containing composition of the present invention described above. Since the fine particle-containing composition of the present invention is used, the ink has high stability when stored for a long period of time and has a good hue (especially a black hue) and a high optical density.
  • the colored film forming ink for a display device of the present invention includes metal fine particles and Z or metal compound fine particles, a polymer compound having at least one thioether group, and a compound that is cured by heat or light, if necessary.
  • it contains other components such as a colorant (preferably a pigment) and can be hardened by heating or application of energy rays such as ultraviolet rays after application of ink to the recording medium.
  • the details of the fine particle-containing composition of the present invention are as described above, and the colored film forming ink for a display device of the present invention appropriately contains components necessary for the ink in addition to the above components. Is possible.
  • the colored film forming ink for a display device of the present invention is suitable for use in a display device such as a liquid crystal display device, a plasma display display device, an EL display device, and a CRT display device, and is provided in the display device.
  • a display device such as a liquid crystal display device, a plasma display display device, an EL display device, and a CRT display device
  • the black outer periphery the grid-like or stripe-like black edges around the pixels (V, a so-called black matrix), and dot-like or linear black patterns for light shielding of thin film transistors (TFT) Is preferred.
  • the light shielding film for a display device of the present invention is formed using the fine particle-containing composition of the present invention described above or the color film forming ink for a display device of the present invention described above. Since this light-shielding film is formed using the fine particle-containing composition of the present invention, even if it is exposed to a high temperature during production, there is little change in color due to alteration of the fat component and fine particles in a high temperature environment. Excellent hue (especially black hue) and high optical density.
  • the light-shielding film for a display device of the present invention is, for example, a method in which the thermosetting or photocurable fine particle-containing composition of the present invention described above is applied to a desired substrate and the resulting coating film is dried. (Coating method) or the above-mentioned thermosetting or photocurable fine particles of the present invention are contained on a temporary support.
  • a method for preparing a transfer material having a thermosetting or photocurable light-shielding layer provided by applying a composition and drying the obtained coating film, and transferring the light-shielding layer to a desired substrate Transfer method
  • the light-shielding film for display device of the present invention is formed into a desired pattern
  • the light-shielding film for display device is a thermosetting or photocuring provided by the above coating method or transfer method. It is formed by patterning a light-shielding layer.
  • the no-turning method includes a method of exposure and development, a method of removing unnecessary portions of the light-shielding layer by laser heat (ablation method), and a photosensitive resist film is applied on the light-shielding layer provided on the substrate. And a method of removing the photosensitive resist film after exposure and development and patterning.
  • abbreviations method a method of removing unnecessary portions of the light-shielding layer by laser heat
  • a photosensitive resist film is applied on the light-shielding layer provided on the substrate.
  • any of removing the photosensitive resist film after exposure and development and patterning can be used.
  • the following methods (1) to (3) are preferable in terms of the simplicity of the process and the resolution of patterning.
  • Method (1) A non-photosensitive fine particle-containing composition is applied onto a substrate, the resulting coating film is dried to form a light-shielding layer, and a photoresist film is applied onto the light-shielding layer.
  • Method (2) A photosensitive fine particle-containing composition is applied onto a substrate, and the resulting coating film is dried to form a photosensitive light-shielding layer.
  • the photosensitive light-shielding layer is exposed and developed (undeveloped). Patterning by removing the hardened part)
  • Method (3) A photosensitive fine particle-containing composition is applied onto a temporary support, and the resulting coating film is dried to form a photosensitive light-shielding layer to form a laminate (photosensitive transfer material).
  • the laminate is laminated on a desired substrate, the temporary support is removed, the photosensitive light-shielding layer is transferred to the substrate, and the photosensitive light-shielding layer transferred and formed on the substrate is exposed and developed.
  • a light-shielding layer can be formed by a simple process as compared with conventional methods using vapor deposition or sputtering.
  • the desired pattern can be formed.
  • a coating method is suitable, and the coating method is not particularly limited.
  • the coating method is described in JP-A-5-224011.
  • the spin coating method described in JP-A-9323472 or the like can be used.
  • the obtained transfer material is thermoplastic as necessary in addition to the light-shielding layer comprising the temporary support and the fine particle-containing composition. It can have a resin layer and a Z or intermediate layer.
  • a desired pattern can be formed using a known light source.
  • the light source should be selected according to the photosensitivity of the photoresist film or photosensitive light-shielding layer!
  • Known light sources such as ultra-high pressure mercury lamp, xenon lamp, carbon arc lamp, and argon laser can be used.
  • an optical filter described in JP-A-6-59119 and having a light transmittance of 2% or less at a wavelength of 400 nm or more may be used in combination with the light source.
  • the exposure may be batch exposure in which the entire surface to be exposed is exposed at once, or may be divided exposure in which regions obtained by dividing the surface to be exposed are sequentially exposed. Furthermore, exposure performed while scanning the surface to be exposed using a laser may be used.
  • Development after exposure can be performed using a developer.
  • a dilute aqueous solution of an alkaline substance is preferable, and the aqueous solution contains a small amount of an organic solvent miscible with water.
  • alkaline substance examples include alkali metal hydroxides (eg, sodium hydroxide or potassium hydroxide), alkali metal carbonates (eg, sodium carbonate or potassium carbonate), alkali metal bicarbonate. Salts (eg, sodium bicarbonate or potassium bicarbonate), alkali metal silicates (eg, sodium silicate or potassium silicate), alkali metal metasilicates (eg, sodium metasilicate or potassium metasilicate), Triethanolamine, dietanolamine, monoethanolamine, morpholine, tetraalkylammonum hydroxides (eg tetramethylammonium hydroxide) or trisodium phosphate are suitable.
  • alkali metal hydroxides eg, sodium hydroxide or potassium hydroxide
  • alkali metal carbonates eg, sodium carbonate or potassium carbonate
  • alkali metal bicarbonate Salts (eg, sodium bicarbonate or potassium bicarbonate)
  • alkali metal silicates eg, sodium silicate or
  • the concentration of the alkaline substance in the aqueous solution is preferably 0.01 to 30% by mass, and the pH of the aqueous solution is preferably 8 to 14.
  • properties such as acidity of the light-sensitive light-shielding layer, for example, It is possible to change the pH of the developer so that development by film-like detachment can be performed.
  • water-miscible organic solvent examples include methanol, ethanol, 2 propanol, 1 propanol, butanol, diacetone alcohol, ethylene glycol monomethino ethenore, ethylene glycol mono eno eno enoate, ethylene glycol.
  • the concentration of the water-miscible organic solvent in the aqueous solution is generally from 0.1 to 30% by mass.
  • the developer may further contain a known surfactant.
  • the concentration of the surfactant in the developer is preferably 0.01 to 10% by mass.
  • the developer may be used as a bath solution or a jetting solution.
  • the uncured portion of the photosensitive light-shielding layer can also be removed in solid form (preferably in the form of a film). In this case, the light-shielding layer is rubbed with a rotating brush or a wet sponge in the developer. It is preferable to use an injection pressure at the time of jetting the developer or the developer.
  • the developer temperature is usually in the range of around 40 ° C force around room temperature!
  • the light-shielding layer may be washed with water after development.
  • the degree of curing of the photosensitive light-shielding layer cured by exposure can be increased, and the solvent resistance and alkali resistance can be further increased.
  • a heating method a method of heating the substrate after development in an electric furnace or a dryer, or a method of heating the substrate after development with an infrared lamp can be applied.
  • the light-shielding film for a display device of the present invention is preferably a film heated after development from the viewpoint of increasing the film strength.
  • the heating conditions depend on the composition and thickness of the light shielding film. It is preferable to heat the light shielding film at 180-300 ° C for 5-60 minutes. It is more preferable to heat at 200-270 ° C for 10-50 minutes. Heat at 200-250 ° C for 10-50 minutes. More preferably.
  • the light shielding film may be further exposed before heating the light shielding film after development. In this case, the exposure can be performed by the same method as the exposure described above.
  • a protective layer may be further provided on the light-shielding layer before the light-shielding layer is exposed in a pattern.
  • the protective layer functions as an oxygen-blocking layer for blocking oxygen during pattern exposure to increase the exposure sensitivity of the photosensitive light-blocking layer.
  • An oxygen-blocking resin such as polyvinyl alcohol is used as the protective layer.
  • a layer contained in the main component is preferred. This layer is unnecessary after the formation of the light-shielding film (light-shielded image), and is removed by development.
  • the thickness of the light-shielding film for a display device of the present invention is preferably from 0.05 to 2.0 ⁇ m, more preferably from 0.1 to 1.5 m. If the thickness is within the above range, the desired optical density is secured and the display contrast is good, and the unevenness of the substrate surface (the difference between the portion where the light shielding film is provided and the portion where it is not provided) increases. This does not cause inconvenience when forming RGB pixels on the light shielding film in a later process.
  • the transmission density (optical density) of the light-shielding film for a display device of the present invention is preferably 3.5 or more, more preferably 4.0 or more, and still more preferably 4.5 or more. When the optical density is within the above range, high contrast and high display quality can be ensured.
  • a glass substrate generally used in a display device is preferable.
  • a substrate made of a known glass such as soda glass, low alkali glass or non-alkali glass is suitable.
  • the glass substrate is described, for example, in “Introduction to Liquid Crystal Display Engineering” (Hanae Suzuki, published by Nikkan Kogyo Shimbun, 1998).
  • a transparent plastic substrate such as a silicon wafer or polyolefin can be used as the substrate.
  • Sarako the TFT element substrate on which TFT elements are arranged is used as the substrate.
  • the thickness of the substrate is preferably in the range of 0.5 to 3 mm, and more preferably in the range of 0.6 to 2 mm.
  • the light-shielding film for a display device of the present invention is preferably close to an ideal black color from the viewpoint of contrast and visibility of a display image.
  • the degree of closeness to the ideal black is the color difference between the chromaticity of the light-shielding film and the ideal black target chromaticity when the chromaticity of the light-shielding film is expressed by the (X, y) value of the xyz color system. Can be represented.
  • the smaller the color difference value the more ideal the color of the light shielding film.
  • the ideal black target chromaticity (X, y) value is (0.33, 0.33)
  • the difference between the target chromaticity and the chromaticity of the light shielding film is XY It is represented by the ⁇ ⁇ value of the color system, and based on this value, the degree of proximity to the ideal black can be evaluated.
  • the light-shielding material of the present invention is a light-shielding material used for forming a light-shielding film for a display device, and has at least one fine particle-containing layer on a support, and if necessary, a thermoplastic resin layer. , An intermediate layer, and a protective film as the outermost layer.
  • the fine particle-containing layer according to the present invention has an aspect ratio of 2 to: LOO metal fine particles and Z or metal compound fine particles, a polymer compound having at least one thioether group, and a compound that is cured by heat or light. And is thermosetting or photocurable. Further, it may further contain other components such as a colorant (more preferably a black colorant) as necessary.
  • the compound curable by heat or light is preferably in the form of a photocurable material containing a polyfunctional monomer and a photopolymerization initiator.
  • the light-shielding material of the present invention is preferably a transfer material in which a fine particle-containing layer that can be transferred to a transfer target is provided on a support.
  • a photosensitive transfer material provided with a photosensitive light-shielding layer will be described in detail as an example.
  • the present invention is not limited to this.
  • the light-shielding material of the present invention is preferably a photosensitive transfer material suitable for the method (3) mentioned as one of the methods suitable for forming the light-shielding film for a display device described above.
  • This photosensitive transfer material is formed by applying a temporary support and the photosensitive fine particle-containing composition of the present invention to the temporary support directly or via another layer, and drying the resulting coating film. And a photosensitive light-shielding layer.
  • the thickness of the light-sensitive light-shielding layer is preferably from 0.05 to 2.0 ⁇ m, more preferably from 0.1 to 1.5 ⁇ m.
  • the thickness is within the above range, a desired optical density is ensured and the display contrast is good, and the unevenness of the substrate surface (the difference between the portion where the light shielding film is provided and the portion where the light shielding film is not provided) is large. This will not cause inconvenience when forming RGB pixels on this in a later process.
  • the photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the photosensitive light-shielding layer, and further includes a thermoplastic resin layer and the photosensitive light-shielding layer. More preferably, it has an alkali-soluble intermediate layer therebetween.
  • the photosensitive transfer material may have a protective film on the exposed surface of the photosensitive light-shielding layer.
  • the temporary support is preferably chemically and thermally stable and made of a flexible material.
  • the temporary support is preferably a thin sheet of Teflon (registered trademark), polyethylene terephthalate, polyethylene naphthalate, polyacrylate, polycarbonate, polyethylene, or polypropylene, or a laminate thereof.
  • Teflon registered trademark
  • the temporary support preferably has good peelability from the layer.
  • the thickness of the temporary support is suitably 5 to 300 / ⁇ ⁇ , and preferably 20 to 150 111 layers.
  • the temporary support can be replaced with the substrate described above.
  • a light-shielded image (including a black matrix) having a desired pattern can be formed on the substrate, and the substrate on which the light-shielded image is formed can be used as the substrate of the display device. it can.
  • the thermoplastic resin layer includes at least a resin having thermoplasticity, and can be generally formed using a preparation liquid containing a solvent and a thermoplastic resin.
  • thermoplastic resin layer examples include acrylic resin, polystyrene resin, polyester, polyurethane, rubber resin, vinyl acetate resin, polyolefin resin, and these resins. Mention may be made of copolymers.
  • the resin of the thermoplastic resin layer is preferably alkali-soluble.
  • thermoplastic resin layer paragraph number [00] of JP 2004-317897 A 46] to [0048] can be used.
  • the thickness of the thermoplastic resin layer is preferably 3 ⁇ m or more. When the thickness of the thermoplastic resin is within the above range, it is possible to completely adapt to the unevenness of the surface (substrate) to be transferred of 1 m or more.
  • the upper limit of the thickness of the thermoplastic resin layer is preferably about 100 ⁇ m or less, more preferably about 50 ⁇ m or less, in terms of alkaline aqueous removability and production suitability.
  • the solvent of the preparation solution containing the thermoplastic resin for forming the thermoplastic resin layer is capable of dissolving the resin of this layer, and is not particularly limited, for example, methyl Ethyl ketone, n-propanol, or isopropanol can be used.
  • the photosensitive transfer material When the photosensitive transfer material has the thermoplastic resin layer, the photosensitive transfer material prevents mixing of the two layers when the preparation liquid is applied between the thermoplastic resin layer and the photosensitive light-shielding layer. Alternatively, it is preferable to further have an intermediate layer for the purpose of blocking oxygen.
  • the intermediate layer contains at least a resin, and is generally formed using a preparation solution containing an aqueous solvent and a resin having a low compatibility with the solvent used for forming a thermoplastic resin layer or a photosensitive light-shielding layer. can do.
  • Examples of such a resin that is preferably soluble in alkali in the intermediate layer include those described in paragraph No. [0050] of JP 2004-317897.
  • the thickness of the intermediate layer is preferably in the range of 0.1 to 5 ⁇ m, and more preferably in the range of 0.5 to 3 ⁇ m.
  • the intermediate layer has excellent oxygen barrier properties, and the intermediate layer can be removed in a short time during image formation.
  • the fine particle-containing layer of the photosensitive transfer material is composed of metal fine particles and / or metal compound fine particles having an aspect ratio of 2 to: a polymer compound having a thioether group and a compound cured with heat or light (and preferably a solvent).
  • a metal-based fine particle system as described above which is formed by coating, for example, it is a thin film and has little change in color due to the alteration of the fat component and fine particles in a high-temperature environment. It has excellent dispersibility in the medium and stability in the system of the dispersed fine particles, and has a good hue, high optical density.
  • a conventionally known laminator or vacuum laminator can be used.
  • an auto-cut laminator can be used in the method in order to improve friction.
  • the heating temperature at the time of lamination is preferably about 60 to 150 ° C, and the pressing pressure is preferably about 0.2 to 20 kgZcm2.
  • the laminate has a substrate line speed of 0.05 to: LOm
  • a light-shielding film for a display device is formed using a photosensitive transfer material
  • the photosensitive transfer material and the substrate are laminated, the temporary support is peeled off, exposure and development are sequentially performed, and heating is further performed. Is preferred. For the exposure, development and heating conditions, those described above can be applied.
  • the substrate with a light-shielding film of the present invention uses the fine particle-containing composition of the present invention described above, the ink for forming a colored film for a display device of the present invention described above, or the light-shielding material of the present invention described above on the substrate. And has a light shielding film.
  • the light shielding film can be formed by the methods (1) to (3) suitable for forming the light shielding film for a display device described above, and more preferably by the method (3).
  • the components of the fine particle-containing composition, the colored film forming ink for display device, and the light shielding material and preferred embodiments thereof are as described above. Further, the thickness and transmission density (optical density) of the light shielding film are the same as those of the light shielding film for a display device described above.
  • the color filter of the present invention has a plurality of pixels exhibiting different hues on a light-transmitting substrate and a light-shielded image (V, a so-called black matrix) separating each of the plurality of pixels.
  • the light-shielded image is the above-described light-shielding film for a display device of the present invention.
  • the light-transmitting substrate for example, the above-described substrate or a driving substrate (TFT element substrate or the like) provided with a TFT element can be used.
  • the color filter of the present invention has the light-shielding film for a display device of the present invention described above, and the display device Since the light shielding film is formed using the fine particle-containing composition of the present invention described above or the colored film forming ink for display device of the present invention described above, the light shielding film is exposed to a high temperature during production. Even in such a case, it has a good hue and a high optical density with little change in color caused by alteration of the resin component and fine particles in a high temperature environment, and is excellent in display image contrast and wiring shielding.
  • a TFT element substrate is used for the color filter of the present invention
  • a plurality of pixels and a light shielding film for a display device that separates each of the plurality of pixels may be provided on the TFT element substrate! .
  • the color filter of the present invention may have only a light shielding film (black matrix) for a display device without providing a plurality of pixels on the TFT element substrate.
  • a plurality of pixels are formed on a light-transmitting substrate different from the TFT element substrate, and the substrate on which the plurality of pixels are formed is disposed so as to face the TFT element substrate. This improves the aperture ratio of the TFT array.
  • a plurality of pixels exhibiting different hues can be formed by a conventional method using a plurality of types of colored photosensitive resin compositions and photosensitive transfer materials for pixel formation. After forming a plurality of pixels, heat treatment is preferably performed.
  • JP-A-2005-3861, JP-A-2004-361448, and JP-A-2004-205731 can be referred to.
  • the liquid crystal display element of the present invention includes the substrate with the light shielding film of the present invention described above, and more specifically, the substrate with the light shielding film of the present invention, more specifically, the fine particle-containing composition of the present invention described above and the colored film for display device. Because it has a light-shielding film formed using a forming ink or a light-shielding material, it has a good hue and a high optical density with little tint change due to exposure to high-temperature environments. It is possible to display an image with good display quality.
  • the liquid crystal display element includes the substrate with the light-shielding film of the present invention, and may further include a component of a known liquid crystal display element that is not particularly limited.
  • a liquid crystal display element includes a color filter substrate, a light-transmitting substrate disposed so as to face the color filter substrate, a liquid crystal layer provided between the substrates, and a liquid crystal that drives the liquid crystal in the liquid crystal layer.
  • Drive unit including a simple matrix drive system and an active matrix drive system
  • the color filter of the present invention described above can be used as a color filter substrate.
  • the liquid crystal display device of the present invention has the liquid crystal display element of the present invention. Since the liquid crystal display element of the present invention has a substrate with a light-shielding film of the present invention described above (in particular, the fine particle-containing composition of the present invention, a color film-forming ink for a display device, or a light-shielding material), It has a good hue with little color change due to exposure and a high optical density, and can display images with good contrast and high display quality.
  • a light-shielding film of the present invention described above in particular, the fine particle-containing composition of the present invention, a color film-forming ink for a display device, or a light-shielding material
  • the liquid crystal display device of the present invention has the liquid crystal display element of the present invention, and can further include components of a known liquid crystal display device that is not particularly limited otherwise.
  • the polymer solution used in the synthesis of the polymer 2 was replaced with a mixture of 67.9 parts of phenylthioethyl acrylate, 47.8 parts of methacrylic acid, and 84.3 parts of methyl methacrylate. 20% solution of polymer 4 (weight average molecular weight 78 000, a polymer dispersant according to the present invention).
  • composition of fine particle-containing composition for black material Components having the following composition were mixed to prepare a light-shielding image-forming coating solution (fine particle-containing composition for black material).
  • the alkali-free glass substrate was cleaned with a UV cleaner, then brush-cleaned with a cleaning agent, and then ultrasonically cleaned with ultrapure water.
  • the cleaned substrate was heated at 120 ° C for 3 minutes to stabilize its surface condition.
  • a glass substrate coater (MH-1600 manufactured by F'S Japan Co., Ltd.) having a slit-like nozzle was used!
  • a light-shielding image-forming coating solution was applied to form a coating film (coating process).
  • the substrate was placed in a vacuum drying apparatus VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to dry part of the solvent to eliminate the fluidity of the coating film, and then the edge 'bead'
  • VCD vacuum drying apparatus
  • the unnecessary coating solution at the edge of the substrate was removed with a rim bar (EBR), and the substrate was pre-baked at 120 ° C for 3 minutes to form a light-shielding layer with a layer thickness of 0.5 ⁇ m.
  • a mask quartz exposure mask having a lattice-like image pattern
  • a non-alkali glass substrate provided with a light shielding layer
  • the distance between the mask surface and the surface of the light shielding layer is set.
  • the light shielding layer was subjected to pattern exposure at an exposure amount of 200 mj / cm 2 (exposure process).
  • ultrapure water is sprayed onto the side of the alkali-free glass substrate on which the black pattern is formed with an ultra-high pressure cleaning nozzle at a pressure of 9.8 MPa to remove the residue, and black (K) is deposited on the alkali-free glass substrate. An image was formed. Thereafter, the substrate was beta-treated at 220 ° C. for 40 minutes (beta process) to obtain a light-shielded image.
  • a photosensitive resin composition according to paragraphs [0075] to [0086] of JP-A No. 2004-347831 is provided on an alkali-free glass substrate (hereinafter referred to as “color filter substrate”;) on which a light-shielding image is formed.
  • color filter substrate an alkali-free glass substrate
  • red (R), green (G), and blue (B) colored patterns (colored pixels) having a predetermined size and shape were formed to produce a color filter.
  • a color filter was produced by the following method.
  • a coupling component solution having 3 strengths was prepared and cooled to a temperature of 10 ° C.
  • the diazo solution obtained above was added dropwise to this so as not to exceed a temperature of 10 ° C., and reacted. Further, add K CO
  • a yellow pigment composition having the following composition was prepared.
  • the yellow pigment composition having the above composition was stirred with a motor mill “M-50” (manufactured by Eiger) for 16 hours at a peripheral speed of 9 mZ seconds using 0.65 mm diameter Zircoyu beads.
  • M-50 motor mill
  • a yellow pigment dispersion PY-139 was prepared.
  • red pixel forming coating solution (R1) for color filters shown in Table 1 below Prepare the red pixel forming coating solution (R1) for color filters shown in Table 1 below, and apply this coating solution on a soda lime glass substrate (100 mm x 100 mm, thickness 1.1 mm) on the spin coater “1H-DX”. (Mikasa Co., Ltd.) was applied at 180 rpm, and then the substrate was placed in an oven and heated at a temperature of 100 ° C. for 2 minutes to dry the resulting coating film.
  • a green pixel forming coating solution (G1) shown in Table 1 below was prepared, and this coating solution was used as the red pixel pattern described above. After coating at 230 rpm on a substrate with a spin coater, a green (G) pixel pattern was formed in the same manner as in the red pixel pattern formation described above.
  • a blue pixel forming coating solution (B1) for a color filter shown in Table 1 below was prepared, and this coating solution was spin-coated on the substrate on which the red pixel pattern and the blue pixel pattern were formed.
  • a blue (B) pixel pattern is formed in the same manner as the above red pixel pattern formation, and the (R) pixel pattern, (G) pixel pattern, and (B) according to the present invention are formed.
  • a substrate (color filter) on which a pixel pattern was laminated was obtained.
  • a liquid crystal display device was produced as follows, and a liquid crystal display device was further produced.
  • a thin film transistor (TFT) and a pixel electrode were formed on a separately prepared glass substrate so as to correspond to the RGB pattern of the obtained color filter, and an active matrix substrate was prepared by providing an alignment film. .
  • an ITO film and an alignment film were further formed on the color filter obtained above to obtain a counter substrate.
  • the obtained active matrix substrate and the counter substrate are arranged so as to face each other so that a predetermined interval (so-called cell thickness) is formed between them, and TN liquid crystal is sealed in the space between the two substrates.
  • a sealing agent were bonded together with a sealing agent to obtain a liquid crystal display element.
  • polarized light is applied to the surfaces of both substrates of the obtained liquid crystal display element.
  • a plate was placed in cross-col, and a knock light was further placed on the active matrix substrate side to obtain a liquid crystal display device.
  • Example 1 a silver fine particle composition was prepared in the same manner as in Example 1, except that the 20% solution of polymer 1 was replaced with a 20% solution of polymer 2 and normal propanol was replaced with methyl ethyl ketone. Then, evaluation 1 was performed, and a light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were obtained. The results of Evaluation 1 are shown in Table 2.
  • a silver fine particle composition was prepared in the same manner as in Example 1, except that the 20% solution of polymer 1 was replaced with the 20% solution of polymer 3 and normal propanol was replaced with methyl ethyl ketone. Then, evaluation 1 was performed, and a light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were obtained. The results of Evaluation 1 are shown in Table 2.
  • a silver fine particle composition was prepared in the same manner as in Example 1, except that the 20% solution of polymer 1 was replaced with the 20% solution of polymer 4 and normal propanol was replaced with methyl ethyl ketone. Then, evaluation 1 was performed, and a light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were obtained. The results of Evaluation 1 are shown in Table 2.
  • Example 1 the average aspect ratio of the rod-shaped silver fine particles is 54.7 to 3.2 (Example 5), 12.2 (Example 6), 78.4 (Example 7), or 1.3 ( A silver fine particle composition was prepared and evaluated 1 in the same manner as in Example 1 except that each of them was replaced with Example 8), and a light shielding image, a color filter, a liquid crystal display element, and a liquid crystal display device were obtained. It was. The results of Evaluation 1 are shown in Table 2.
  • thermoplastic resin coating solution prepared with the following formulation HI.
  • the coating film is dried at 100 ° C for 3 minutes to form a thermoplastic resin layer with a dry thickness of 5 m.
  • an intermediate layer coating solution prepared by the following formulation P1 was applied using a slit coater, and the coating film was dried at lOO ° C for 3 minutes to obtain a dry thickness of 1.
  • An intermediate layer (oxygen barrier film) of / z m was laminated.
  • the light-shielding image-forming coating solution prepared in Example 1 was applied using a slit coater, and the coating film was dried at 100 ° C. for 3 minutes to obtain a dry film thickness of 0.5 ⁇ m.
  • the photosensitive light-shielding layer (metal black layer) was formed.
  • thermoplastic resin layer As described above, a film in which a thermoplastic resin layer, an intermediate layer, and a photosensitive light-shielding layer were sequentially laminated on a PET temporary support was prepared, and a protective film having a thickness of 12 m was formed on the light-shielding layer.
  • a polypropylene film was pressure-bonded to obtain a photosensitive transfer material.
  • thermoplastic resin layer Hl ⁇ Prescription of coating solution for thermoplastic resin layer Hl>
  • the alkali-free glass substrate is washed with a rotating brush having nylon hair while spraying a glass detergent solution on the alkali-free glass substrate for 20 seconds, shower-washed with pure water, and then a silane coupling solution (N- ⁇ (Aminoethyl) ⁇ -aminopropyltrimethoxy silane 0.3% aqueous solution, Shin-Etsu Chemical Co., Ltd. ⁇ 603) was sprayed for 20 seconds with a shower, and then washed with pure water. Further, this substrate was heated at 100 ° C. for 2 minutes using a substrate preheating apparatus.
  • a silane coupling solution N- ⁇ (Aminoethyl) ⁇ -aminopropyltrimethoxy silane 0.3% aqueous solution, Shin-Etsu Chemical Co., Ltd. ⁇ 603
  • the exposed photosensitive light-shielding layer was superposed so as to be in contact with the surface of the heated glass substrate, and a laminator Lamiell type [( Ltd.) using a Hitachi-in dust Ryizu], rubber roller temperature 130 ° C, linear pressure Loon / cm 2, bonding the photosensitive transfer material and the substrate under the condition of a conveying speed of 2. 2MZ minute (laminate).
  • the PET temporary support was peeled from the obtained laminate (transfer process).
  • a mask (a quartz exposure mask having an image pattern) and a glass substrate disposed so that the mask and the thermoplastic resin layer face each other are set substantially parallel and perpendicular to each other, and the surface of the mask is sensed.
  • the distance between the surface of the photosensitive resin layer on the side in contact with the intermediate layer was set to 100 m.
  • a proximity type exposure machine manufactured by Hitachi Electronics Engineering Co., Ltd.
  • an ultra-high pressure mercury lamp pattern the photosensitive light-shielding layer with an exposure amount of 70 mjZcm 2 from the thermoplastic resin layer side through the mask. Exposed (exposure process).
  • a triethanolamine developer T-PD1 (containing 2.5% triethanolamine, a nonionic surfactant, and a polypropylene antifoaming agent, manufactured by Fuji Photo Film Co., Ltd.)
  • the flat nozzle cover was 30 ° C, the nozzle pressure was 0.04 MPa, sprayed from above the thermoplastic resin layer for 50 seconds to perform shower development, and the thermoplastic resin layer and the intermediate layer were developed and removed.
  • KOH developer CDK—1 Fluji Film Elect Mouth-Cusmaterials ( Co., Ltd .; KOH and non-surfactant-containing alkaline developer) diluted 100 times with pure water, sprayed from flat nozzle at 23 ° C, nozzle pressure 0.04MPa iron for 80 seconds.
  • the photosensitive light-shielding layer was shower-developed (development process) to obtain a pattern image.
  • the chromaticity of the light-shielded image obtained in each Example and Comparative Example was measured at a pinhole diameter of 5 m using a microspectrophotometer OSP100 (manufactured by Olympus Optical Co., Ltd.).
  • the smaller the color difference ⁇ , the better the black hue, and the evaluation results are shown in Table 2 below.
  • the transmission density (OD) of the light-shielded image (film) obtained in each Example and Comparative Example was measured using a Macbeth densitometer (TD-904 manufactured by Macbeth). At that time, the measured density was corrected by the optical density of the glass substrate.
  • Table 2 The evaluation results are shown in Table 2 below.
  • Comparative Example 1 in which a polymer compound having a thioether group was not used, the dispersion stability was insufficient, and silver particles were aggregated and a light-shielded image could not be obtained.

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Abstract

Disclosed is a fine particle-containing composition which contains at least metal fine particles and/or metal compound fine particles, a polymer compound having at least one thioether group, and a compound which is cured by heat or light.

Description

明 細 書  Specification
微粒子含有組成物、表示装置用着色膜形成用インク、表示装置用遮光 膜、遮光材料、遮光膜付き基板、カラーフィルタ、液晶表示素子、及び液晶表示 装置  Fine particle-containing composition, colored film forming ink for display device, light shielding film for display device, light shielding material, substrate with light shielding film, color filter, liquid crystal display element, and liquid crystal display device
技術分野  Technical field
[0001] 本発明は、プラズマディスプレイ表示装置、 EL表示装置、及び CRT表示装置など の表示装置の内部に設けられる遮光用の膜 (遮光膜)を作製するのに好適な微粒子 含有組成物並びに、該微粒子含有組成物を用いた表示装置用着色膜形成用インク 、表示装置用遮光膜、遮光材料、遮光膜付き基板、カラーフィルタ、液晶表示素子、 及び液晶表示装置に関する。  [0001] The present invention relates to a fine particle-containing composition suitable for producing a light-shielding film (light-shielding film) provided in a display device such as a plasma display device, an EL display device, and a CRT display device, and The present invention relates to an ink for forming a colored film for a display device, a light shielding film for a display device, a light shielding material, a substrate with a light shielding film, a color filter, a liquid crystal display element, and a liquid crystal display device.
背景技術  Background art
[0002] 表示装置用の遮光膜は、液晶表示装置、プラズマディスプレイ表示装置、 EL表示 装置、及び CRT表示装置などの装置内部に、黒色の縁や、画素周囲の格子状若し くはストライプ状の黒色の縁部 (V、わゆるブラックマトリックス）、又は薄膜トランジスタ 一 (TFT)遮光のためのドット状若しくは線状の黒色パターンなどとして設けられてい る。  [0002] A light-shielding film for a display device is formed inside a device such as a liquid crystal display device, a plasma display display device, an EL display device, and a CRT display device with a black edge, a lattice shape or a stripe shape around a pixel. It is provided as a black edge (V, a so-called black matrix), or a dot-like or linear black pattern for shielding a thin film transistor (TFT).
[0003] 例えばブラックマトリックスは、例えば、液晶表示装置の遮光膜の例であり、液晶表 示装置の内部に備えられたカラーフィルタの複数の着色画素（赤、緑、青）の各々を 取り囲むように設けられており、画素間の光漏れによるコントラストの低下を防止する 。また、遮光膜の他の例として、 TFTを用いたアクティブマトリックス駆動方式の液晶 表示素子において、光による TFTの電流リークに伴なう画質低下を防ぐために TFT 上に設ける遮光膜がある。  [0003] For example, a black matrix is an example of a light shielding film of a liquid crystal display device, and surrounds each of a plurality of colored pixels (red, green, blue) of a color filter provided in the liquid crystal display device. And prevents a decrease in contrast due to light leakage between pixels. As another example of the light shielding film, there is a light shielding film provided on the TFT in an active matrix liquid crystal display element using TFT in order to prevent deterioration of image quality due to TFT current leakage due to light.
これらの遮光膜には一般に、光学濃度 2以上の遮光性が要求されており、遮光膜 の色調は表示装置の表示品位の点から黒色が好ましい。  These light-shielding films are generally required to have a light-shielding property with an optical density of 2 or more, and the color tone of the light-shielding film is preferably black from the viewpoint of display quality of the display device.
[0004] 上記に関連して、金属微粒子の分散物を利用して遮光膜を作製する方法に関する 開示がある（例えば、特許文献 1参照)。この方法では、金属微粒子の分散のために 一般に広く知られて 、る分散剤が用いられて 、る。 [0005] また、ハロゲンィ匕銀粒子の保護コロイドとして、ハロゲンィ匕銀粒子と共にチォエーテ ル基を有する高分子化合物を用いる例がある（例えば、特許文献 2〜4参照)。 特許文献 1 :特開 2004— 334182号公報 [0004] In relation to the above, there is a disclosure regarding a method for producing a light shielding film using a dispersion of metal fine particles (see, for example, Patent Document 1). In this method, a dispersant that is generally known for dispersing metal fine particles is used. [0005] In addition, there is an example in which a high molecular compound having a thioether group is used together with a halogenated silver particle as a protective colloid of the halogenated silver particle (see, for example, Patent Documents 2 to 4). Patent Document 1: Japanese Patent Application Laid-Open No. 2004-334182
特許文献 2：特開平 2 - 166442号公報  Patent Document 2: JP-A-2-166442
特許文献 3：特開平 4 - 151140号公報  Patent Document 3: Japanese Patent Laid-Open No. 4-151140
特許文献 4：米国特許 3615624号明細書  Patent Document 4: US Patent 3615624 Specification
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] し力しながら、上記した遮光膜の作製方法において金属微粒子の分散に用いる分 散剤は通常広く用いられるものであり、このような方法で作製された遮光膜は表示装 置用遮光膜として用いるには、金属微粒子の分散が不充分で満足できる遮光性能 は得られない。 However, the dispersing agent used for dispersing the metal fine particles in the above-described method for producing a light shielding film is generally widely used, and the light shielding film produced by such a method is a light shielding film for a display device. Therefore, satisfactory dispersion of the metal fine particles is not obtained.
[0007] また、表示装置用の遮光膜を作製する場合、製造中に膜が高温に曝されること (例 えば現像後のポストベータ）がある。従来から広く知られた分散剤を含む金属微粒子 の分散系から得られた膜の色味は高温下で変化しやすぐ所期の遮光性能や表示 コントラストが得られない。  [0007] Further, when producing a light-shielding film for a display device, the film is exposed to a high temperature during production (for example, post-development post-beta). The color of a film obtained from a dispersion of metal fine particles containing a widely known dispersing agent changes at high temperatures, and the desired light shielding performance and display contrast cannot be obtained immediately.
課題を解決するための手段  Means for solving the problem
[0008] 本発明の第 1のアスペクトは、少なくとも、金属微粒子及び Z又は金属化合物微粒 子と、少なくとも 1つのチォエーテル基を有する高分子化合物（以下、「本発明に係る 高分子分散剤」ということがある。）と、熱もしくは光で硬化する化合物とを含有する微 粒子含有組成物を提供する。  [0008] The first aspect of the present invention is a polymer compound having at least metal fine particles and Z or metal compound fine particles and at least one thioether group (hereinafter referred to as "polymer dispersant according to the present invention"). And a fine particle-containing composition comprising a compound that is cured by heat or light.
[0009] 本発明の第 2のアスペクトは、前記微粒子含有組成物を含む表示装置用着色膜形 成用インクを提供する。  [0009] A second aspect of the present invention provides an ink for forming a colored film for a display device comprising the fine particle-containing composition.
本発明の第 3のアスペクトは、表示装置用遮光膜の形成に用いられる遮光材料で あって、 支持体上に、アスペクト比が 2〜： LOOの金属微粒子及び Z又は金属化合 物微粒子と、少なくとも 1つのチォエーテル基を有する高分子化合物と、熱もしくは光 で硬化する化合物とを少なくとも含有する微粒子含有層を少なくとも 1層有する遮光 材料を提供する。 本発明の第 4のアスペクトは、前記微粒子含有組成物、前記表示装置用着色膜形 成用インク、又は前記遮光材料を用いて形成された遮光膜を有する遮光膜付き基板 を提供する。 A third aspect of the present invention is a light-shielding material used for forming a light-shielding film for a display device, and on a support, metal fine particles having an aspect ratio of 2 to: LOO and Z or metal compound fine particles, and at least Provided is a light-shielding material having at least one fine particle-containing layer containing at least a polymer compound having one thioether group and a compound that is cured by heat or light. A fourth aspect of the present invention provides a substrate with a light-shielding film having a light-shielding film formed using the fine particle-containing composition, the colored film forming ink for a display device, or the light-shielding material.
本発明の第 5のアスペクトは、光透過性の基板上に、異なる色相を呈する複数の画 素と、前記複数の画素の各々を離隔する遮光画像とを有するカラーフィルタにおい て、前記遮光画像が前記表示装置用遮光膜であるカラーフィルタを提供する。  According to a fifth aspect of the present invention, there is provided a color filter having a plurality of pixels exhibiting different hues and a light-shielded image separating each of the plurality of pixels on a light-transmitting substrate. Provided is a color filter which is a light shielding film for the display device.
本発明の第 6のアスペクトは、前記遮光膜付き基板を備えた液晶表示素子を提供 する。  According to a sixth aspect of the present invention, there is provided a liquid crystal display device comprising the light-shielding film-coated substrate.
本発明の第 7のアスペクトは、前記液晶表示素子を備えた液晶表示装置を提供す る。  A seventh aspect of the present invention provides a liquid crystal display device comprising the liquid crystal display element.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0010] 以下、本発明の微粒子含有組成物について詳細に説明すると共に、該説明を通じ て本発明の表示装置用着色膜形成用インク、表示装置用遮光膜、遮光材料、遮光 膜付き基板、カラーフィルタ、液晶表示素子、及び液晶表示装置の詳細についても 詳述する。 Hereinafter, the fine particle-containing composition of the present invention will be described in detail, and through the description, the colored film-forming ink for display device, the light-shielding film for display device, the light-shielding material, the substrate with the light-shielding film, the color Details of the filter, the liquid crystal display element, and the liquid crystal display device will also be described in detail.
[0011] <微粒子含有組成物 > [0011] <Fine particle-containing composition>
本発明の微粒子含有組成物は、金属微粒子及び Z又は金属化合物微粒子と、少 なくとも 1つのチォエーテル基を有する高分子化合物と、熱もしくは光で硬化する化 合物とを少なくとも含有し、必要に応じて、他の成分を含むことができる。  The fine particle-containing composition of the present invention contains at least metal fine particles and Z or metal compound fine particles, a polymer compound having at least one thioether group, and a compound that is cured by heat or light. Depending on the situation, other components may be included.
[0012] 本発明においては、着色剤 (特に黒色の着色剤）としての、分散された金属微粒子 及び Z又は金属化合物微粒子、及び該金属微粒子の分散のための分散剤としての In the present invention, dispersed metal fine particles and Z or metal compound fine particles as a colorant (particularly a black colorant), and a dispersant for dispersing the metal fine particles
、本発明に係る高分子分散剤 (チォエーテル基を有する高分子化合物)の使用は、 金属系の微粒子の、凝集防止等の挙動に寄与し、製造中に膜が高温に曝されても、 高温環境での榭脂成分及び微粒子の変質に伴なう色味変化が抑制されるので、既 述の金属系の微粒子の系中での分散性及び分散した該微粒子の系中で安定性が 向上し、良好な色相と高い光学濃度を確保することができる。 The use of the polymer dispersant (polymer compound having a thioether group) according to the present invention contributes to the behavior of metal-based fine particles such as aggregation prevention, and even if the film is exposed to high temperature during production, Since the color change associated with the alteration of the oil component and fine particles in the environment is suppressed, the dispersibility of the metallic fine particles described above in the system and the stability of the dispersed fine particles are improved. In addition, good hue and high optical density can be ensured.
[0013] 本発明の微粒子含有組成物では、金属微粒子及び/又は金属化合物微粒子が、 後述するチォエーテル基を有する高分子化合物 (本発明に係る高分子分散剤）中に 分散されて 、ることが好ま 、。 In the fine particle-containing composition of the present invention, the metal fine particles and / or the metal compound fine particles are contained in a polymer compound having a thioether group (a polymer dispersant according to the present invention) described later. Preferred to be distributed.
[0014] 金属微粒子及び Z又は金属化合物微粒子 [0014] Metal fine particles and Z or metal compound fine particles
本発明の微粒子含有組成物は、（特に黒色の)着色剤として、金属微粒子及び金 属化合物微粒子の少なくとも 1種を含有する。金属系の微粒子を着色剤として用いる ことで、薄膜で高濃度の像形成が可能であり、特に遮光画像 (ブラックマトリクスを含 む。）などの黒色像の形成に有効である。  The fine particle-containing composition of the present invention contains at least one of metal fine particles and metal compound fine particles as a (particularly black) colorant. By using metallic fine particles as a colorant, it is possible to form a high-density image with a thin film, and it is particularly effective for forming a black image such as a light-shielded image (including a black matrix).
[0015] 本発明において、金属微粒子における「金属」とは、「岩波理化学辞典 (第 5版)」（1[0015] In the present invention, "metal" in the metal fine particles means "Iwanami Dictionary of Chemical Sciences (5th edition)" (1
998年、岩波書店発行）に記載の「金属」（352頁）による。また、「金属化合物」とは、 金属と金属以外の元素との化合物であり、ここでの金属も前記金属微粒子における 金属と同義である。 According to “Metal” (page 352) described in 998, published by Iwanami Shoten. The “metal compound” is a compound of a metal and an element other than the metal, and the metal here is also synonymous with the metal in the metal fine particles.
[0016] 金属微粒子としては、特に限定はなく適宜選択することができ、例えば、長周期型 周期表 (IUPAC 1991)の第 4周期、第 5周期、及び第 6周期に含まれる金属群より 選択される金属を主成分として含むことが好ましぐまた、第 2族、第 8族、第 9族、第 1 0族、第 11族、第 12族、第 13族、及び第 14族に含まれる金属群から選ばれる金属 を主成分として含むことが好まし 、。  [0016] The metal fine particles are not particularly limited and may be appropriately selected. For example, the metal fine particles may be selected from a group of metals included in the fourth period, the fifth period, and the sixth period of the long-period periodic table (IUPAC 1991). In addition, it is preferable to include the metal as a main component. Also included in Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, and Group 14. It is preferable to contain as a main component a metal selected from a group of metals.
これら金属のうち、金属微粒子は、第 4周期、第 5周期、又は第 6周期の金属であつ て、第 2族、第 10族、第 11族、第 12族、又は第 14族の金属を含むことがより好まし い。  Among these metals, fine metal particles are metals of the 4th, 5th, or 6th period, and the metals of Group 2, Group 10, Group 11, Group 12, or Group 14 are used. It is more preferable to include it.
[0017] 金属微粒子の形状には、特に制限はなぐ不定形、棒状 (針状、円柱状、直方体等 の角柱形、ラグビーボール形等)、平板状 (鱗片状、楕円板状、板状)、繊維状、コィ ル状等であってもよい。好ましくは、金属微粒子の形状は、板状粒子、棒状 (ロッド状 )である。  [0017] There are no particular restrictions on the shape of the metal fine particles. The shape is irregular, rod-shaped (acicular, cylindrical, rectangular parallelepiped, rugby ball, etc.), flat plate (scale, elliptical plate, plate). It may be in the form of a fiber or coil. Preferably, the shape of the metal fine particles is plate-like particles or rod-like (rod-like).
[0018] 前記金属微粒子の金属は、銅、銀、金、白金、ノラジウム、ニッケル、錫、コノ レト、 ロジウム、イリジウム、鉄、ルテニウム、オスミウム、マンガン、モリブデン、タングステン 、ニオブ、タンタル、カルシウム、チタン、ビスマス、アンチモン、鉛、又はこれらの合金 より選ばれる少なくとも一種であることが好ましぐ銅、銀、金、白金、パラジウム、 -ッ ケル、錫、コバルト、ロジウム、イリジウム、又はこれらの合金であることがより好ましぐ 銅、銀、金、白金、錫、又はこれらの合金より選ばれる少なくとも一種であることがさら に好ましい。 [0018] Metals of the fine metal particles are copper, silver, gold, platinum, noradium, nickel, tin, conoleto, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, titanium. Copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, or an alloy thereof, which is preferably at least one selected from bismuth, antimony, lead, and alloys thereof. It is more preferable to be at least one selected from copper, silver, gold, platinum, tin, or alloys thereof. Is preferred.
[0019] 中でも、容易に微粒子が得られやすいという点で、前記金属微粒子の金属は、金、 銀、銅、錫であることがさらに好ましぐ銀が最も好ましい。本発明における金属微粒 子は、前記金属の合金、好ましくは銀とスズの合金、カゝら形成されてもよい。  [0019] Among them, the metal of the metal fine particles is most preferably silver, more preferably gold, silver, copper, or tin in that fine particles can be easily obtained. The metal fine particles in the present invention may be formed from an alloy of the metal, preferably an alloy of silver and tin, or a metal.
[0020] 金属微粒子の数平均粒径は膜厚を超えてはならないが、それ以外の点では特に 制限はない。数平均粒径は 10〜1000nmの範囲が好ましぐ 10〜500nmの範囲 力 り好ましぐ 10〜200nmの範囲が更に好ましい。該数平均粒径が前記範囲内で あると、金属微粒子の生成が容易で、力かる範囲内の金属微粒子を用いてカラーフ ィルタを作製した場合に、その特性に起因して目視により良好な黒色 (茶褐色がかつ た色相にならない）に見えるブラックマトリクス等の黒色像部が得られ、粒子径が大き すぎることに起因する金属微粒子分散後の分散物の安定性の低下や、遮光性の悪 化もない。  [0020] The number average particle diameter of the metal fine particles should not exceed the film thickness, but is not particularly limited in other respects. The number average particle size is preferably in the range of 10 to 1000 nm, more preferably in the range of 10 to 500 nm, and even more preferably in the range of 10 to 200 nm. When the number average particle size is within the above range, the formation of metal fine particles is easy, and when a color filter is produced using metal fine particles within the range of strength, a good black color is visually observed due to the characteristics. A black image part such as a black matrix that looks like a brownish brown color does not appear, and the stability of the dispersion after dispersion of metal fine particles due to the particle size being too large, or the light shielding property is deteriorated. Nor.
[0021] ここで、「粒径」とは、粒子の電子顕微鏡写真画像力も求めた、該粒子の面積と同じ 面積の円の直径をいい、「数平均粒径」とは、 100個の粒子の粒径を求め、求められ た粒径を平均することにより得られる。なお、粒径分布については特に制約はない。  [0021] Here, "particle size" refers to the diameter of a circle having the same area as that of the particles, and the number-average particle size is 100 particles. It is obtained by calculating the particle size of the particles and averaging the obtained particle sizes. The particle size distribution is not particularly limited.
[0022] また、金属微粒子は、均一な組成を有してもょ 、し、不均一な組成を有してもょ 、。  [0022] The metal fine particles may have a uniform composition or a non-uniform composition.
不均一な組成を持つ金属微粒子として、金属の母粒子の表面に該母粒子の内部の 金属と異なる金属のコーティング層を設けた粒子等が挙げられる。  Examples of the metal fine particles having a non-uniform composition include particles in which a metal coating layer different from the metal inside the mother particles is provided on the surface of the metal mother particles.
[0023] 前記金属化合物微粒子は、金属と金属以外の元素との化合物で作られ、このような 化合物としては、例えば、金属の酸化物、硫化物、硫酸塩、炭酸塩などが挙げられる 。このうち、色調や微粒子形成のしゃすさの点で、金属化合物は硫ィ匕物であることが 好ましい。金属化合物の具体例として、酸化銅 (Π)、硫化鉄、硫化銀、硫化銅 (11)、 チタンブラックなどが挙げられ、色調、微粒子形成のしゃすさ、安定性の点で、金属 化合物は硫ィ匕銀であることがさらに好まし 、。  [0023] The metal compound fine particles are made of a compound of a metal and an element other than the metal. Examples of such a compound include metal oxides, sulfides, sulfates and carbonates. Of these, the metal compound is preferably a sulfate from the viewpoint of color tone and fine particle formation. Specific examples of the metal compound include copper oxide (Π), iron sulfide, silver sulfide, copper sulfide (11), titanium black, and the like. From the viewpoint of color tone, fine particle formation, and stability, the metal compound is sulfurated. It ’s even better to be a silver candy.
[0024] また、前記金属化合物微粒子は、均一な組成を有してもよ!、し、不均一な組成を有 してもよい。不均一な組成を持つ金属化合物微粒子として、金属化合物の母粒子の 表面に該母粒子の内部の組成と異なる組成のコーティング層を設けた粒子等が挙げ られる。 [0025] 本発明における金属微粒子及び金属化合物微粒子の製造方法には特に制限は なぐ気相法、液相法などの公知の方法を使用することができる。金属化合物微粒子 の作製方法は、例えば、「超微粒子の技術と応用における最新動向 II」（住べテクノリ サーチ (株）、 2002年発行）に記載されて 、る。 [0024] The metal compound fine particles may have a uniform composition, or may have a non-uniform composition. Examples of the metal compound fine particles having a non-uniform composition include particles in which a coating layer having a composition different from the composition inside the mother particle is provided on the surface of the metal compound mother particle. [0025] The production method of the metal fine particles and metal compound fine particles in the present invention may be a known method such as a gas phase method or a liquid phase method without particular limitation. A method for producing metal compound fine particles is described in, for example, “Latest Trends in Technology and Application of Ultrafine Particles II” (Sumibe Techno Search Co., Ltd., issued in 2002).
[0026] 金属微粒子には、市販のものを用いることができる。或いは金属微粒子は金属ィォ ンの化学的還元法、無電解メツキ法、又は金属の蒸発法等により調製することが可能 である。  [0026] Commercially available metal fine particles can be used. Alternatively, the metal fine particles can be prepared by a metal ion chemical reduction method, an electroless plating method, a metal evaporation method, or the like.
特にロッド状の銀微粒子の製造方法については、例えば Adv. Mater. 2002, 14 , 80— 82の記載を参照することができ、すなわち、種粒子としての球形の銀微粒子 に銀塩を添カ卩し、得られたものに CTAB (セチルトリメチルアンモ -ゥムブロマイド)等 の界面活性剤の存在下で、ァスコルビン酸などの比較的還元力の弱 、還元剤を添 加することにより、銀ロッドやワイヤーを得ることができる。また、同様の記載が、 Mate r. Chem. Phys. 2004, 84, 197— 204、 Adv. Funct. Mater. 2004, 14, 183 189にある。  For the method for producing rod-shaped silver fine particles in particular, reference can be made to, for example, the description of Adv. Mater. 2002, 14, 80-82. That is, a silver salt is added to spherical silver fine particles as seed particles. Then, in the presence of a surfactant such as CTAB (cetyltrimethylammonium bromide), a silver rod or wire can be obtained by adding a reducing agent such as ascorbic acid with a relatively weak reducing power. Obtainable. Similar descriptions can be found in Mater. Chem. Phys. 2004, 84, 197-204, Adv. Funct. Mater. 2004, 14, 183 189.
[0027] また、 Mater. Lett. 2001, 49, 91 95には、電気分解を用いた方法が、 J. Mat er. Res. 2004, 19, 469— 473には、マイクロ波を照射することにより銀ロッドを生 成する方法が、それぞれ記載されている。また、逆ミセルと超音波を併用した方法に つ ヽて、 Phys. Chem. B, 2003, 107, 3679— 3683に記載力 ^ある。  [0027] In Mater. Lett. 2001, 49, 91 95, a method using electrolysis is used. In J. Mater. Res. 2004, 19, 469-473, microwave irradiation is performed. Each method for producing a silver rod is described. In addition, the method using reverse micelles and ultrasonic waves is described in Phys. Chem. B, 2003, 107, 3679-3683.
金微粒子の製造方法 ίま、 Phys. Chem. B 1999, 103、 3073— 3077及び La ngmuir 1999, 15, 701 - 709, J. Am. Chem. Soc. 2002, 124, 14316— 14 317に記載されている。  Manufacturing method of gold fine particles described in ί, Phys. Chem. B 1999, 103, 3073-3077 and Langmuir 1999, 15, 701-709, J. Am. Chem. Soc. 2002, 124, 14316-14 317. ing.
[0028] ロッド状の粒子は、界面活性剤の存在下で還元法により作製することができる。基 本的には、界面活性剤の種類や還元剤の種類、添加量調整、 pH制御により、種々 のロッド状粒子の調製が可能である。具体的には、金属との相互作用の少ない界面 活性剤をはじめに系に添加し、系中の金属化合物を還元して金属粒子を成長させ、 次 、で金属と大きく相互作用する界面活性剤を系に添加し、該粒子のさらなる成長 を抑える。つまり、還元剤の種類と時間で金属粒子の形状を制御することができる。  [0028] Rod-like particles can be produced by a reduction method in the presence of a surfactant. Basically, various rod-shaped particles can be prepared by controlling the type of surfactant, the type of reducing agent, adjusting the amount added, and controlling the pH. Specifically, a surfactant with less interaction with the metal is first added to the system, the metal compound in the system is reduced to grow metal particles, and then a surfactant that interacts greatly with the metal is added. Add to system to prevent further growth of the particles. That is, the shape of the metal particles can be controlled by the type and time of the reducing agent.
[0029] 金属化合物微粒子は、ロッド状の粒子を酸化や硫化することによって調製すること ができる。 [0029] Metal compound fine particles are prepared by oxidizing or sulfiding rod-shaped particles. Can do.
[0030] 本発明において、前記金属微粒子には、金属と他の金属との複合微粒子が含まれ 、前記金属化合物微粒子には、金属と金属化合物との複合微粒子、金属化合物と 他の金属化合物との複合微粒子が含まれる。  [0030] In the present invention, the metal fine particles include composite fine particles of a metal and another metal, and the metal compound fine particles include a composite fine particle of a metal and a metal compound, a metal compound and another metal compound, and Composite fine particles.
[0031] 複合微粒子の形状には、特に制限はない。例えば、粒子の内部と表面で組成の異 なる粒子、 2種類の粒子が合一した粒子等を挙げることができる。また、金属と金属化 合物との複合微粒子の場合、この複合微粒子は 1種以上の金属化合物及び 1種以上 の金属を含むことができる。  [0031] The shape of the composite fine particles is not particularly limited. For example, particles having different compositions between the inside and the surface of the particles, particles in which two types of particles are combined, and the like can be mentioned. In the case of composite fine particles of a metal and a metal compound, the composite fine particles can contain one or more kinds of metal compounds and one or more kinds of metals.
前記「金属と金属化合物との複合微粒子」の具体例としては、銀と硫化銀との複合 微粒子、銀と酸化銅 (II)との複合微粒子などが挙げられる。  Specific examples of the “composite fine particles of metal and metal compound” include composite fine particles of silver and silver sulfide, composite fine particles of silver and copper (II) oxide, and the like.
[0032] 上記の粒子以外に、本発明における金属微粒子及び金属化合物微粒子は、コア' シェル構造を有する複合粒子であってもよ ヽ。コア'シェル構造を有する複合粒子は 、コア材料と、コア材料の表面を被覆するシェル材料とを有する。コア'シェル構造を 有する複合粒子を用いる場合、シェル材料としては、例えば、 Si、 Ge、 AlSb、 InP、 Ga 、 As、 GaP、 ZnS、 ZnSe、 ZnTe、 CdS、 CdSe、 CdTe、 PbS、 PbSe、 PbTe、 Se、 Te、 Cu Cl、 CuBr、 Cul、 TICU TlBr、 T1I、及びこれらの固溶体もしくはこれらを 90mol%以上 含む固溶体より選択される少なくとも一種の半導体、又は銅、銀、金、白金、パラジゥ ム、ニッケル、錫、コノ ルト、ロジウム、イリジウム、鉄、ルテニウム、オスミウム、マンガ ン、モリブデン、タングステン、ニオブ、タンタル、チタン、ビスマス、アンチモン、鉛、 又はこれらの合金より選択される少なくとも一種の金属を挙げることができる。これらシ エル材料は、利用される波長域である 300〜800nmにおいて、量子閉じ込め効果に より離散化した量子レベルに共鳴する光吸収ピークを有するという点で好ましい。  In addition to the above particles, the metal fine particles and metal compound fine particles in the present invention may be composite particles having a core-shell structure. A composite particle having a core'shell structure has a core material and a shell material that covers the surface of the core material. When using composite particles having a core-shell structure, examples of shell materials include Si, Ge, AlSb, InP, Ga, As, GaP, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, and PbTe. , Se, Te, CuCl, CuBr, Cul, TICU TlBr, T1I, and at least one semiconductor selected from these solid solutions or solid solutions containing 90 mol% or more thereof, or copper, silver, gold, platinum, palladium, List at least one metal selected from nickel, tin, connort, rhodium, iridium, iron, ruthenium, osmium, manganone, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, lead, or alloys thereof. be able to. These shell materials are preferable in that they have a light absorption peak that resonates with a quantum level discretized by the quantum confinement effect in a wavelength range of 300 to 800 nm.
[0033] コア材料は、好ましくは銅、銀、金、パラジウム、ニッケル、錫、ビスマス、アンモチン 、鉛、又はこれらの合金より選択される少なくとも一種である。 [0033] The core material is preferably at least one selected from copper, silver, gold, palladium, nickel, tin, bismuth, ammotine, lead, or alloys thereof.
前記シェル材料は、反射率を低下させる目的で、屈折率の調整剤としても好適に 用いられる。  The shell material is also suitably used as a refractive index adjuster for the purpose of reducing the reflectance.
[0034] コア 'シェル構造を有する複合粒子のコア材料としては、例えば、銅、銀、金、パラ ジゥム、又はこれらの合金より選択される少なくとも一種の金属を用いることができる。 [0035] コア'シェル構造を有する複合粒子の作製方法には、特に制限はなぐ代表的な方 法を以下に示す。 [0034] As the core material of the composite particles having a core 'shell structure, for example, at least one metal selected from copper, silver, gold, palladium, or an alloy thereof can be used. [0035] As a method for producing a composite particle having a core-shell structure, a typical method without particular limitation is shown below.
(1)公知の方法で作製した金属微粒子の表面に、酸化、硫ィ匕などにより金属化合 物のシェルを形成する方法がある。例えば、金属微粒子を水などの分散媒に分散さ せた分散物に硫ィ匕ナトリウムや硫ィ匕アンモ-ゥムなどの硫ィ匕物を添加する方法がある oこの方法により、金属微粒子表面が硫化されてコア'シェル複合粒子が形成される この場合、用いる金属微粒子は、気相法、液相法などの公知の方法で作製すること ができ、金属微粒子の作製方法については、例えば「超微粒子の技術と応用におけ る最新動向 II」（住べテクノリサーチ (株）、 2002年発行）に記載がある。  (1) There is a method of forming a metal compound shell on the surface of a metal fine particle produced by a known method by oxidation, sulfurization or the like. For example, there is a method of adding a sulfide such as sodium sulfate or ammonium sulfate to a dispersion in which metal fine particles are dispersed in a dispersion medium such as water. In this case, the metal fine particles to be used can be prepared by a known method such as a gas phase method or a liquid phase method. Latest trends in ultrafine particle technology and applications II ”(Sumibe Techno Research Co., Ltd., published in 2002).
(2)金属微粒子を作製する過程で連続的にコア表面に金属化合物のシェルを形成 する方法がある。例えば、金属塩溶液に還元剤を添加し、金属イオンの一部を還元 して金属微粒子を作製し、得られた混合物に硫ィ匕物を添加し、作製した金属微粒子 の周囲に金属硫化物を形成することにより、コア'シェル複合粒子が形成される。  (2) There is a method of continuously forming a metal compound shell on the core surface in the process of producing metal fine particles. For example, a reducing agent is added to a metal salt solution, a part of the metal ions is reduced to produce metal fine particles, a sulfide is added to the resulting mixture, and a metal sulfide is formed around the produced metal fine particles. To form core-shell composite particles.
[0036] 吸収スペクトルの制御ができ、色相を黒色に近づけることができる点で、上記した金 属微粒子及び金属化合物微粒子のアスペクト比 (粒子の長軸長 Z粒子の短軸長の 比）は 2〜： LOOであることが好ましい。吸収スペクトルの制御ができ、色相をより黒色に 近づけることができる点で、前記アスペクト比は 4〜80がより好ましぐ 10〜60が更に 好ましぐ 15〜50が最も好ましい。アスペクト比が前記範囲内であると、黒色粒子を 得るのが比較的容易であり、可視光城の吸収が良好で画質 (解像力）の低下を招来 することちない。  [0036] The aspect ratio of the metal fine particles and metal compound fine particles described above (the ratio of the long axis length of the particles to the short axis length of the particles) is 2 in that the absorption spectrum can be controlled and the hue can be made close to black. ~: LOO is preferred. The aspect ratio is preferably 4 to 80, more preferably 10 to 60, and most preferably 15 to 50 in that the absorption spectrum can be controlled and the hue can be made closer to black. When the aspect ratio is within the above range, it is relatively easy to obtain black particles, the absorption of visible light is good, and the image quality (resolution) is not lowered.
[0037] アスペクト比とは、金属微粒子又は金属化合物微粒子の、後述のように定義された 長軸長を短軸長で割った値を意味し、 100個の金属微粒子及び Z又は金属化合物 微粒子のアスペクト比を測定し、その測定値を平均することで得られる。なお、粒子の 投影面積は電子顕微鏡写真力 面積を測定し、その測定面積に撮影倍率を掛ける こと〖こより得られる。  [0037] The aspect ratio means a value obtained by dividing a major axis length defined as described later by a minor axis length of metal fine particles or metal compound fine particles, and 100 metal fine particles and Z or metal compound fine particles. It is obtained by measuring the aspect ratio and averaging the measured values. The projected area of the particles can be obtained by measuring the photographic power area of the electron microscope and multiplying the measured area by the photographing magnification.
[0038] 次に、粒子の径 (長軸長、短軸長)を説明する。ここでは金属微粒子を例として用い る。 金属微粒子の粒子長として以下のような 3つの長さを用いる。 1個の金属粒子がちょ うど (きっちりと)収まる箱（直方体)を仮想し、この箱の長さ L、幅 b、高さ又は厚み tを もってこの金属粒子の寸法と定義する。このような箱を想定するにはいくつかの方法 があるが、本発明では以下の方法を採用する。 Next, the particle diameter (major axis length, minor axis length) will be described. Here, metal fine particles are used as an example. The following three lengths are used as the particle length of the metal fine particles. A box (a rectangular parallelepiped) in which one metal particle fits tightly is imagined, and the size of this metal particle is defined by the length L, width b, height, or thickness t of this box. There are several methods for assuming such a box. In the present invention, the following method is adopted.
まず、仮想平面上に金属粒子を、最も重心が低くて安定に静止するように置くよう 仮想する。次に、仮想平面に対し直角に立てた 2枚の平行な仮想平板により、その仮 想平板間隔が最も短くなるように金属粒子を挟む。このときの平板間隔を「幅 とす る。次に、前記幅 bを決する 2枚の仮想平板に対し直角で前記仮想平面に対しても直 角の 2枚の仮想平行な平板により金属粒子を挟み、この 2枚の平板間隔を「長さ L」と する。最後に金属粒子の最も高い位置に接触するように仮想天板を前記仮想平面に 平行に載せ、仮想天板と仮想平面との間隔を高さ又は厚み tとする。（この方法により 仮想平面、各 2枚の仮想平板及び仮想天板によって画される直方体が形成される。 ) このように求めた金属粒子の三つの寸法 b、 L及び tの最も長 、ものを「長軸」と定義し 、長軸方向における長さを「長軸長」と、また、長軸に平行な光を金属粒子に照射し て得られる投影面積と同じ面積の真円を求め、その直径を「短軸長」と定義する。  First, hypothesize that metal particles are placed on a virtual plane so that the center of gravity is the lowest and remains stable. Next, the metal particles are sandwiched between two parallel virtual flat plates standing at right angles to the virtual plane so that the distance between the virtual flat plates is the shortest. The distance between the plates at this time is defined as “width. Next, the metal particles are formed by two virtual parallel plates that are perpendicular to the two virtual plates that determine the width b and perpendicular to the virtual plane. The distance between the two plates is “length L”. Finally, the virtual top plate is placed parallel to the virtual plane so as to contact the highest position of the metal particles, and the distance between the virtual top plate and the virtual plane is defined as height or thickness t. (This method forms a cuboid defined by a virtual plane, two virtual flat plates, and a virtual top plate.) The longest of the three dimensions b, L, and t of the metal particles determined in this way Defined as `` major axis '', the length in the major axis direction is `` major axis length '', and a perfect circle with the same area as the projected area obtained by irradiating metal particles with light parallel to the major axis is obtained, The diameter is defined as “short axis length”.
[0039] 金属微粒子又は金属化合物微粒子の短軸長は、 4〜50nmの範囲内が好ましぐ 15〜50nmの範囲内がより好ましぐ 15〜30nmの範囲内が最も好ましい。また、金 属微粒子又は金属化合物微粒子の長軸長（最大長）は、 10〜： LOOOnmの範囲内が 好ましぐ更には 100〜1000nmの範囲内がより好ましぐ 400〜800nmの範囲内 が好ましい。 [0039] The short axis length of the metal fine particles or metal compound fine particles is preferably within the range of 4 to 50 nm, more preferably within the range of 15 to 50 nm, and most preferably within the range of 15 to 30 nm. Also, the long axis length (maximum length) of metal fine particles or metal compound fine particles is preferably in the range of 10 to: LOOOnm, more preferably in the range of 100 to 1000 nm, and in the range of 400 to 800 nm. preferable.
[0040] アスペクト比を調整 (異なるアスペクト比の粒子を混合)することにより、すなわち同 一金属から形成され、異なるアスペクト比の微粒子を併用することにより、金属微粒子 及び Z又は金属化合物微粒子の吸収スペクトルを制御でき、色相を黒色に近づける こともできる。他の金属や金属化合物微粒子など、種々のアスペクト比を持つ粒子を 組み合わせることによつても、黒色に近い色相の金属微粒子及び z又は金属化合物 微粒子を得ることができる。  [0040] By adjusting the aspect ratio (mixing particles with different aspect ratios), that is, using fine particles of the same metal and different aspect ratios together, absorption spectra of metal fine particles and Z or metal compound fine particles The hue can be made closer to black. By combining particles having various aspect ratios such as other metal and metal compound fine particles, metal fine particles having a hue close to black and z or metal compound fine particles can be obtained.
[0041] 本発明における金属微粒子又は金属化合物微粒子の形状を球形力 例えばロッド 形状へ変化させると、可視光線の吸収量も約 2倍高められ、球状粒子の場合よりトー タルの吸収係数が大きくなり、透過濃度を高めることが可能である。これにより、高濃 度を保持しながら金属微粒子又は金属化合物微粒子の層を薄膜ィ匕することができる [0041] If the shape of the metal fine particles or metal compound fine particles in the present invention is changed to a spherical force, for example, a rod shape, the amount of absorption of visible light is also increased about twice, which is higher than the case of spherical particles. It is possible to increase the transmission density by increasing the absorption coefficient of tall. As a result, the layer of metal fine particles or metal compound fine particles can be thinned while maintaining a high concentration.
[0042] 微粒子含有組成物中における金属微粒子及び Z又は金属化合物微粒子の所望 の含有率は、微粒子の種類や性状により異なるが、該組成物の全固形分中の金属 微粒子及び Z又は金属化合物微粒子の含有率は 10〜98質量％が好ましぐ 20〜 95質量％がより好ましぐ 30〜93質量％が最も好ましい。該含有率が前記範囲内で あると、金属微粒子又は金属化合物微粒子の層が薄膜でも高濃度が得られ、現像 性に支障を来すこともない。 [0042] Although the desired content of metal fine particles and Z or metal compound fine particles in the fine particle-containing composition varies depending on the type and properties of the fine particles, the metal fine particles and Z or metal compound fine particles in the total solid content of the composition The content of is preferably 10 to 98% by mass, more preferably 20 to 95% by mass, and most preferably 30 to 93% by mass. When the content is within the above range, a high concentration can be obtained even if the layer of metal fine particles or metal compound fine particles is a thin film, and development performance is not hindered.
[0043] 高分子化合物  [0043] Polymer compound
本発明の微粒子含有組成物は、前記金属微粒子及び Z又は金属化合物微粒子 の分散剤として、少なくとも 1つのチォエーテル基を有する高分子化合物の少なくとも 1種 (本発明に係る高分子分散剤)を含有する。チォエーテル基を有する高分子化 合物を分散剤とするので、既述の金属系の微粒子の系中での分散性及び分散した 該微粒子の系中で安定性が向上し、色相（特に黒色相）が良好で、高い光学濃度の 画像形成が可能となる。  The fine particle-containing composition of the present invention contains at least one polymer compound having at least one thioether group (polymer dispersant according to the present invention) as a dispersant for the metal fine particles and Z or metal compound fine particles. . Since the polymer compound having a thioether group is used as the dispersant, the dispersibility of the metal fine particles described above in the system and the stability of the dispersed fine particles are improved, and the hue (particularly the black phase) is improved. ) Is good, and high optical density image formation is possible.
[0044] 本発明に係る高分子分散剤は、分子中に少なくとも一つのチォエーテル基を有す る高分子化合物の中から選択することができ、側鎖部分にチォエーテル基を有する 高分子化合物であることが好適である。  [0044] The polymer dispersant according to the present invention is a polymer compound that can be selected from polymer compounds having at least one thioether group in the molecule, and having a thioether group in the side chain portion. Is preferred.
[0045] より詳しくは、本発明に係る高分子分散剤は、高分子の構成単位として、少なくとも 一種のチォエーテル構造を側鎖に含むエチレン性不飽和単量体力 誘導される繰り 返し単位を分子中に有する高分子化合物であることがより好ましぐ下記一般式（1) で表される繰り返し単位の少なくとも 1種を有する高分子化合物であることがさらに好 ましい。  [0045] More specifically, the polymer dispersant according to the present invention includes, as a polymer structural unit, an ethylenically unsaturated monomer force-induced repeating unit containing at least one thioether structure in the side chain in the molecule. It is more preferable that the polymer compound has at least one kind of repeating unit represented by the following general formula (1).
[0046] [化 2] 一般式（1 ) [0046] [Chemical 2] General formula (1)
o  o
Z— Y— S— R  Z— Y— S— R
[0047] 前記一般式（1)において、 R1は、水素原子、又は総炭素数 1〜4のアルキル基を表 す。 In the general formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms in total.
総炭素数 1〜4のアルキル基としては、例えば、メチル基、ェチル基、ノルマルプロ ピル基、イソプロピル基、ノルマルブチル基、 secブチル基、イソブチル基、 tert—ブチ ル基等が挙げられ、中でも、メチル基が好ましい。  Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a sec butyl group, an isobutyl group, and a tert-butyl group. A methyl group is preferred.
[0048] 前記一般式（1)において、 R2は、水素原子、総炭素数 1〜18のアルキル基、総炭 素数 6〜14のァリール基、又は総炭素数 7〜16のァラルキル基を表し、このアルキ ル基、ァリール基、及びァラルキル基の各々は無置換でもよいし、 1以上の置換基を 有して 、てもよ 、し、飽和又は不飽和の環状構造を形成して 、てもよ 、。 In the general formula (1), R 2 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 16 carbon atoms. Each of the alkyl group, aryl group, and aralkyl group may be unsubstituted or may have one or more substituents, and may form a saturated or unsaturated cyclic structure. Moyo.
[0049] 前記 R2で表される総炭素数 1〜18のアルキル基は、無置換でもよいし、置換基を 有していてもよぐ例えば、メチル基、ェチル基、ノルマルプロピル基、イソプロピル基 、ノルマルブチル基、 sec—ブチル基、イソブチル基、 tert—ブチル基、へキシル基、 ォクチル基、ドデシル基、及びステアリル基が挙げられる。 R2が置換アルキル基であ る場合の置換基としては、ハロゲン原子、水酸基、アミノ基、アミド基、カルボキシル基 、エステル基、又はスルホ-ル基が好適である。 [0049] The alkyl group having 1 to 18 carbon atoms represented by R 2 may be unsubstituted or substituted. For example, a methyl group, an ethyl group, a normal propyl group, isopropyl Group, normal butyl group, sec-butyl group, isobutyl group, tert-butyl group, hexyl group, octyl group, dodecyl group, and stearyl group. As the substituent when R 2 is a substituted alkyl group, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, or a sulfonyl group is preferable.
[0050] R2がアルキル基の場合、該アルキル基は総炭素数 1〜 12のアルキル基であること が好ましぐ総炭素数 1〜8のアルキル基であることがより好ましぐメチル基、ェチル 基、ノルマルプロピル基、イソプロピル基、ノルマルブチル基、又は tert—ブチル基で あることがさらに好ましい。 [0050] When R 2 is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group having 1 to 8 carbon atoms. And more preferably an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, or a tert-butyl group.
[0051] 前記 R2で表される総炭素数 6〜14のァリール基は、無置換でもよいし、置換基を有 していてもよぐ例えば、フエ-ル基、トルィル基、キシリル基、ナフチル基、アントラセ -ル基が挙げられる。 R2が置換ァリール基である場合の置換基としては、ハロゲン原 子、水酸基、アミノ基、アミド基、カルボキシル基、エステル基、又はスルホ-ル基が 好適である。 [0051] The aryl group having 6 to 14 carbon atoms in total represented by R 2 may be unsubstituted or substituted. For example, a phenyl group, a tolyl group, a xylyl group, A naphthyl group and an anthracyl group are mentioned. Examples of the substituent when R 2 is a substituted aryl group include a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, or a sulfonyl group. Is preferred.
R2がァリール基の場合、該ァリール基は総炭素数 6〜： LOのァリール基であることが 好ましぐフエ-ル基であることがより好ましい。 When R 2 is an aryl group, the aryl group is preferably an aryl group having a total carbon number of 6 to LO and more preferably a phenol group.
[0052] 前記 R2で表される総炭素数 7〜16のァラルキル基は、無置換でもよいし、置換基を 有していてもよぐ例えば、ベンジル基、フエネチル基、ナフチルメチル基、アントラセ -ルメチル基が挙げられる。 R2が置換ァラルキル基である場合の置換基としては、ハ ロゲン原子、水酸基、アミノ基、アミド基、カルボキシル基、エステル基、又はスルホ二 ル基が好適である。 [0052] The aralkyl group having 7 to 16 total carbon atoms represented by R 2 may be unsubstituted or may have a substituent. For example, a benzyl group, a phenethyl group, a naphthylmethyl group, an anthracene group may be substituted. -Rumethyl group. As the substituent when R 2 is a substituted aralkyl group, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, or a sulfonyl group is preferable.
R2がァラルキル基の場合、該ァラルキル基は総炭素数 7〜： L 1のァラルキル基であ ることが好ましぐベンジル基であることがより好ましい。 When R 2 is an aralkyl group, the aralkyl group is more preferably a benzyl group, preferably an aralkyl group having a total carbon number of 7 to: L 1.
[0053] 前記一般式（1)において、 Zは、 O 又は NH を表す。また、 Yは、総炭素数 1〜8の 2価の連結基を表す。 [0053] In the general formula (1), Z represents O or NH. Y represents a divalent linking group having 1 to 8 carbon atoms in total.
Yで表される総炭素数 1〜8の 2価の連結基は、アルキレン基 (例、メチレン基、ェチ レン基、プロピレン基、ブチレン基、ペンチレン基）、ァルケ-レン基（例、エテュレン 基、プロぺ-レン基）、アルキ-レン基（例、ェチ-レン基、プロピ-レン基）、ァリーレ ン基（例、フエ-レン基）、二価のへテロ環基（例、 6 クロロー 1, 3, 5 トリアジンー 2 , 4ージィノレ基、ピリミジン 2, 4 ジィノレ基、キノキサリン 2, 3 ジィノレ基、ピリダ ジン— 3, 6—ジィル基）、 O—、— CO—、— NR— (Rは水素原子、アルキル基、 又はァリール基を表す。）、又はこれらの組み合わせ（例えば、 NHCH CH NH- The divalent linking group having a total carbon number of 1 to 8 represented by Y is an alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, pentylene group), alkene group (eg, etylene). Group, propylene group), alkylene group (eg, ethylene group, propylene group), arylene group (eg, phenylene group), divalent hetero ring group (eg, 6 Chloro-1, 3, 5 Triazine-2,4-diinole group, pyrimidine 2,4 dinore group, quinoxaline 2,3 dinore group, pyridazine— 3, 6-diyl group), O—, — CO—, — NR— ( R represents a hydrogen atom, an alkyl group, or an aryl group, or a combination thereof (for example, NHCH CH NH—
2 2twenty two
、 一NHCONH )であることが好ましい。 , 1 NHCONH).
[0054] 前記 Yで表されるアルキレン基、ァルケ-レン基、アルキ-レン基、ァリーレン基、又 は二価のへテロ環基、並びに Rで表されるアルキル基又はァリール基は、 1以上の置 換基を有していてもよい。該置換基の例としては、前記 R2で表されるァリール基の置 換基の例と同じである。 Rで表されるアルキル基及びァリール基は、既述の R2で表さ れるアルキル基及びァリール基と同義である。 [0054] The alkylene group, alkylene group, alkylene group, arylene group, or divalent heterocyclic group represented by Y, and the alkyl group or aryl group represented by R are one or more. It may have a substituent. Examples of the substituent are the same as the examples of the substituent of the aryl group represented by R 2 . The alkyl group and aryl group represented by R are synonymous with the alkyl group and aryl group represented by R 2 described above.
[0055] Yで表される総炭素数 1〜8の 2価の連結基は、総炭素数 1〜6の 2価の連結基であ ることが好ましぐエチレン基、プロピレン基、ブチレン基、へキシレン基、 CH—C  [0055] The divalent linking group having 1 to 8 carbon atoms in total represented by Y is preferably an ethylene group, propylene group, or butylene group having 1 to 6 carbon atoms in total. , Hexylene group, CH-C
2 2
H (OH)—CH—、又は C H -O-C H一であることがより好ましい。 [0056] 本発明に係る高分子分散剤は、前記一般式（1)で表される繰り返し単位を 1種の み含んでもょ 、し、 2種以上の前記繰り返し単位を含むモノマーを共重合して得られ る高分子化合物であってもよい。また、側鎖を構成するチォエーテル構造は、硫黄原 子を 1つのみ有してもよいし、前記 Z、 R2として硫黄原子を有する基を使用すること〖こ より、 2つ以上の硫黄原子を有する側鎖とすることもできる。 More preferably, it is H (OH) —CH— or CH 2 —OC 2 H. [0056] The polymer dispersant according to the present invention may contain only one type of repeating unit represented by the general formula (1), and may copolymerize a monomer containing two or more types of repeating units. It may be a polymer compound obtained in this way. Further, the thioether structure constituting the side chain may have only one sulfur atom, or two or more sulfur atoms can be used by using a group having a sulfur atom as Z and R 2. It can also be a side chain having
[0057] 本発明に係る高分子分散剤は、所望の高分子化合物に (好ましくは側鎖として)チ ォエーテル構造を導入することにより、あるいはチォエーテル基を (好ましくは側鎖に [0057] The polymer dispersant according to the present invention introduces a thioether structure into a desired polymer compound (preferably as a side chain) or a thioether group (preferably into a side chain).
)持つ単量体の単独重合、又はチォエーテル基を (好ましくは側鎖に)持つ単量体と 他の単量体との共重合により得ることができる。好ましくは、チォエーテル構造を側鎖 に含むエチレン性不飽和単量体の単独重合、又はチォエーテル構造を側鎖に含む エチレン性不飽和単量体と他の共重合成分との共重合により得ることができる。 ) Or a copolymer of a monomer having a thioether group (preferably in the side chain) with another monomer. Preferably, it can be obtained by homopolymerization of an ethylenically unsaturated monomer having a thioether structure in the side chain, or by copolymerization of an ethylenically unsaturated monomer having a thioether structure in the side chain with another copolymerization component. it can.
[0058] 以下、前記一般式（1)で表される繰り返し単位の具体例を示す。但し、本発明はこ れらによって制限されるものではない。  [0058] Specific examples of the repeating unit represented by the general formula (1) are shown below. However, the present invention is not limited by these.
[0059] [化 3] [0059] [Chemical 3]
Figure imgf000015_0001
Figure imgf000015_0001
[0060] 上記した中でも、 R1が水素原子又はメチル基であって、 R2がメチル基、ェチル基、 ノルマルプロピル基、ノルマルブチル基、 tert—ブチル基、又はフエニル基であって Zが— O—であって、 Yがエチレン基である繰り返し単位が好まし 、。 [0060] Among the above, a R 1 is a hydrogen atom or a methyl group, R 2 is a methyl group, Echiru group, n-propyl group, n-butyl group, tert- butyl group, or a phenyl group Z is - Preferred is a repeating unit O—, where Y is an ethylene group.
[0061] 本発明に係る高分子分散剤は、前記一般式（1)で表される繰り返し単位を有する モノマーと、 1以上の他のビュルモノマーとの共重合体であってもよい。 [0061] The polymer dispersant according to the present invention has a repeating unit represented by the general formula (1). It may be a copolymer of a monomer and one or more other bull monomers.
他のビュルモノマーは、芳香族ビュル化合物（例、スチレン、 OCーメチルスチレン、 p —ヒドロキシスチレン、クロロメチルスチレン、及びビュルトルエン）、シアン化ビュル（ 例、（メタ）アクリロニトリル、及びひ クロ口アクリロニトリル）、カルボン酸ビュルエステ ル (例、酢酸ビニル、安息香酸ビニル、及びギ酸ビニル）、脂肪族共役ジェン (例、 1, 3-ブタジエン、及びイソプレン）、（メタ）アクリル酸アルキルエステル（例、メチル (メタ） アタリレート、ェチル (メタ）アタリレート、 n ブチル (メタ）アタリレート、 i ブチル (メタ） アタリレート、及び 2-ェチルへキシル (メタ）アタリレート）、 （メタ）アクリル酸アルキルァ リールエステル（例、ベンジル (メタ）アタリレート）、 （メタ）アクリル酸置換アルキルエス テル (例、グリシジル (メタ）アタリレート、 2—ヒドロキシェチル (メタ）アタリレート、ジメチ ルアミノエチル (メタ）アタリレート、及びジメチルァミノプロピル (メタ）アタリレート）、ァ ルキル (メタ)アクリルアミド (例、（メタ)アクリルアミド、ジメチル (メタ)アクリルアミド、 N —イソプロピル (メタ）アクリルアミド、 n—ブチル (メタ）アクリルアミド、 tert—ブチル (メ タ）アクリルアミド、及び tert—ォクチル (メタ）アクリルアミド）、置換アルキル (メタ）ァク リルアミド（例、ジメチルアミノエチル (メタ）アクリルアミド、及びジメチルァミノプロピル（ メタ)アクリルアミド）、及び重合性オリゴマー（例、片末端メタクリロイル化ポリメチルメ タクリレートオリゴマー、片末端メタタリロイルイ匕ポリスチレンオリゴマー、及び片末端メ タクリロイル化ポリエチレングリコール）の少なくとも 1つであることが好ましい。  Other bur monomers include aromatic bur compounds (eg, styrene, OC-methyl styrene, p-hydroxy styrene, chloromethyl styrene, and butyltoluene), cyanide bur (eg, (meth) acrylonitrile, and acrylonitrile acrylonitrile), Carboxylate butyl esters (eg, vinyl acetate, vinyl benzoate, and vinyl formate), aliphatic conjugates (eg, 1,3-butadiene and isoprene), (meth) acrylic acid alkyl esters (eg, methyl (meta ) Atarylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 2-ethyl hexyl (meth) acrylate), (meth) acrylate alkyl ester , Benzyl (meth) acrylate), (meth) acrylic acid substituted alkyl ester Tell (eg, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate), alkyl (meth) acrylamide (eg , (Meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, and tert-octyl (meth) acrylamide), substituted alkyl ( (Meth) acrylamide (eg, dimethylaminoethyl (meth) acrylamide, and dimethylaminopropyl (meth) acrylamide), and polymerizable oligomer (eg, one-end methacryloylated polymethylmethacrylate oligomer, one-end methallyloyl-polystyrene) It is preferably at least one of an oligomer and a single-terminal methacryloylated polyethylene glycol.
[0062] 少なくとも 1つのチォエーテル基を有する高分子化合物 (本発明に係る高分子分散 剤）における前記一般式（1)で表される繰り返し単位の重合比率は、質量分率で 1〜 100%力 S好ましく、 5〜80%がより好ましぐ 10〜50%が特に好ましい。この重合比 率が前記範囲内であると、金属系の微粒子の系中での分散性、分散した該微粒子 の系中で安定性、色相及び光学濃度を向上させるのに効果的である。  [0062] The polymerization ratio of the repeating unit represented by the general formula (1) in the polymer compound having at least one thioether group (polymer dispersant according to the present invention) is 1 to 100% force in mass fraction. S, preferably 5 to 80%, more preferably 10 to 50%. When the polymerization ratio is within the above range, it is effective to improve the dispersibility of the metallic fine particles in the system and the stability, hue and optical density in the dispersed fine particles.
[0063] また、本発明の高分子分散剤は、必要に応じてアルカリ現像適性を付与できる点で 、分子中に酸基を有する高分子化合物が好ましい。前記酸基としては、カルボン酸 基、スルホン酸、リン酸、ボロン酸、フエノール類、スルホアミドなどの基が好適である 。本発明の高分子分散剤は、カルボン酸基を少なくとも一つ有する高分子化合物で あることがより好ましい。 [0064] アルカリ現像が必要な場合には、本発明の高分子分散剤の酸価は 20〜250mgK OHZgであることが好ましぐ 50〜200mgKOHZgであることがより好ましぐ 70〜 180mgKOHZgであることが最も好ましい。酸価が前記範囲内であると、金属系の 微粒子の系中での分散性及び分散した該微粒子の系中で安定性が良好であり、か つ微粒子含有組成物のアルカリ現像性も良好である。 [0063] In addition, the polymer dispersant of the present invention is preferably a polymer compound having an acid group in the molecule from the viewpoint that alkali developability can be imparted if necessary. As the acid group, a group such as a carboxylic acid group, a sulfonic acid, a phosphoric acid, a boronic acid, phenols, and a sulfoamide is preferable. The polymer dispersant of the present invention is more preferably a polymer compound having at least one carboxylic acid group. [0064] When alkali development is required, the acid value of the polymer dispersant of the present invention is preferably 20 to 250 mgK OHZg, more preferably 50 to 200 mgKOHZg, and 70 to 180 mgKOHZg. Most preferred. When the acid value is within the above range, the dispersibility of the metal-based fine particles in the system and the stability of the dispersed fine particles in the system are good, and the alkali developability of the fine particle-containing composition is also good. is there.
[0065] 本発明に係る高分子分散剤の重量平均分子量は、 2, 000〜1, 000, 000である こと力 S好ましく、 3, 000〜200, 000であること力 Sより好ましく、 5, 000〜100, 000で あることが最も好ましい。前記範囲内の重量平均分子量を有する高分子分散剤は金 属系の微粒子の系中での分散性向上に有効で、良好な膜強度を提供できると共に、 現像性に支障を来すこともな 、。  [0065] The weight average molecular weight of the polymer dispersant according to the present invention is preferably 2,000 to 1,000,000, preferably S, more preferably 3,000 to 200,000, more preferably S. Most preferably, it is between 000 and 100,000. A polymer dispersant having a weight average molecular weight within the above range is effective for improving dispersibility of metal-based fine particles in the system, can provide good film strength, and does not interfere with developability. ,.
[0066] 少なくとも 1つのチォエーテル基を有する高分子化合物の、既述の金属微粒子及 び Z又は金属化合物微粒子に対する含有率は、 1〜40質量％が好ましぐ 3〜30質 量％がより好ましぐ 5〜20質量％がより好ましい。該含有量が前記範囲内であると、 高分子化合物が微粒子に充分に吸着して微粒子の分散性が向上すると共に、熱に よる色相変化を抑えて色相及び光学濃度の向上に効果的であり、現像性に支障を 来すこともない。  [0066] The content of the polymer compound having at least one thioether group with respect to the aforementioned metal fine particles and Z or metal compound fine particles is preferably 1 to 40% by mass, more preferably 3 to 30% by mass. It is more preferably 5 to 20% by mass. When the content is within the above range, the polymer compound is sufficiently adsorbed on the fine particles to improve the dispersibility of the fine particles, and it is effective in improving the hue and optical density by suppressing the hue change due to heat. Also, it does not interfere with developability.
[0067] 熱もしくは光で硬化する化合物  [0067] Compound cured by heat or light
本発明の微粒子含有組成物は、少なくとも 1種の熱もしくは光で硬化する化合物を 含有する。  The fine particle-containing composition of the present invention contains at least one compound that is cured by heat or light.
熱もしくは光で硬化する化合物として、例えば、多官能モノマーを用いることができ る。多官能モノマーは重合してポリマーを形成し、このポリマーがバインダーとして機 能する。本発明の微粒子含有組成物は該多官能モノマーを含有しているので、本発 明の微粒子含有組成物を使用して形成した膜の強度は高い。多官能モノマーとして は、光重合可能なモノマーが好ましぐ更に熱重合性を有しているものがより好ましい 。多官能モノマーが熱重合性を有する場合には、多官能モノマーの光重合により得 られたポリマーを熱処理することで硬化度をより一層高めることができる。  As the compound that is cured by heat or light, for example, a polyfunctional monomer can be used. The polyfunctional monomer is polymerized to form a polymer, and this polymer functions as a binder. Since the fine particle-containing composition of the present invention contains the polyfunctional monomer, the strength of the film formed using the fine particle-containing composition of the present invention is high. As the polyfunctional monomer, a photopolymerizable monomer is preferred, and more preferred is a polymer having thermal polymerizability. When the polyfunctional monomer has thermal polymerizability, the degree of cure can be further increased by heat-treating the polymer obtained by photopolymerization of the polyfunctional monomer.
[0068] 前記多官能モノマーは、沸点が常圧で 100°C以上の化合物であり得る。そのような 化合物としては、例えば、エチレングリコールジ (メタ）アタリレート、トリエチレングリコ ールジ（メタ）アタリレート、テトラメチレングリコールジ (メタ）アタリレート、プロピレング リコールジ (メタ）アタリレート、ポリエチレングリコールジ (メタ）アタリレート、ポリプロピ レングリコールジ（メタ）アタリレート、 1, 3—ブタンジオールジ（メタ）アタリレート、トリメ チロールェタントリアタリレート、トリメチロールプロパントリ（メタ）アタリレート、トリメチロ ールプロパンジ（メタ）アタリレート、ネオペンチルグリコールジ（メタ）アタリレート、ペン タエリスリトールテトラ (メタ）アタリレート、ペンタエリスリトールトリ（メタ）アタリレート、ぺ ンタエリスリトールへキサ (メタ）アタリレート、ジペンタエリスリトールへキサ（メタ）アタリ レート、ジペンタエリスリトールペンタ（メタ）アタリレート、 1, 4一へキサンジオール（メ タ）アタリレート、へキサンジオールジ (メタ）アタリレート、トリメチロールプロパントリ（ァ クリロイルォキシプロピル）エーテル、トリ（アタリロイルォキシェチル)イソシァヌレート[0068] The polyfunctional monomer may be a compound having a boiling point of 100 ° C or higher at normal pressure. Examples of such compounds include ethylene glycol di (meth) acrylate and triethyleneglycol. Ruji (meth) Atari rate, tetramethylene glycol di (meth) Atari rate, propylene grayed Rikoruji (meth) Atari, polyethylene glycol di (meth) Atari rate, Polypropylene glycol di (meth) Atari rate, 1, 3 - butane Diol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane tri (meth) acrylate, trimethylol propane di (meth) acrylate, neopentyl glycol di (meth) acrylate, penta erythritol tetra (meta ) Atarylate, pentaerythritol tri (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) Tarireto, 1, 4 one hexanediol (meth) Atari rate, hexanediol di (meth) Atari rate, trimethylolpropane tri (§ methacryloyl Ruo propyl) ether, tri (Atari Roy Ruo key shell chill) Isoshianureto
、トリ（アタリロイルォキシェチル)シァヌレート、グリセリントリ（メタ）アタリレート、トリメチ ロールプロパンもしくはグリセリン等の多官能アルコールにエチレンォキシドゃプロピ レンォキシドを付加反応させたものを (メタ)アタリレートイ匕したもの等の多官能 (メタ） アタリレートを挙げることができる。 , Tri (atalyloxyxetyl) cyanurate, glycerin tri (meth) atalylate, trimethylolpropane, or glycerin and other polyfunctional alcohols that have been reacted by addition of ethylene oxide or propylene oxide to (meth) ataretoy Mention may be made of polyfunctional (meth) acrylates such as cocoons.
[0069] さらに、特公昭 48— 41708号、同 50— 6034号、特開昭 51— 37193号の各公報 に記載のウレタンアタリレート類、特開昭 48— 64183号、特公昭 49 43191号、同 52— 30490号の各公報に記載のポリエステルアタリレート類、エポキシ榭脂と (メタ） アクリル酸との反応生成物であるエポキシアタリレート類等の多官能アタリレートやメタ タリレートを上記化合物として挙げることができる。  [0069] Further, urethane acrylates described in JP-B-48-41708, JP-A-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49 43191, Polyfunctional talates and metatalates such as the polyester acrylates and epoxy acrylates which are the reaction products of epoxy resin and (meth) acrylic acid described in each publication of No. 52-30490 are listed as the above compounds. be able to.
[0070] 上記の中でも、多官能モノマーとしてはトリメチロールプロパントリ（メタ）アタリレート 、ペンタエリスリトールテトラ (メタ）アタリレート、ジペンタエリスリトールへキサ (メタ）ァク リレート、又はジペンタエリスリトールペンタ (メタ）アタリレートなどの多官能アクリルモ ノマーを用いることが好まし 、。  [0070] Among the above, as the polyfunctional monomer, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or dipentaerythritol penta (meth) ) It is preferable to use a polyfunctional acrylic monomer such as acrylate.
[0071] 多官能モノマーを用いる場合、多官能モノマーの微粒子含有組成物中における添 加量に対して特に限定はなぐ該組成物の全固形分に対して、 5〜50質量％が一般 的であり、 10〜40質量％が好ましい。該添加量が前記範囲内であると、光感度や画 像を構成する膜の強度も良好であり、膜形成したときの膜の粘着性が過剰になること もない。 [0072] 前記多官能モノマーは、光や熱を用いて重合可能な化合物である。微粒子含有組 成物を光硬化性もしくは熱硬化性にする場合、重合開始剤を前記多官能モノマーと 併用することが好ましぐ微粒子含有組成物が光重合開始剤を含み、光硬化性であ ることがより好ましい。さらに、微粒子含有糸且成物が前記多官能モノマー以外にオリゴ マーを含んでいてもよい。 [0071] When a polyfunctional monomer is used, it is generally 5 to 50% by mass with respect to the total solid content of the composition, with no particular limitation on the amount of polyfunctional monomer added in the fine particle-containing composition. Yes, 10 to 40% by mass is preferable. When the addition amount is within the above range, the photosensitivity and the strength of the film constituting the image are good, and the adhesiveness of the film when the film is formed does not become excessive. [0072] The polyfunctional monomer is a compound that can be polymerized using light or heat. When the fine particle-containing composition is made photocurable or thermosetting, the fine particle-containing composition in which it is preferable to use a polymerization initiator in combination with the polyfunctional monomer contains a photopolymerization initiator and is photocurable. More preferably. Furthermore, the fine particle-containing yarn composition may contain an oligomer in addition to the polyfunctional monomer.
[0073] 前記光重合開始剤としては、特開 2004— 347831号公報の段落番号 [0024]に 記載の化合物が挙げられる。更に、特開平 11— 133600号公報に記載の「重合開 始剤 C」も好適なものとして挙げることができる。  [0073] Examples of the photopolymerization initiator include compounds described in paragraph No. [0024] of JP-A No. 2004-347831. Furthermore, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.
[0074] 上記のうち、光感度が高ぐ黄ばみなどの着色が少なぐ良好な表示特性を得ること ができる例として、トリノ、ロメチルォキサジァゾール系の光重合開始剤とトリノ、ロメチル —s トリァジン系の光重合開始剤との組み合わせが挙げられ、中でも、 2—トリクロ口 メチルー 5—（p—スチリルメチル） 1, 3, 4 ォキサジァゾールと 2, 4 ビス（トリクロ ロメチル）— 6— [4'— (N, N ビスエトキシカルボ-ルメチルァミノ）—3'—プロモフ ェ -ル] s トリァジンとの組み合わせが好まし 、。  [0074] Among the above, as an example of obtaining good display characteristics with high photosensitivity and less coloring such as yellowing, a photopolymerization initiator based on trino and romethyloxadiazole and trino and romethyl —S Combinations with triazine-based photopolymerization initiators, including 2-trichloromethyl-5- (p-styrylmethyl) 1, 3, 4 oxaziazole and 2,4 bis (trichloromethyl) — 6— [ 4 '— (N, N bisethoxycarboromethylamino) —3′—promophor] s A combination with triazine is preferred.
[0075] 上記のように光重合開始剤を組み合わせる場合の比率（トリノ、ロメチルォキサジァ ゾール系 Zトリハロメチル— s トリァジン系の質量比率）は、 95Z5〜20Z80である の力 S好ましく、 90/10〜30/70力 Sより好ましく、最ち好ましく ίま 80/20〜40/60で ある。  [0075] The ratio when the photopolymerization initiator is combined as described above (mass ratio of trino, romethyloxadiazole-based Z-trihalomethyl-s-triazine-based) is 95Z5 to 20Z80. 90/10 to 30/70 force S is more preferable, and most preferable is ί 80/20 to 40/60.
[0076] また、上記の光重合開始剤の詳細については、特開平 1— 152449号公報、特開 平 1— 254918号公報、特開平 2— 153353号公報の記載を参照することができる。 上記以外に好適な光重合開始剤の例として、ベンゾフエノン系の光重合開始剤を 挙げることができる。  [0076] For details of the photopolymerization initiator, the descriptions in JP-A-1-152449, JP-A-1-254918, and JP-A-2-153353 can be referred to. In addition to the above, examples of suitable photopolymerization initiators include benzophenone photopolymerization initiators.
[0077] 光重合開始剤と共に、クマリン系化合物を併用することで光感度が高ぐ黄ばみな どの着色が少なぐ良好な表示特性を得ることが可能である。  [0077] By using a coumarin compound in combination with a photopolymerization initiator, it is possible to obtain good display characteristics with little coloration such as yellow with high photosensitivity.
[0078] 前記クマリン系化合物としては、 7— [2— [4一（3 ヒドロキシメチルビペリジノ） 6[0078] Examples of the coumarin compounds include 7- [2- [4 (3-hydroxymethylbiperidino) 6
—ジェチルァミノ]トリアジ-ルァミノ]— 3—フエ-ルクマリンが好ましい。 —Jetylamino] triazylamino] —3-phenolicumarin is preferred.
[0079] クマリン系化合物を用いる場合、光重合開始剤とクマリン系化合物との比率 (光重 合開始剤 Ζクマリン系化合物の質量比率）は、 20Ζ80〜80Ζ20が好ましぐ 30/7 0〜70Z30力 り好ましく、最も好ましくは 40Ζ60〜60Ζ40である。 [0079] When a coumarin compound is used, the ratio of the photopolymerization initiator to the coumarin compound (the photopolymerization initiator and the mass ratio of the coumarin compound) is preferably 20-80 to 80-20. 0 to 70 Z30 force is more preferable, and 40 to 60 to 40 is most preferable.
[0080] なお、本発明に使用可能な光重合開始剤は、上記した重合開始剤に制限されるも のではなぐ他の公知のものの中力 適宜選択することできる。 [0080] The photopolymerization initiator that can be used in the present invention is not limited to the above-described polymerization initiators, and can be appropriately selected from other known ones.
[0081] 微粒子含有組成物は光重合開始剤を 1種単独で含んでも良いし、 2種類以上を含 んでもよいが、 2種類以上を含むことが好ましい。 [0081] The fine particle-containing composition may contain one kind of photopolymerization initiator alone or two or more kinds, but preferably contains two or more kinds.
本発明の微粒子含有組成物が光重合開始剤を含有する場合、光重合開始剤の微 粒子含有組成物中の全固形分における含有率は、 0. 1〜20質量％が一般的であり When the fine particle-containing composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator in the total solid content in the fine particle-containing composition is generally 0.1 to 20% by mass.
、 0. 3〜15質量％が好ましい。該含有率が前記範囲内であると、光感度や画像の膜 の強度低下を効果的に防止することができる。 0.3 to 15% by mass is preferable. When the content is within the above range, it is possible to effectively prevent photosensitivity and strength reduction of the image film.
[0082] 本発明の微粒子含有組成物は熱もしくは光で硬化する化合物を感光性榭脂組成 物の形で含むことが好まし 、。 [0082] The fine particle-containing composition of the present invention preferably contains a compound curable by heat or light in the form of a photosensitive resin composition.
前記感光性榭脂組成物としては、既述の多官能モノマー及び Ζ又はオリゴマーと 光重合開始剤とを含む感光性榭脂組成物、並びに特開平 10— 160926号公報の 段落番号 [0016]〜 [0022]及び [0029]に記載のものが好適である。更に、他の光 重合性のモノマーを多官能モノマーと併用してもよい。  Examples of the photosensitive resin composition include a photosensitive resin composition containing the polyfunctional monomer and resin or oligomer described above and a photopolymerization initiator, and paragraph numbers [0016] to JP-A-10-160926. [0022] and [0029] are preferred. Furthermore, other photopolymerizable monomers may be used in combination with the polyfunctional monomer.
[0083] また、銀コロイドのように金属微粒子又は金属化合物微粒子を水分散物として用い る場合には、前記感光性榭脂組成物として水系のものが有用である。水系の感光性 榭脂組成物としては、特開平 8— 271727号公報の段落番号 [0015]〜[0023]に 記載のもの、並びに市販のものとして、例えば東洋合成工業 (株)製の「SPP— Μ20[0083] When metal fine particles or metal compound fine particles are used as an aqueous dispersion, such as silver colloid, an aqueous one is useful as the photosensitive resin composition. Examples of the aqueous photosensitive resin composition include those described in paragraphs [0015] to [0023] of JP-A-8-271727, and commercially available products such as “SPP” manufactured by Toyo Gosei Co., Ltd. — Μ20
」、「SPP—H—13」等が挙げられる。 And “SPP-H-13”.
[0084] 他の成分 [0084] Other ingredients
本発明の微粒子含有組成物は、上記以外に必要に応じて、少なくとも 1種の下記 の公知の顔料、少なくとも 1種の界面活性剤、チォエーテル基を有する高分子化合 物と併用できる少なくとも 1種のポリマー、少なくとも 1種の分散剤、及び Z又は少なく とも 1種の分散安定剤等の他の成分を含むことができる。  In addition to the above, the fine particle-containing composition of the present invention can be used in combination with at least one kind of the following known pigment, at least one surfactant, and a polymer compound having a thioether group, if necessary. Other components such as a polymer, at least one dispersant, and Z or at least one dispersion stabilizer can be included.
[0085] 〜顔料〜 [0085] ~ Pigment ~
顔料としては、カーボンブラックなどの黒色顔料を用いることができる。  As the pigment, a black pigment such as carbon black can be used.
顔料の添加率は、既述の金属微粒子及び Z又は金属化合物微粒子に対して、 50 質量％以下が好ましぐ 30質量％以下がより好ましい。顔料の添加率が 50質量％を 越えると、所望の光学濃度を得るために必要な遮光膜の厚みが増大し、遮光膜上に 形成される赤、青、及び緑の画素の品位が低下することがある。 The addition rate of the pigment is 50% of the metal fine particles and Z or metal compound fine particles described above. Less than 30% by mass is more preferable. When the pigment addition rate exceeds 50% by mass, the thickness of the light shielding film necessary to obtain a desired optical density increases, and the quality of red, blue, and green pixels formed on the light shielding film decreases. Sometimes.
[0086] また、色味調整のため、本発明の微粒子含有組成物は黒色以外に青色その他の 顔料を含んでもよ!ヽ。本発明の微粒子含有組成物が黒色以外の顔料を含む場合の 該顔料の含有率は、既述の金属微粒子及び Z又は金属化合物微粒子に対して、 4 0質量％以下が好ましぐ 20質量％以下がより好ましい。該含有率が 40質量％を越 えると、形成した膜の色味が悪ィ匕していることがある。  [0086] Further, in order to adjust the color tone, the fine particle-containing composition of the present invention may contain blue and other pigments in addition to black. When the fine particle-containing composition of the present invention contains a pigment other than black, the content of the pigment is preferably 40% by mass or less, preferably 20% by mass with respect to the above-described metal fine particles and Z or metal compound fine particles. The following is more preferable. When the content exceeds 40% by mass, the color of the formed film may be deteriorated.
[0087] 〜界面活性剤〜  [0087] -Surfactant-
本発明の微粒子含有組成物は、塗布性、微粒子の分散安定性の改良などの目的 で、少なくとも 1種の界面活性剤を含むことができる。少なくとも 1種の界面活性剤の 各々としては、ノ-オン系、ァ-オン系、又はカチオン系の界面活性剤を特に制限な く使用可能である。中でも、液の安定性の観点から、界面活性剤はァ-オン性である ことが好ましい。また、フッ素系界面活性剤も好ましい。  The fine particle-containing composition of the present invention can contain at least one surfactant for the purpose of improving coating properties and dispersion stability of fine particles. As each of the at least one surfactant, a non-one, ar-on, or cationic surfactant can be used without particular limitation. Among these, from the viewpoint of the stability of the liquid, the surfactant is preferably ionic. Also preferred are fluorosurfactants.
[0088] 前記界面活性剤の典型的な例として、 C F SO N (C H ) (C H O) H、 C F SO  [0088] As a typical example of the surfactant, C F SO N (C H) (C H O) H, C F SO
8 17 2 2 5 2 4 14 8 17 8 17 2 2 5 2 4 14 8 17
Li、 C F COONH、及び C F SO N (C H ) C H OPO (OH)等が挙げられる。Li, C F COONH, C F SO N (C H) C H OPO (OH) and the like.
3 7 15 4 8 17 2 2 5 2 4 2 3 7 15 4 8 17 2 2 5 2 4 2
市販品として、 F110、 F113、 F120、 F150、 F176PF、 F177、及び F780 (いずれ も大日本インキ化学工業 (株)製、オリゴマータイプフッ素系界面活性剤)などを挙げ ることがでさる。  Examples of commercially available products include F110, F113, F120, F150, F176PF, F177, and F780 (all manufactured by Dainippon Ink and Chemicals, Inc., oligomer type fluorosurfactants).
[0089] 〜チォエーテル基を有する高分子化合物と併用できるポリマー〜  [0089] -Polymer that can be used in combination with polymer compound having thioether group-
本発明の微粒子含有組成物は、アルカリ現像性を有するバインダーとして、あるい は既述の金属微粒子及び Z又は金属化合物微粒子の分散安定性を更に良化する ために、既述の「チォエーテル基を有する高分子化合物」以外のポリマーを含むこと ができる。該ポリマーの種類には特に制限はない。このポリマーに求められる性質、 共重合する成分、酸価、及び分子量は、「チォエーテル基を有する高分子化合物」 のそれらと同じである。  The fine particle-containing composition of the present invention is used as a binder having alkali developability, or in order to further improve the dispersion stability of the metal fine particles and Z or metal compound fine particles described above, Polymers other than “having a polymer compound” can be included. There is no restriction | limiting in particular in the kind of this polymer. The properties required for this polymer, the components to be copolymerized, the acid value, and the molecular weight are the same as those of the “polymer compound having a thioether group”.
[0090] 〜分散安定剤〜 [0090] ~ Dispersion stabilizer ~
本発明の微粒子含有組成物は分散安定剤を含むことができ、分散安定剤としては 、例えば「顔料分散技術」（技術情報協会 (株)、 1999年発行)に記載のものを使用 できる。 The fine particle-containing composition of the present invention can contain a dispersion stabilizer. For example, those described in “Pigment Dispersion Technology” (Technical Information Association, Inc., issued in 1999) can be used.
[0091] 微粒子含有組成物の調製  [0091] Preparation of fine particle-containing composition
本発明の微粒子含有組成物は、金属微粒子及び Z又は金属化合物微粒子、チォ エーテル基を有する高分子化合物、熱もしくは光で硬化する化合物、及び必要に応 じて他の成分を (好ましくは溶剤を加えて)混合し、攪拌することにより調製できる。好 ましくは、予め金属微粒子及び Z又は金属化合物微粒子をチォエーテル基を有す る高分子化合物と共に溶剤に分散して微粒子分散液を調製し、該微粒子分散液に 熱もしくは光で硬化する化合物と他の成分とを添加し、混合することにより調製するこ とがでさる。  The fine particle-containing composition of the present invention comprises metal fine particles and Z or metal compound fine particles, a polymer compound having a polyether group, a compound curable by heat or light, and other components as necessary (preferably a solvent). In addition) it can be prepared by mixing and stirring. Preferably, metal fine particles and Z or metal compound fine particles are preliminarily dispersed in a solvent together with a polymer compound having a thioether group to prepare a fine particle dispersion, and the fine particle dispersion is cured with heat or light. It can be prepared by adding and mixing other ingredients.
[0092] 調製に用いる溶剤の種類には特に制限ないが、特に 9. 0以上の SP値を有すること が好ましい。溶剤が 9. 0以上の SP値を有すると、例えば、金属微粒子及び Z又は金 属化合物微粒子の分散性が良好となり、薄膜でも充分な光学濃度を達成することが できる。  [0092] The type of solvent used for the preparation is not particularly limited, but it is particularly preferable that the SP value is 9.0 or more. When the solvent has an SP value of 9.0 or more, for example, the dispersibility of metal fine particles and Z or metal compound fine particles becomes good, and a sufficient optical density can be achieved even with a thin film.
[0093] SP値は、溶解性パラメーターとも!/、われるもので、凝集エネルギー密度の平方根で 表され、本発明においては、「接着ハンドブック」（日本接着学会編、日刊工業新聞 社発行、 1971年初版発行)の 838頁に記載のものを意味する。  [0093] The SP value is both a solubility parameter and is expressed by the square root of the cohesive energy density. In the present invention, the “adhesion handbook” (edited by the Adhesion Society of Japan, published by Nikkan Kogyo Shimbun, 1971) Means the one described on page 838 of the first edition).
[0094] 溶剤の SP値に関しては、例えば、 n—へキサンの SP値は 7. 3、トルエンの SP値は 8. 9、酢酸ェチルの SP値は 9. 1、メチルェチルケトンの SP値は 9. 3、アセトンの SP 値 ίま 10. 0、ェチノレアノレコーノレの SP値 ίま 12. 7、メチノレアノレコーノレの SP値 ίま 14. 5、 水の SP値は 23. 4である。ここで、 SP値の単位は「（cal/cm3) 1/2」である。 [0094] Regarding the SP value of the solvent, for example, the SP value of n-hexane is 7.3, the SP value of toluene is 8.9, the SP value of ethyl acetate is 9.1, and the SP value of methyl ethyl ketone 9.3, SP value of acetone ί 10.0, SP value of ethinorea nore cornore ί ma 12.7, SP value of methino leno eno konole ί ma 15.5, SP value of water 23 4 is. Here, the unit of SP value is “(cal / cm 3 ) 1/2 ”.
[0095] 本発明の微粒子含有組成物は、金属微粒子及び/又は金属化合物微粒子を少 なくとも「チォエーテル基を有する高分子化合物」（及び好ましくは溶剤）と共に混合 した混合液を、超音波分散機、ペイントシェーカー、ボールミル、アイガーミルなどの 公知の分散機を用いて攪拌することにより調製することができる。中でも、分散機は 超音波分散機が好ましい。  [0095] The fine particle-containing composition of the present invention comprises an ultrasonic disperser prepared by mixing a mixed liquid obtained by mixing metal fine particles and / or metal compound fine particles together with at least a “polymer compound having a thioether group” (and preferably a solvent). It can be prepared by stirring using a known disperser such as a paint shaker, ball mill, Eiger mill or the like. Among these, an ultrasonic disperser is preferable as the disperser.
[0096] 本発明の微粒子含有組成物は、分散した金属微粒子及び Z又は金属化合物微粒 子を含む用途、例えば、（好ましくは黒色の)着色膜形成用インク、遮光膜、カラーフ ィルタの黒色画像 (ブラックマトリクスを含む。）、に好適に用いることができる。 [0096] The fine particle-containing composition of the present invention is used for applications containing dispersed metal fine particles and Z or metal compound fine particles, for example, (preferably black) colored film forming ink, light-shielding film, color filter, and the like. It can be suitably used for a black image of a filter (including a black matrix).
[0097] <表示装置用着色膜形成用インク >  <Colored film forming ink for display device>
本発明の表示装置用着色膜形成用インクは、既述の本発明の微粒子含有組成物 を用いて調製される。本発明の微粒子含有組成物を用いているので、インクの長期 保存時の安定性が高ぐ色相が良好 (特に黒色相が良好)で高い光学濃度を有する  The ink for forming a colored film for a display device of the present invention is prepared using the fine particle-containing composition of the present invention described above. Since the fine particle-containing composition of the present invention is used, the ink has high stability when stored for a long period of time and has a good hue (especially a black hue) and a high optical density.
[0098] 本発明の表示装置用着色膜形成用インクは、金属微粒子及び Z又は金属化合物 微粒子、少なくとも 1つのチォエーテル基を有する高分子化合物、及び熱もしくは光 で硬化する化合物を含み、必要に応じて着色剤 (好ましくは顔料)など他の成分を含 み、記録媒体へのインクの付与後に加熱又は紫外線などのエネルギー線の付与に より硬ィ匕させ得るちのである。 [0098] The colored film forming ink for a display device of the present invention includes metal fine particles and Z or metal compound fine particles, a polymer compound having at least one thioether group, and a compound that is cured by heat or light, if necessary. In addition, it contains other components such as a colorant (preferably a pigment) and can be hardened by heating or application of energy rays such as ultraviolet rays after application of ink to the recording medium.
[0099] なお、本発明の微粒子含有組成物の詳細については、既述の通りであり、本発明 の表示装置用着色膜形成用インクは、前記成分以外に、インクに必要な成分を適宜 含有することが可能である。  [0099] The details of the fine particle-containing composition of the present invention are as described above, and the colored film forming ink for a display device of the present invention appropriately contains components necessary for the ink in addition to the above components. Is possible.
[0100] 本発明の表示装置用着色膜形成用インクは、例えば、液晶表示装置、プラズマデ イスプレイ表示装置、 EL表示装置、及び CRT表示装置の表示装置の用途に好適で あり、表示装置内に設けられる黒色の外周縁や画素周囲の格子状もしくはストライプ 状の黒色の縁部 (V、わゆるブラックマトリックス）、薄膜トランジスター (TFT)遮光のた めのドット状もしくは線状の黒色パターンなどの形成に好適である。  [0100] The colored film forming ink for a display device of the present invention is suitable for use in a display device such as a liquid crystal display device, a plasma display display device, an EL display device, and a CRT display device, and is provided in the display device. For forming the black outer periphery, the grid-like or stripe-like black edges around the pixels (V, a so-called black matrix), and dot-like or linear black patterns for light shielding of thin film transistors (TFT) Is preferred.
[0101] <表示装置用遮光膜 >  [0101] <Light shielding film for display device>
本発明の表示装置用遮光膜は、既述の本発明の微粒子含有組成物、あるいは既 述の本発明の表示装置用着色膜形成用インクを用いて形成される。この遮光膜は本 発明の微粒子含有組成物を用いて形成されるので、製造中に高温に曝されても高 温環境での榭脂成分、及び微粒子の変質に伴なう色味変化が少なぐ色相が良好（ 特に黒色相が良好)で高い光学濃度を有する。  The light shielding film for a display device of the present invention is formed using the fine particle-containing composition of the present invention described above or the color film forming ink for a display device of the present invention described above. Since this light-shielding film is formed using the fine particle-containing composition of the present invention, even if it is exposed to a high temperature during production, there is little change in color due to alteration of the fat component and fine particles in a high temperature environment. Excellent hue (especially black hue) and high optical density.
[0102] 本発明の表示装置用遮光膜は、例えば、既述の本発明の熱硬化性もしくは光硬化 性の微粒子含有組成物を所望の基板に塗布し、得られた塗膜を乾燥させる方法 (塗 布法)、又は仮支持体上に既述の本発明の熱硬化性もしくは光硬化性の微粒子含 有組成物を塗布し、得られた塗膜を乾燥させて設けられた熱硬化性もしくは光硬化 性の遮光性層を有する転写材料を準備し、前記遮光性層を所望の基板に転写する 方法 (転写法)を利用して作製することができる。 [0102] The light-shielding film for a display device of the present invention is, for example, a method in which the thermosetting or photocurable fine particle-containing composition of the present invention described above is applied to a desired substrate and the resulting coating film is dried. (Coating method) or the above-mentioned thermosetting or photocurable fine particles of the present invention are contained on a temporary support. A method for preparing a transfer material having a thermosetting or photocurable light-shielding layer provided by applying a composition and drying the obtained coating film, and transferring the light-shielding layer to a desired substrate (Transfer method) can be used.
[0103] 本発明の表示装置用遮光膜が所望のパターンにパターン化されてなるものである 場合、該表示装置用遮光膜は上記の塗布法又は転写法により設けられた熱硬化性 もしくは光硬化性の遮光性層をパターニングして形成される。  [0103] When the light-shielding film for display device of the present invention is formed into a desired pattern, the light-shielding film for display device is a thermosetting or photocuring provided by the above coating method or transfer method. It is formed by patterning a light-shielding layer.
ノターニング方法としては、露光'現像による方法、レーザーの熱により遮光性層の 不要部分を除去する方法 (アブレーシヨン法)、基板上に設けられた遮光性層の上に 感光性レジスト膜を塗布し、これを露光 '現像してパターユングした後、感光性レジス ト膜を除去する方法が挙げられる。本発明では、これらの方法のいずれも使用できる 力 下記方法（1)〜（3)は工程の簡便さやパターユングの解像度などの点で好まし い。  The no-turning method includes a method of exposure and development, a method of removing unnecessary portions of the light-shielding layer by laser heat (ablation method), and a photosensitive resist film is applied on the light-shielding layer provided on the substrate. And a method of removing the photosensitive resist film after exposure and development and patterning. In the present invention, any of these methods can be used. The following methods (1) to (3) are preferable in terms of the simplicity of the process and the resolution of patterning.
[0104] 方法（1)基板上に非感光性の微粒子含有組成物を塗布し、得られた塗膜を乾燥し て遮光性層を形成し、この遮光性層上にフォトレジスト膜を塗布し、該フォトレジスト膜 を露光及び現像によりパターユングし、フォトレジスト膜のない部分の遮光性層をエツ チングにより除去し、次いでフォトレジスト膜を除去する方法  [0104] Method (1) A non-photosensitive fine particle-containing composition is applied onto a substrate, the resulting coating film is dried to form a light-shielding layer, and a photoresist film is applied onto the light-shielding layer. A method of patterning the photoresist film by exposure and development, removing the light-shielding layer without the photoresist film by etching, and then removing the photoresist film
方法 (2)基板上に感光性の微粒子含有組成物を塗布し、得られた塗膜を乾燥して 感光性の遮光性層を形成し、該感光性の遮光性層を露光、現像 (未硬化部分を除 去）してパターニングする方法  Method (2) A photosensitive fine particle-containing composition is applied onto a substrate, and the resulting coating film is dried to form a photosensitive light-shielding layer. The photosensitive light-shielding layer is exposed and developed (undeveloped). Patterning by removing the hardened part)
方法 (3)仮支持体の上に感光性の微粒子含有組成物を塗布し、得られた塗膜を乾 燥して感光性の遮光性層を形成して積層体 (感光性転写材料)を得、この積層体を 所望の基板上にラミネートし、仮支持体を除去して感光性の遮光性層を基板に転写 し、基板上に転写形成された感光性の遮光性層を露光、現像 (未硬化部分を除去） してパターニングする方法  Method (3) A photosensitive fine particle-containing composition is applied onto a temporary support, and the resulting coating film is dried to form a photosensitive light-shielding layer to form a laminate (photosensitive transfer material). The laminate is laminated on a desired substrate, the temporary support is removed, the photosensitive light-shielding layer is transferred to the substrate, and the photosensitive light-shielding layer transferred and formed on the substrate is exposed and developed. A method of patterning by removing uncured parts
[0105] 上記の方法（1)〜（3)はいずれも、蒸着法やスパッタリング法を用いた従来の方法 に比べて簡単な工程で遮光性層を形成することができ、該遮光性層から所望のバタ ーンを形成することができる。  [0105] In any of the above methods (1) to (3), a light-shielding layer can be formed by a simple process as compared with conventional methods using vapor deposition or sputtering. The desired pattern can be formed.
[0106] 〜微粒子含有組成物の付与 (塗布等）工程〜 微粒子含有組成物を基板又は仮支持体に付与する方法としては、塗布方法が好 適であり、該塗布方法には特に制限はなぐ例えば、該塗布方法として特開平 5— 2 24011号公報に記載のスピンコート法、又は特開平 9 323472号公報に記載のダ ィコート法などを用いることができる。 [0106] ~ Application of fine particle-containing composition (coating etc.) ~ As a method for applying the fine particle-containing composition to a substrate or a temporary support, a coating method is suitable, and the coating method is not particularly limited. For example, the coating method is described in JP-A-5-224011. The spin coating method described in JP-A-9323472 or the like can be used.
[0107] 仮支持体に微粒子含有組成物を付与する場合、後述するように、得られた転写材 料は仮支持体と微粒子含有組成物からなる遮光性層の他に必要に応じて熱可塑性 榭脂層及び Z又は中間層を有することができる。  [0107] When the fine particle-containing composition is applied to the temporary support, as will be described later, the obtained transfer material is thermoplastic as necessary in addition to the light-shielding layer comprising the temporary support and the fine particle-containing composition. It can have a resin layer and a Z or intermediate layer.
[0108] 〜露光'現像工程〜  [0108] -Exposure 'development process-
露光では、公知の光源を用いて所望のパターンを形成することができる。光源は、 フォトレジスト膜又は感光性の遮光性層の感光性に応じて選択すればよ!、。超高圧 水銀灯、キセノン灯、カーボンアーク灯、アルゴンレーザーのような公知の光源を使 用することができる。また、例えば、特開平 6— 59119号公報に記載の、 400nm以 上の波長の光透過率が 2%以下である光学フィルターを光源と併用してもよい。  In exposure, a desired pattern can be formed using a known light source. The light source should be selected according to the photosensitivity of the photoresist film or photosensitive light-shielding layer! Known light sources such as ultra-high pressure mercury lamp, xenon lamp, carbon arc lamp, and argon laser can be used. In addition, for example, an optical filter described in JP-A-6-59119 and having a light transmittance of 2% or less at a wavelength of 400 nm or more may be used in combination with the light source.
[0109] 露光は、被露光面の全面を 1回で露光する一括露光でもよいし、被露光面を分割 して得られた領域を順次露光する分割露光としてもよい。さらに、レーザーを用いて 被露光面をスキャンしながら行なう露光を使用してもよい。  [0109] The exposure may be batch exposure in which the entire surface to be exposed is exposed at once, or may be divided exposure in which regions obtained by dividing the surface to be exposed are sequentially exposed. Furthermore, exposure performed while scanning the surface to be exposed using a laser may be used.
[0110] 露光後の現像は、現像液を用いて行なうことができる。現像液としては、アルカリ性 物質の希薄水溶液が好適であり、該水溶液は水と混和性の有機溶剤を少量含むこと ちでさる。  [0110] Development after exposure can be performed using a developer. As the developer, a dilute aqueous solution of an alkaline substance is preferable, and the aqueous solution contains a small amount of an organic solvent miscible with water.
[0111] 前記アルカリ性物質としては、アルカリ金属水酸化物類 (例、水酸化ナトリウム、又 は水酸ィ匕カリウム）、アルカリ金属炭酸塩類 (例、炭酸ナトリウム、又は炭酸カリウム）、 アルカリ金属重炭酸塩類 (例、炭酸水素ナトリウム、又は炭酸水素カリウム）、アルカリ 金属ケィ酸塩類 (例、ケィ酸ナトリウム、又はケィ酸カリウム）、アルカリ金属メタケイ酸 塩類 (例、メタケイ酸ナトリウム、又はメタケイ酸カリウム）、トリエタノールァミン、ジエタ ノールァミン、モノエタノールァミン、モルホリン、テトラアルキルアンモン-ゥムヒドロキ シド類 (例えばテトラメチルアンモ-ゥムヒドロキシド）、又は燐酸三ナトリウムが適当で ある。水溶液中のアルカリ性物質の濃度は、 0. 01〜30質量％が好ましぐ水溶液の pHは 8〜14が好ましい。感光性の遮光性層の酸ィ匕性のような性質に応じて例えば、 現像液の pHを変化させて、膜状脱離による現像が行えるようにすることができる。 [0111] Examples of the alkaline substance include alkali metal hydroxides (eg, sodium hydroxide or potassium hydroxide), alkali metal carbonates (eg, sodium carbonate or potassium carbonate), alkali metal bicarbonate. Salts (eg, sodium bicarbonate or potassium bicarbonate), alkali metal silicates (eg, sodium silicate or potassium silicate), alkali metal metasilicates (eg, sodium metasilicate or potassium metasilicate), Triethanolamine, dietanolamine, monoethanolamine, morpholine, tetraalkylammonum hydroxides (eg tetramethylammonium hydroxide) or trisodium phosphate are suitable. The concentration of the alkaline substance in the aqueous solution is preferably 0.01 to 30% by mass, and the pH of the aqueous solution is preferably 8 to 14. Depending on properties such as acidity of the light-sensitive light-shielding layer, for example, It is possible to change the pH of the developer so that development by film-like detachment can be performed.
[0112] 前記水と混和性の有機溶剤としては、メタノール、エタノール、 2 プロパノール、 1 プロパノール、ブタノール、ジアセトンアルコール、エチレングリコーノレモノメチノレエ ーテノレ、エチレングリコーノレモノエチノレエーテノレ、エチレングリコーノレモノー n—ブチ ルエーテル、ベンジルアルコール、アセトン、メチルェチルケトン、シクロへキサノン、 ε 一力プロラタトン、 γ ブチロラタトン、ジメチルホルムアミド、ジメチルァセトアミド、 へキサメチルホスホルアミド、乳酸ェチル、乳酸メチル、 ε一力プロラタタム、及び Ν —メチルピロリドンが適当である。水溶液中の水と混和性の有機溶剤の濃度は、 0. 1 〜30質量％が一般的である。  [0112] Examples of the water-miscible organic solvent include methanol, ethanol, 2 propanol, 1 propanol, butanol, diacetone alcohol, ethylene glycol monomethino ethenore, ethylene glycol mono eno eno enoate, ethylene glycol. Noremono-n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-strength prolatatone, γ butyrolatathone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, lactic acid ethyl, methyl lactate, ε-strength prolatatam and Ν-methylpyrrolidone are suitable. The concentration of the water-miscible organic solvent in the aqueous solution is generally from 0.1 to 30% by mass.
[0113] 現像液はさらに公知の界面活性剤を含むことができる。現像液が界面活性剤を含 む場合、現像液中の界面活性剤の濃度は 0. 01〜10質量％が好ましい。  [0113] The developer may further contain a known surfactant. When the developer contains a surfactant, the concentration of the surfactant in the developer is preferably 0.01 to 10% by mass.
[0114] 現像液は、浴液として用いてもよいし、あるいは噴射液として用いてもよい。感光性 の遮光性層の未硬化部分を固形状 (好ましくは膜状)で除去することもでき、この場 合には、現像液中で遮光性層を回転ブラシで擦るか、湿潤スポンジで擦るカゝ、あるい は現像液を噴射する際の噴射圧を利用することが好ましい。現像液の温度は、通常 室温付近力 40°Cの範囲が好まし!/、。  [0114] The developer may be used as a bath solution or a jetting solution. The uncured portion of the photosensitive light-shielding layer can also be removed in solid form (preferably in the form of a film). In this case, the light-shielding layer is rubbed with a rotating brush or a wet sponge in the developer. It is preferable to use an injection pressure at the time of jetting the developer or the developer. The developer temperature is usually in the range of around 40 ° C force around room temperature!
また、現像後に遮光性層を水洗してもよい。  Further, the light-shielding layer may be washed with water after development.
[0115] 〜加熱その他工程〜  [0115]-Heating and other processes-
現像後には、遮光性層を加熱することが好ましい。加熱により、露光により硬化した 感光性の遮光性層の硬化の程度を高め、耐溶剤性や耐アルカリ性をより高めること ができる。加熱方法は、現像後の基板を電気炉、又は乾燥器の中に入れて加熱する 方法、又は赤外線ランプで現像後の基板を加熱する方法などを適用できる。  After the development, it is preferable to heat the light-shielding layer. By heating, the degree of curing of the photosensitive light-shielding layer cured by exposure can be increased, and the solvent resistance and alkali resistance can be further increased. As a heating method, a method of heating the substrate after development in an electric furnace or a dryer, or a method of heating the substrate after development with an infrared lamp can be applied.
[0116] 本発明の表示装置用遮光膜は、膜強度を高める観点から、現像後に加熱された膜 であるのが好ましい。加熱条件は、遮光膜の組成、及び厚みによる。力 180〜300 °Cで 5〜60分間遮光膜を加熱することが好ましぐ 200〜270°Cで 10〜50分間加熱 することがより好ましぐ 200〜250°Cで 10〜50分間加熱することがさらに好ましい。 また、現像後遮光膜を加熱する前に、遮光膜の硬化促進のために更に遮光膜を露 光してもよぐこの場合の露光も既述の露光と同様の方法により行なうことができる。 [0117] 感光性の遮光性層の形成した後、この遮光性層をパターン状に露光する前に遮光 性層の上に更に保護層を設けてもよい。 [0116] The light-shielding film for a display device of the present invention is preferably a film heated after development from the viewpoint of increasing the film strength. The heating conditions depend on the composition and thickness of the light shielding film. It is preferable to heat the light shielding film at 180-300 ° C for 5-60 minutes. It is more preferable to heat at 200-270 ° C for 10-50 minutes. Heat at 200-250 ° C for 10-50 minutes. More preferably. Further, in order to accelerate the curing of the light shielding film, the light shielding film may be further exposed before heating the light shielding film after development. In this case, the exposure can be performed by the same method as the exposure described above. [0117] After the formation of the photosensitive light-shielding layer, a protective layer may be further provided on the light-shielding layer before the light-shielding layer is exposed in a pattern.
保護層は、パターン露光時に酸素を遮断して感光性の遮光性層の露光感度を高 めるための酸素遮断層として機能するものであり、酸素遮断性の榭脂、例えばポリビ -ルアルコールを主成分に含む層であることが好ましい。なお、この層は、遮光膜（ 遮光画像)形成後は不要であるので、現像により除去される。  The protective layer functions as an oxygen-blocking layer for blocking oxygen during pattern exposure to increase the exposure sensitivity of the photosensitive light-blocking layer. An oxygen-blocking resin such as polyvinyl alcohol is used as the protective layer. A layer contained in the main component is preferred. This layer is unnecessary after the formation of the light-shielding film (light-shielded image), and is removed by development.
[0118] 本発明の表示装置用遮光膜の厚みは、 0. 05-2. 0 μ mが好ましぐ 0. 1〜1. 5 mがより好ましい。該厚みが前記範囲内であると、所望の光学濃度が確保され表 示コントラストが良好であると共に、基板表面の凹凸 (遮光膜の設けられた部分と設け られていない部分の格差）が大きくなりすぎることによる、後工程で RGBの画素を遮 光膜の上に形成する際の不都合を来すこともない。 [0118] The thickness of the light-shielding film for a display device of the present invention is preferably from 0.05 to 2.0 μm, more preferably from 0.1 to 1.5 m. If the thickness is within the above range, the desired optical density is secured and the display contrast is good, and the unevenness of the substrate surface (the difference between the portion where the light shielding film is provided and the portion where it is not provided) increases. This does not cause inconvenience when forming RGB pixels on the light shielding film in a later process.
[0119] 本発明の表示装置用遮光膜の透過濃度 (光学濃度）は、 3. 5以上が好ましぐ 4. 0 以上がより好ましぐさらに好ましくは 4. 5以上である。光学濃度が前記範囲内である と、コントラストが高く良好な表示品質を確保することができる。 [0119] The transmission density (optical density) of the light-shielding film for a display device of the present invention is preferably 3.5 or more, more preferably 4.0 or more, and still more preferably 4.5 or more. When the optical density is within the above range, high contrast and high display quality can be ensured.
[0120] 一基板 [0120] One board
前記基板としては、表示装置に一般に用いられるガラス基板が好ましい。 ガラス基板としては、例えば、ソーダガラス、低アルカリガラス、無アルカリガラス等の 公知のガラスで作られる基板が好適である。ガラス基板については、例えば、「液晶 ディスプレイ工学入門」（鈴木ハナエ著、日刊工業新聞社発行 (1998年)）に記載が ある。また、基板として、シリコンウェハやポリオレフイン系などの透明プラスチック基 板も用いることができる。さら〖こ、 TFT素子が配された TFT素子基板を基板として用 いることちでさる。  As the substrate, a glass substrate generally used in a display device is preferable. As the glass substrate, for example, a substrate made of a known glass such as soda glass, low alkali glass or non-alkali glass is suitable. The glass substrate is described, for example, in “Introduction to Liquid Crystal Display Engineering” (Hanae Suzuki, published by Nikkan Kogyo Shimbun, 1998). In addition, a transparent plastic substrate such as a silicon wafer or polyolefin can be used as the substrate. Sarako, the TFT element substrate on which TFT elements are arranged is used as the substrate.
[0121] 前記基板の厚みは、 0. 5〜3mmの範囲が好ましぐ 0. 6〜2mmの範囲がより好ま しい。  [0121] The thickness of the substrate is preferably in the range of 0.5 to 3 mm, and more preferably in the range of 0.6 to 2 mm.
[0122] 本発明の表示装置用遮光膜は、表示画像のコントラスト、視認性の観点から、理想 的な黒色に近いことが好ましい。理想的な黒色に対する近さの程度は、遮光膜の色 度を xyz表色系の (X, y)値で表すとき、遮光膜の色度と理想的な黒色の目標色度と の色差として表すことができる。すなわち、色差の値が小さいほど遮光膜の色は理想 的な黒色に近づき、色差の値が大きいほど遮光膜の色は黒色力も外れることになる。 具体的には、理想的な黒色の目標色度 (X, y)値を (0. 33, 0. 33)としたときの該目 標色度と遮光膜の色度との差は、 XY表色系の Δ Ε値で表され、この値に基づき理想 的な黒色に対する近さの程度を評価することができる。 [0122] The light-shielding film for a display device of the present invention is preferably close to an ideal black color from the viewpoint of contrast and visibility of a display image. The degree of closeness to the ideal black is the color difference between the chromaticity of the light-shielding film and the ideal black target chromaticity when the chromaticity of the light-shielding film is expressed by the (X, y) value of the xyz color system. Can be represented. In other words, the smaller the color difference value, the more ideal the color of the light shielding film. The closer the color is to black, and the larger the color difference value, the more the black color of the light shielding film is removed. Specifically, when the ideal black target chromaticity (X, y) value is (0.33, 0.33), the difference between the target chromaticity and the chromaticity of the light shielding film is XY It is represented by the Δ Δ value of the color system, and based on this value, the degree of proximity to the ideal black can be evaluated.
[0123] <遮光材料 >  [0123] <Shading material>
本発明の遮光材料は、表示装置用遮光膜の形成に用いられる遮光材料であり、支 持体上に少なくとも一層の微粒子含有層を有してなり、必要に応じて更に、熱可塑性 榭脂層、中間層、及び最表層としての保護フィルムを有することができる。  The light-shielding material of the present invention is a light-shielding material used for forming a light-shielding film for a display device, and has at least one fine particle-containing layer on a support, and if necessary, a thermoplastic resin layer. , An intermediate layer, and a protective film as the outermost layer.
[0124] 本発明に係る微粒子含有層は、アスペクト比が 2〜： LOOの金属微粒子及び Z又は 金属化合物微粒子と、少なくとも 1つのチォエーテル基を有する高分子化合物と、熱 もしくは光で硬化する化合物とを少なくとも含み、熱硬化性もしくは光硬化性である。 また、必要に応じて更に、着色剤 (より好ましくは黒色の着色剤)など他の成分を含む ことができる。  [0124] The fine particle-containing layer according to the present invention has an aspect ratio of 2 to: LOO metal fine particles and Z or metal compound fine particles, a polymer compound having at least one thioether group, and a compound that is cured by heat or light. And is thermosetting or photocurable. Further, it may further contain other components such as a colorant (more preferably a black colorant) as necessary.
本発明においては、熱もしくは光で硬化する化合物は、多官能モノマー及び光重 合開始剤を含む光硬化性材料の形であることが好ましい。  In the present invention, the compound curable by heat or light is preferably in the form of a photocurable material containing a polyfunctional monomer and a photopolymerization initiator.
[0125] なお、微粒子含有層の、金属微粒子及び Z又は金属化合物微粒子、チォエーテ ル基を有する高分子化合物、及び熱もしくは光で硬化する化合物、並びに着色剤な ど他の成分の詳細及び好ま 、態様は、既述の本発明の微粒子含有組成物のそれ らと同じである。 [0125] Details and preferences of other components such as metal fine particles and Z or metal compound fine particles, polymer compounds having a thioether group, and compounds cured by heat or light, and colorants in the fine particle-containing layer, The embodiment is the same as those of the fine particle-containing composition of the present invention described above.
[0126] 本発明の遮光材料は、支持体上に被転写体への転写が可能な微粒子含有層が設 けられた転写材料であることが好ま 、。  [0126] The light-shielding material of the present invention is preferably a transfer material in which a fine particle-containing layer that can be transferred to a transfer target is provided on a support.
以下、感光性の遮光性層が設けられた感光性転写材料を例に詳細に説明する。 但し、本発明はこれに限定されるものではない。  Hereinafter, a photosensitive transfer material provided with a photosensitive light-shielding layer will be described in detail as an example. However, the present invention is not limited to this.
[0127] 本発明の遮光材料は、既述の表示装置用遮光膜の形成に好適な方法の一つとし て挙げた方法 (3)に好適な感光性転写材料であることが好ましい。この感光性転写 材料は、仮支持体と、該仮支持体に直接もしくは他の層を介して本発明の感光性を 持つ微粒子含有組成物を塗布し、得られた塗膜を乾燥させて形成された感光性の 遮光性層とを有することができる。 [0128] 感光性の遮光性層の層厚は、 0. 05-2. 0 μ mが好ましぐ 0. 1〜1. 5 μ mがより 好ましい。該厚みが前記範囲内であると、所望の光学濃度が確保され表示コントラス トが良好であると共に、基板表面の凹凸 (遮光膜の設けられた部分と設けられていな い部分の格差）が大きくなりすぎることによる、後工程で RGBの画素をこの上に形成 する際の不都合を来すこともない。 [0127] The light-shielding material of the present invention is preferably a photosensitive transfer material suitable for the method (3) mentioned as one of the methods suitable for forming the light-shielding film for a display device described above. This photosensitive transfer material is formed by applying a temporary support and the photosensitive fine particle-containing composition of the present invention to the temporary support directly or via another layer, and drying the resulting coating film. And a photosensitive light-shielding layer. [0128] The thickness of the light-sensitive light-shielding layer is preferably from 0.05 to 2.0 µm, more preferably from 0.1 to 1.5 µm. When the thickness is within the above range, a desired optical density is ensured and the display contrast is good, and the unevenness of the substrate surface (the difference between the portion where the light shielding film is provided and the portion where the light shielding film is not provided) is large. This will not cause inconvenience when forming RGB pixels on this in a later process.
[0129] 感光性転写材料は、仮支持体と感光性の遮光性層との間に熱可塑性榭脂層を有 することが好ましく、更に熱可塑性榭脂層と感光性の遮光性層との間にアルカリ可溶 性の中間層を有することがより好ましい。また、感光性転写材料は、感光性の遮光性 層の露出面上に保護フィルムを有してもよい。  [0129] The photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the photosensitive light-shielding layer, and further includes a thermoplastic resin layer and the photosensitive light-shielding layer. More preferably, it has an alkali-soluble intermediate layer therebetween. The photosensitive transfer material may have a protective film on the exposed surface of the photosensitive light-shielding layer.
[0130] 仮支持体は、化学的及び熱的に安定であって、可撓性の物質で作られることが好 ましい。具体的には、仮支持体は、テフロン (登録商標）、ポリエチレンテレフタレート 、ポリエチレンナフタレート、ポリアタリレート、ポリカーボネート、ポリエチレン、若しく はポリプロピレンの薄いシート又はこれらの積層物であることが好ましい。また、感光 性転写材料が後述の熱可塑性榭脂層を有する場合には、仮支持体は該層に対する 良好な剥離性を有することが好ましい。仮支持体の厚さは、 5〜300 /ζ πιが適当であ り、 20〜150 111カ^好まし1ヽ。  [0130] The temporary support is preferably chemically and thermally stable and made of a flexible material. Specifically, the temporary support is preferably a thin sheet of Teflon (registered trademark), polyethylene terephthalate, polyethylene naphthalate, polyacrylate, polycarbonate, polyethylene, or polypropylene, or a laminate thereof. Further, when the photosensitive transfer material has a thermoplastic resin layer to be described later, the temporary support preferably has good peelability from the layer. The thickness of the temporary support is suitably 5 to 300 / ζ πι, and preferably 20 to 150 111 layers.
[0131] 本発明の遮光材料が微粒子含有層の転写が可能な転写材料でな!、場合は、前記 仮支持体を既述の基板に代えることができる。この場合には、基板上に所望のバタ ーンを有する遮光画像 (ブラックマトリクスを含む。）を形成することができ、該遮光画 像が形成された基板をそのまま表示装置の基板として用いることができる。  [0131] In the case where the light-shielding material of the present invention is not a transfer material capable of transferring the fine particle-containing layer !, the temporary support can be replaced with the substrate described above. In this case, a light-shielded image (including a black matrix) having a desired pattern can be formed on the substrate, and the substrate on which the light-shielded image is formed can be used as the substrate of the display device. it can.
[0132] 熱可塑性榭脂層  [0132] Thermoplastic resin layer
熱可塑性榭脂層は、熱可塑性を有する榭脂を少なくとも含み、一般には溶剤と熱 可塑性榭脂を含有する調製液を用いて形成することができる。  The thermoplastic resin layer includes at least a resin having thermoplasticity, and can be generally formed using a preparation liquid containing a solvent and a thermoplastic resin.
[0133] 熱可塑性榭脂層の榭脂としては、例えば、アクリル榭脂、ポリスチレン榭脂、ポリエ ステル、ポリウレタン、ゴム系榭脂、酢酸ビニル系榭脂、ポリオレフイン系榭脂、及びこ れらの共重合体を挙げることができる。熱可塑性榭脂層の榭脂はアルカリ可溶である ことが好ましい。  [0133] Examples of the resin of the thermoplastic resin layer include acrylic resin, polystyrene resin, polyester, polyurethane, rubber resin, vinyl acetate resin, polyolefin resin, and these resins. Mention may be made of copolymers. The resin of the thermoplastic resin layer is preferably alkali-soluble.
また、熱可塑性榭脂層の榭脂として、特開 2004— 317897号公報の段落番号 [00 46]〜 [0048]に記載のものを使用できる。 In addition, as a resin for the thermoplastic resin layer, paragraph number [00] of JP 2004-317897 A 46] to [0048] can be used.
[0134] 熱可塑性榭脂層の厚みは、 3 μ m以上が好ま 、。熱可塑性榭脂の厚みが前記範 囲内であると、 1 m以上の被転写体 (下地)面の凹凸に完全に順応することが可能 である。また、熱可塑性榭脂層の厚みの上限は、アルカリ水溶液除去性、製造適性 力も約 100 μ m以下が好ましぐより好ましくは約 50 μ m以下である。  [0134] The thickness of the thermoplastic resin layer is preferably 3 μm or more. When the thickness of the thermoplastic resin is within the above range, it is possible to completely adapt to the unevenness of the surface (substrate) to be transferred of 1 m or more. In addition, the upper limit of the thickness of the thermoplastic resin layer is preferably about 100 μm or less, more preferably about 50 μm or less, in terms of alkaline aqueous removability and production suitability.
[0135] 熱可塑性榭脂層を形成するための熱可塑性榭脂含有の調製液の溶媒は、この層 の榭脂を溶解し得るものであり、それ以外の点では特に制限はなぐ例えば、メチル ェチルケトン、 n—プロパノール、又はイソプロパノールを使用することができる。  [0135] The solvent of the preparation solution containing the thermoplastic resin for forming the thermoplastic resin layer is capable of dissolving the resin of this layer, and is not particularly limited, for example, methyl Ethyl ketone, n-propanol, or isopropanol can be used.
[0136] 中間層  [0136] Middle layer
感光性転写材料が前記熱可塑性榭脂層を有する場合、感光性転写材料は、熱可 塑性榭脂層と感光性の遮光性層との間に、調製液塗布時の両層の混合を防止する 、あるいは酸素遮断の目的で、さらに中間層を有することが好ましい。  When the photosensitive transfer material has the thermoplastic resin layer, the photosensitive transfer material prevents mixing of the two layers when the preparation liquid is applied between the thermoplastic resin layer and the photosensitive light-shielding layer. Alternatively, it is preferable to further have an intermediate layer for the purpose of blocking oxygen.
[0137] 中間層は少なくとも榭脂を含み、一般には熱可塑性榭脂層や感光性の遮光性層 の形成に用いる溶剤と相溶性の小さい水系溶媒と榭脂を含有する調製液を用いて 形成することができる。 [0137] The intermediate layer contains at least a resin, and is generally formed using a preparation solution containing an aqueous solvent and a resin having a low compatibility with the solvent used for forming a thermoplastic resin layer or a photosensitive light-shielding layer. can do.
[0138] 中間層の榭脂はアルカリ可溶であることが好ましぐそのような榭脂の例として、特 開 2004— 317897号公報の段落番号 [0050]に記載のものが挙げられる。  [0138] Examples of such a resin that is preferably soluble in alkali in the intermediate layer include those described in paragraph No. [0050] of JP 2004-317897.
[0139] 中間層の厚みは、 0. 1〜5 μ mの範囲が好ましぐ 0. 5〜3 μ mの範囲がより好まし い。中間層の厚みが前記範囲内であると、中間層は酸素遮断性に優れると共に、現 像時の中間層除去を短時間に行なうことができる。  [0139] The thickness of the intermediate layer is preferably in the range of 0.1 to 5 µm, and more preferably in the range of 0.5 to 3 µm. When the thickness of the intermediate layer is within the above range, the intermediate layer has excellent oxygen barrier properties, and the intermediate layer can be removed in a short time during image formation.
[0140] 感光性転写材料の微粒子含有層は、アスペクト比が 2〜： LOOの金属微粒子及び/ 又は金属化合物微粒子、チォエーテル基を有する高分子化合物及び熱もしくは光 で硬化する化合物（並びに好ましくは溶剤）を含む調製液の、例えば、塗布により形 成されるので、薄膜でかつ高温環境での榭脂成分、微粒子の変質に伴なう色味変化 が少なぐ既述の金属系の微粒子の系中での分散性及び分散した該微粒子の系中 で安定性に優れており、良好な色相と高 、光学濃度を有する。  [0140] The fine particle-containing layer of the photosensitive transfer material is composed of metal fine particles and / or metal compound fine particles having an aspect ratio of 2 to: a polymer compound having a thioether group and a compound cured with heat or light (and preferably a solvent). In the case of a metal-based fine particle system as described above, which is formed by coating, for example, it is a thin film and has little change in color due to the alteration of the fat component and fine particles in a high-temperature environment. It has excellent dispersibility in the medium and stability in the system of the dispersed fine particles, and has a good hue, high optical density.
[0141] 次に、感光性転写材料を用いて微粒子含有層を基板に転写、形成する方法を中 心に述べる。最表層である微粒子含有層の表面と基板表面とを密着させて感光性転 写材料と基板をラミネートし、得られた積層体力ゝら仮支持体を剥離することにより微粒 子含有層を基板に転写する方法が好ましい。 [0141] Next, a method for transferring and forming a fine particle-containing layer on a substrate using a photosensitive transfer material will be mainly described. The surface of the fine particle-containing layer, which is the outermost layer, and the surface of the substrate are brought into close contact with each other. A method of transferring the fine particle-containing layer to the substrate by laminating the printing material and the substrate and peeling off the temporary support from the obtained laminate strength is preferable.
前記ラミネートの方法には、例えば、従来公知のラミネーター、真空ラミネーターを 用いることができる。また、摩擦性を高めるため、該方法にオートカットラミネーターを 使用することちできる。  For the laminating method, for example, a conventionally known laminator or vacuum laminator can be used. In addition, an auto-cut laminator can be used in the method in order to improve friction.
[0142] ラミネートの際の加熱温度は、 60〜150°C程度が好ましぐ加圧圧力は 0. 2〜20k gZcm2程度が好ましい。本発明では、ラミネートは基板のライン速度が 0. 05〜： LOm[0142] The heating temperature at the time of lamination is preferably about 60 to 150 ° C, and the pressing pressure is preferably about 0.2 to 20 kgZcm2. In the present invention, the laminate has a substrate line speed of 0.05 to: LOm
Z分程度である範囲で行なうことが好まし 、。 It is preferable to do it in a range that is about Z minutes.
[0143] 感光性転写材料を用いて表示装置用遮光膜を形成する場合、感光性転写材料と 基板とをラミネートし、仮支持体を剥離し、露光及び現像を順次行ない、さらに加熱を 施すことが好ましい。露光、現像及び加熱の条件については既述の方法のそれらを 適用することができる。 [0143] When a light-shielding film for a display device is formed using a photosensitive transfer material, the photosensitive transfer material and the substrate are laminated, the temporary support is peeled off, exposure and development are sequentially performed, and heating is further performed. Is preferred. For the exposure, development and heating conditions, those described above can be applied.
[0144] く遮光膜付き基板〉 [0144] Substrate with light-shielding film>
本発明の遮光膜付き基板は、基板上に、既述の本発明の微粒子含有組成物、既 述の本発明の表示装置用着色膜形成用インク、又は既述の本発明の遮光材料を用 いて遮光膜を有する。  The substrate with a light-shielding film of the present invention uses the fine particle-containing composition of the present invention described above, the ink for forming a colored film for a display device of the present invention described above, or the light-shielding material of the present invention described above on the substrate. And has a light shielding film.
遮光膜の形成は、既述の表示装置用遮光膜を形成するのに好適な方法（1)〜（3) により行なえ、方法（3)によるのがより好ましい。  The light shielding film can be formed by the methods (1) to (3) suitable for forming the light shielding film for a display device described above, and more preferably by the method (3).
[0145] なお、微粒子含有組成物、表示装置用着色膜形成用インク、及び遮光材料の各成 分及びその好ましい態様は既述の通りである。また、遮光膜の厚み及び透過濃度（ 光学濃度）は、既述の表示装置用遮光膜のそれらと同じである。 [0145] The components of the fine particle-containing composition, the colored film forming ink for display device, and the light shielding material and preferred embodiments thereof are as described above. Further, the thickness and transmission density (optical density) of the light shielding film are the same as those of the light shielding film for a display device described above.
[0146] くカラーフィノレタ> [0146] Kukarafinoreta>
本発明のカラーフィルタは、光透過性の基板上に、異なる色相を呈する複数の画 素と、前記複数の画素の各々を離隔する遮光画像 (V、わゆるブラックマトリックス）とを 有し、前記遮光画像が既述の本発明の表示装置用遮光膜である。  The color filter of the present invention has a plurality of pixels exhibiting different hues on a light-transmitting substrate and a light-shielded image (V, a so-called black matrix) separating each of the plurality of pixels. The light-shielded image is the above-described light-shielding film for a display device of the present invention.
[0147] 光透過性の基板としては、例えば、既述した基板、 TFT素子が設けられた駆動基 板 (TFT素子基板等)を用いることができる。 [0147] As the light-transmitting substrate, for example, the above-described substrate or a driving substrate (TFT element substrate or the like) provided with a TFT element can be used.
[0148] 本発明のカラーフィルタは既述の本発明の表示装置用遮光膜を有し、該表示装置 用遮光膜は既述の本発明の微粒子含有組成物、あるいは既述の本発明の表示装 置用着色膜形成用インクを用いて形成されるので、かかる遮光膜は、製造中に高温 に曝されても、高温環境での榭脂成分、微粒子の変質に伴なう色味変化が少なぐ 良好な色相と高い光学濃度を有しており、表示画像のコントラスト及び配線の遮蔽性 に優れる。 [0148] The color filter of the present invention has the light-shielding film for a display device of the present invention described above, and the display device Since the light shielding film is formed using the fine particle-containing composition of the present invention described above or the colored film forming ink for display device of the present invention described above, the light shielding film is exposed to a high temperature during production. Even in such a case, it has a good hue and a high optical density with little change in color caused by alteration of the resin component and fine particles in a high temperature environment, and is excellent in display image contrast and wiring shielding.
[0149] 本発明のカラーフィルタに TFT素子基板を用いる場合には、 TFT素子基板上に、 複数の画素と該複数の画素の各々を離隔する表示装置用遮光膜とを設けてもよ!、。 或いは、本発明のカラーフィルタは、 TFT素子基板の上に、複数の画素を設けず に、表示装置用遮光膜 (ブラックマトリックス）のみを有してもよい。この場合は、この T FT素子基板とは別の光透過性の基板上に複数の画素を形成し、複数の画素が形 成された基板を前記 TFT素子基板に対向するように配置する。これにより、 TFTァレ ィの開口率が良好となる。  [0149] When a TFT element substrate is used for the color filter of the present invention, a plurality of pixels and a light shielding film for a display device that separates each of the plurality of pixels may be provided on the TFT element substrate! . Alternatively, the color filter of the present invention may have only a light shielding film (black matrix) for a display device without providing a plurality of pixels on the TFT element substrate. In this case, a plurality of pixels are formed on a light-transmitting substrate different from the TFT element substrate, and the substrate on which the plurality of pixels are formed is disposed so as to face the TFT element substrate. This improves the aperture ratio of the TFT array.
[0150] 異なる色相を呈する複数の画素は、複数種の画素形成用の着色感光性榭脂組成 物や感光性転写材料を用い、常法により形成することができる。複数の画素を形成し た後は、熱処理を行なうことが好ましい。  [0150] A plurality of pixels exhibiting different hues can be formed by a conventional method using a plurality of types of colored photosensitive resin compositions and photosensitive transfer materials for pixel formation. After forming a plurality of pixels, heat treatment is preferably performed.
着色感光性榭脂組成物、及び感光性転写材料については、例えば、特開 2005— 3861号公報や、特開 2004— 361448号公報、特開 2004— 205731公報を参照 できる。  Regarding the colored photosensitive resin composition and the photosensitive transfer material, for example, JP-A-2005-3861, JP-A-2004-361448, and JP-A-2004-205731 can be referred to.
[0151] <液晶表示素子、液晶表示装置 >  [0151] <Liquid crystal display element, liquid crystal display device>
本発明の液晶表示素子は、既述の本発明の遮光膜付き基板を備え、本発明の遮 光膜付き基板、詳細には、既述した本発明の微粒子含有組成物、表示装置用着色 膜形成用インク、又は遮光材料を用いて形成された遮光膜を有するので、高温環境 に曝されることに伴なう色味変化が少なぐ良好な色相と高い光学濃度を有しており、 コントラストが高ぐ良好な表示品質の画像を表示可能である。  The liquid crystal display element of the present invention includes the substrate with the light shielding film of the present invention described above, and more specifically, the substrate with the light shielding film of the present invention, more specifically, the fine particle-containing composition of the present invention described above and the colored film for display device. Because it has a light-shielding film formed using a forming ink or a light-shielding material, it has a good hue and a high optical density with little tint change due to exposure to high-temperature environments. It is possible to display an image with good display quality.
[0152] 液晶表示素子は本発明の遮光膜付き基板を備え、それ以外の点では特に限定は なぐ公知の液晶表示素子の構成要素を更に有することができる。例えば、液晶表示 素子はカラーフィルタ基板と、該カラーフィルタ基板と対向するように配置された光透 過性の基板と、これら基板間に設けられた液晶層と、液晶層の液晶を駆動する液晶 駆動ユニット（単純マトリックス駆動方式及びアクティブマトリックス駆動方式を含む。） とを備え、カラーフィルタ基板として既述の本発明のカラーフィルタを用いることがで きる。 [0152] The liquid crystal display element includes the substrate with the light-shielding film of the present invention, and may further include a component of a known liquid crystal display element that is not particularly limited. For example, a liquid crystal display element includes a color filter substrate, a light-transmitting substrate disposed so as to face the color filter substrate, a liquid crystal layer provided between the substrates, and a liquid crystal that drives the liquid crystal in the liquid crystal layer. Drive unit (including a simple matrix drive system and an active matrix drive system), and the color filter of the present invention described above can be used as a color filter substrate.
[0153] 本発明の液晶表示装置は、本発明の液晶表示素子を有する。本発明の液晶表示 素子、詳細には、既述した本発明の遮光膜付き基板 (本発明の微粒子含有組成物、 表示装置用着色膜形成用インク、又は遮光材料)を有するので、高温環境に曝され ることに伴なう色味変化が少なぐ良好な色相と高い光学濃度を有しており、コントラ ストが高ぐ良好な表示品質の画像を表示可能である。  [0153] The liquid crystal display device of the present invention has the liquid crystal display element of the present invention. Since the liquid crystal display element of the present invention has a substrate with a light-shielding film of the present invention described above (in particular, the fine particle-containing composition of the present invention, a color film-forming ink for a display device, or a light-shielding material), It has a good hue with little color change due to exposure and a high optical density, and can display images with good contrast and high display quality.
[0154] 本発明の液晶表示装置は本発明の液晶表示素子を有し、それ以外の点では特に 限定はなぐ公知の液晶表示装置の構成要素を更に有することができる。  [0154] The liquid crystal display device of the present invention has the liquid crystal display element of the present invention, and can further include components of a known liquid crystal display device that is not particularly limited otherwise.
実施例  Example
[0155] 以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越え ない限り、以下の実施例に限定されるものではない。なお、特に断りのない限り、「部 」及び「％」はそれぞれ「質量部」及び「質量％」を意味する。  [0155] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist of the present invention. Unless otherwise specified, “part” and “%” mean “part by mass” and “% by mass”, respectively.
[0156] <高分子分散剤の合成 >  [0156] <Synthesis of polymer dispersant>
ポリマー 1の合成  Synthesis of polymer 1
ノルマルプロパノール 200部を 80°Cに加熱した後、これに窒素気流下で、ェチル チォェチルアタリレー卜 52. 2部、メタクリル酸 20. 0部、及びジメチルアクリルアミド 12 7. 8部の混合物（モノマー液）と、 2, 2' ァゾビス (イソ酪酸)ジメチル (和光純薬ェ 業 (株)製 V— 601) 1. 70部及びノルマルプロパノール 100部の混合物（開始剤溶液 )と、をそれぞれ 2時間かけて同時に滴下した。滴下終了後、窒素気流下で、得られ た混合物を 80°Cで 2時間加熱し、得られた反応系にノルマルプロパノール 500部を 添加して、ポリマー 1の 20%溶液 (重量平均分子量 84000、本発明に係る高分子分 散剤)を得た。  After 200 parts of normal propanol was heated to 80 ° C, this was mixed with 52.2 parts of ethyl thioethylatreylate, 20.0 parts of methacrylic acid, and 127.8 parts of dimethylacrylamide under a nitrogen stream ( Monomer solution) and 2, 2 'azobis (isobutyric acid) dimethyl (V-601 manufactured by Wako Pure Chemical Industries, Ltd.) 1. Mix 2 parts of 70 parts and 100 parts of normal propanol (initiator solution). It was dripped simultaneously over time. After completion of the dropwise addition, the resulting mixture was heated at 80 ° C for 2 hours under a nitrogen stream, and 500 parts of normal propanol was added to the resulting reaction system to prepare a 20% solution of polymer 1 (weight average molecular weight 84000, A polymer dispersant according to the present invention was obtained.
[0157] [化 4]
Figure imgf000033_0001
[0158] ポリマー 2の合成 [0157] [Chemical 4]
Figure imgf000033_0001
[0158] Synthesis of Polymer 2
メチルェチルケトン 200部を 80°Cに加熱した後、これに窒素気流下で、ェチルチオ ェチルアタリレート 52. 2部、メタクリル酸 47. 8部、及びスチレン 100. 0部の混合物（ モノマー液）と、 2, 2'—ァゾビス (イソ酪酸)ジメチル（商品名： V— 601 ;和光純薬ェ 業 (株)製） 1. 70部、及びメチルェチルケトン 100部の混合物（開始剤溶液）とを、そ れぞれ 2時間かけて同時に滴下した。滴下終了後、窒素気流下で、得られた混合物 を 80°Cで 2時間加熱し、得られた反応系にメチルェチルケトン 500部を添カ卩して、ポ リマー 2の 20%溶液 (重量平均分子量 70000、本発明に係る高分子分散剤）を得た  After heating 200 parts of methyl ethyl ketone to 80 ° C, this was mixed with 52.2 parts of ethyl thioethyl acrylate, 47.8 parts of methacrylic acid, and 100.0 parts of styrene (monomer solution) under a nitrogen stream. ) And 2, 2'-azobis (isobutyric acid) dimethyl (trade name: V-601; manufactured by Wako Pure Chemical Industries, Ltd.) 1. 70 parts and 100 parts of methyl ethyl ketone (initiator solution) ) Were simultaneously added dropwise over 2 hours. After completion of the dropwise addition, the resulting mixture was heated at 80 ° C for 2 hours under a nitrogen stream, and 500 parts of methyl ethyl ketone was added to the resulting reaction system to prepare a 20% solution of polymer 2 ( A weight average molecular weight 70000, a polymer dispersant according to the present invention) was obtained.
[0159] [化 5] [0159] [Chemical 5]
1 : 52. 1
Figure imgf000034_0001
1: 52. 1
Figure imgf000034_0001
[0160] ポリマー 3の合成 [0160] Synthesis of Polymer 3
前記ポリマー 2の合成で用いたモノマー液を、メチルチオェチルアタリレート 47. 7 部、メタクリル酸 47. 8部、及びスチレン 104. 5部の混合物に代えたこと以外、前記 ポリマー 2の溶液と同じ方法で、ポリマー 3の 20%溶液（重量平均分子量 68000、本 発明に係る高分子分散剤)を得た。  Same as the solution of Polymer 2 except that the monomer solution used in the synthesis of Polymer 2 was replaced with a mixture of 47.7 parts of methylthioethyl acrylate and 47.8 parts of methacrylic acid and 104.5 parts of styrene. By the method, a 20% solution of polymer 3 (weight average molecular weight 68000, polymer dispersant according to the present invention) was obtained.
[0161] [化 6]  [0161] [Chemical 6]
Figure imgf000034_0002
Figure imgf000034_0002
[0162] ポリマー 4の合成 [0162] Synthesis of Polymer 4
前記ポリマー 2の合成で用いたモノマー液を、フエ-ルチオェチルアタリレート 67. 9部、メタクリル酸 47. 8部、及びメタクリル酸メチル 84. 3部の混合物に代えたこと以 外、前記ポリマー 2の溶液と同じ方法で、ポリマー 4の 20%溶液 (重量平均分子量 78 000、本発明に係る高分子分散剤)を得た。 The polymer solution used in the synthesis of the polymer 2 was replaced with a mixture of 67.9 parts of phenylthioethyl acrylate, 47.8 parts of methacrylic acid, and 84.3 parts of methyl methacrylate. 20% solution of polymer 4 (weight average molecular weight 78 000, a polymer dispersant according to the present invention).
[0163] [化 7]  [0163] [Chemical 7]
Figure imgf000035_0001
Figure imgf000035_0001
[0164] 実施例 1 [0164] Example 1
<銀微粒子組成物の調製 >  <Preparation of silver fine particle composition>
まず、 Mater. Chem. Phys. 2004, 84, p.197— 204に記載の微粒子の調製方 法にしたがって、銀塩還元時の pH、反応温度を変化させることにより、各種ァスぺク ト比を持つロッド状銀微粒子の分散液を調製し、得られた分散液を遠心分離 (回転数 lOOOOr.p.m., 20分間）し、上澄み液を捨て残渣を適宜濃縮して、ロッド状銀微粒子 を得た。  First, according to the fine particle preparation method described in Mater. Chem. Phys. 2004, 84, p.197-204, various aspect ratios were obtained by changing the pH and reaction temperature during silver salt reduction. A dispersion of rod-shaped silver fine particles having a particle diameter, centrifuge the resulting dispersion (rotation speed lOOOOr.pm, 20 minutes), discard the supernatant, and concentrate the residue appropriately to obtain rod-shaped silver fine particles. It was.
[0165] 上記より得たロッド状銀微粒子のうち、平均アスペクト比が 54. 7のロッド状銀微粒 子 20. 0咅と、上記より得たポリマー 1の 20%溶液 20. 0咅と、ノノレマノレプロノ ノ一ノレ 80. 0部とを混合し、超音波分散機（Ultrasonic generator model US— 6000 ccvpゝ（株)エッセィ製)を用いて攪拌し、銀微粒子組成物を調製した。  [0165] Among the rod-shaped silver fine particles obtained from the above, 20.0% of rod-shaped silver fine particles having an average aspect ratio of 54.7, 20.0% of a 20% solution of polymer 1 obtained above, 80.0 parts of Remanoleprono Mononore were mixed and stirred using an ultrasonic disperser (Ultrasonic generator model US—6000 ccvp ゝ manufactured by Essey Co., Ltd.) to prepare a silver fine particle composition.
[0166] 評価 1  [0166] Rating 1
1.銀微粒子分散性の評価  1. Evaluation of silver fine particle dispersibility
前記銀微粒子組成物を 25°Cにて 3日間放置した後、目視により前記組成物中の銀 微粒子の分散性を下記の評価基準にしたがって評価した。評価結果は表 2に示す。 〈評価基準〉  After the silver fine particle composition was allowed to stand at 25 ° C. for 3 days, the dispersibility of the silver fine particles in the composition was visually evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2. <Evaluation criteria>
A：銀微粒子が沈降することなく均一に分散されて!、た。  A: The silver fine particles were uniformly dispersed without settling!
B：銀微粒子の一部が沈降して 、た。  B: A part of silver fine particles settled.
C：銀微粒子が完全に沈降して 、た。  C: Silver fine particles were completely settled.
[0167] <遮光画像形成用塗布液の調製 > [0167] <Preparation of shading image forming coating solution>
下記組成の成分を混合し、遮光画像形成用塗布液 (黒色材料用の微粒子含有組 成物)を調製した。 〈黒色材料用の微粒子含有組成物の組成〉 Components having the following composition were mixed to prepare a light-shielding image-forming coating solution (fine particle-containing composition for black material). <Composition of fine particle-containing composition for black material>
•上記の銀微粒子組成物（アスペクト比 = 54 180咅  • Silver fine particle composition (Aspect ratio = 54 180 咅)
•フッ素系界面活性剤 1. 68咅  • Fluorosurfactant 1.68 咅
(大日本インキ化学工業 (株)製 F780F)  (F780F, manufactured by Dainippon Ink & Chemicals, Inc.)
.ジペンタエリスリトールへキサアタリレート 6. 27  Dipentaerythritol hexaatalylate 6. 27
(日本化薬 (株）製 KAYARAD DPHA)  (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)
'ビス [4— [N— (4, 6—ビストリクロロメチル一 s—トリァジン一 2—ィル）フエ-ル]カル バモイル]フエ二ノレ]セノケート 0. 6  'Bis [4— [N— (4, 6-Bistrichloromethyl 1 s-triazine 1 2-yl) phenol] carbamoyl] phenolino] senocate 0. 6
，アセトン 1500咅  , Acetone 1500 咅
[0168] <遮光画像の形成 >  [0168] <Shadow image formation>
無アルカリガラス基板を UV洗浄装置で洗浄後、洗浄剤を用いてブラシ洗浄し、更 に超純水で超音波洗浄した。洗浄後の基板を 120°Cで 3分間加熱し、その表面状態 を安定ィ匕させた。続いて、この基板を冷却して 23°Cに温調した後、スリット状ノズルを 有するガラス基板用コーター（エフ'ェ一'エス'ジャパン社製 MH— 1600)を用!、て 、上記の遮光画像形成用塗布液を塗布し塗布膜を形成した (塗布工程)。  The alkali-free glass substrate was cleaned with a UV cleaner, then brush-cleaned with a cleaning agent, and then ultrasonically cleaned with ultrapure water. The cleaned substrate was heated at 120 ° C for 3 minutes to stabilize its surface condition. Subsequently, after cooling this substrate and adjusting the temperature to 23 ° C., a glass substrate coater (MH-1600 manufactured by F'S Japan Co., Ltd.) having a slit-like nozzle was used! A light-shielding image-forming coating solution was applied to form a coating film (coating process).
[0169] 引き続き、真空乾燥装置 VCD (東京応化工業 (株)製)に前記基板を 30秒間置い て、溶媒の一部を乾燥させて前記塗布膜の流動性をなくした後、エッジ'ビード 'リム 一バー (EBR)にて基板の縁の不要な塗布液を除去し、 120°Cで 3分間基板をプリべ ークし、層厚 0. 5 μ mの遮光層を形成した。  [0169] Subsequently, the substrate was placed in a vacuum drying apparatus VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to dry part of the solvent to eliminate the fluidity of the coating film, and then the edge 'bead' The unnecessary coating solution at the edge of the substrate was removed with a rim bar (EBR), and the substrate was pre-baked at 120 ° C for 3 minutes to form a light-shielding layer with a layer thickness of 0.5 μm.
[0170] 次に、マスク (格子状の画像パターンを有する石英露光マスク）と遮光層が設けられ た無アルカリガラス基板とを垂直に立てて、マスク面と遮光層の表面との間の距離を 100 /z mに設定した。この状態で、超高圧水銀灯を備えたプロキシミティー型露光機 (日立電子エンジニアリング (株)製)を用い、遮光層を露光量 200mj/cm2でパター ン露光した (露光工程)。 [0170] Next, a mask (quartz exposure mask having a lattice-like image pattern) and a non-alkali glass substrate provided with a light shielding layer are vertically set, and the distance between the mask surface and the surface of the light shielding layer is set. Set to 100 / zm. In this state, using a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) equipped with an ultra high pressure mercury lamp, the light shielding layer was subjected to pattern exposure at an exposure amount of 200 mj / cm 2 (exposure process).
[0171] 次に、純水をシャワーノズル力 遮光層に噴霧し、遮光層の表面を均一に湿らせた 。その後、 KOH系現像液 CDK—1 (富士フィルムエレクト口-クスマテリアルズ (株） 製; KOH及びノ-オン界面活性剤含有アルカリ現像液)を純水で 100倍に薄めたも のを、フラットノズルから 23°C、ノズル圧力 0. 04MPaにて 80秒間遮光層に噴射して 遮光層をシャワー現像し、黒色パターンを得た (現像工程)。続いて、無アルカリガラ ス基板の黒色パターンが形成された側に超純水を超高圧洗浄ノズルにより 9. 8MPa の圧力で噴射して残渣を除去し、無アルカリガラス基板上にブラック (K)画像を形成 した。その後、該基板を 220°Cで 40分間ベータし (ベータ工程）、遮光画像を得た。 [0171] Next, pure water was sprayed onto the light shielding layer of the shower nozzle force to uniformly wet the surface of the light shielding layer. After that, KOH developer CDK-1 (manufactured by Fuji Film Elect Kokusu Materials Co., Ltd .; KOH and non-surfactant-containing alkali developer) was diluted 100 times with pure water. Spray from the nozzle at 23 ° C and nozzle pressure 0.04MPa for 80 seconds on the light shielding layer. The light shielding layer was shower developed to obtain a black pattern (development process). Subsequently, ultrapure water is sprayed onto the side of the alkali-free glass substrate on which the black pattern is formed with an ultra-high pressure cleaning nozzle at a pressure of 9.8 MPa to remove the residue, and black (K) is deposited on the alkali-free glass substrate. An image was formed. Thereafter, the substrate was beta-treated at 220 ° C. for 40 minutes (beta process) to obtain a light-shielded image.
[0172] <カラーフィルタの作製 >  [0172] <Production of color filter>
遮光画像が形成された無アルカリガラス基板 (以下、「カラーフィルタ基板」と称する 。；)に、特開 2004— 347831号公報の段落番号 [0075]〜[0086]に記載の感光性 榭脂組成物を用いて、所定サイズ、形状よりなる赤色 (R)、緑色 (G)、青色 (B)の着 色パターン (着色画素）を形成し、カラーフィルタを作製した。具体的には、以下の方 法によりカラーフィルターを作製した。  A photosensitive resin composition according to paragraphs [0075] to [0086] of JP-A No. 2004-347831 is provided on an alkali-free glass substrate (hereinafter referred to as “color filter substrate”;) on which a light-shielding image is formed. Using the product, red (R), green (G), and blue (B) colored patterns (colored pixels) having a predetermined size and shape were formed to produce a color filter. Specifically, a color filter was produced by the following method.
[0173] 顔料分散物の合成  [0173] Synthesis of pigment dispersion
(1) 5 -トロイソフタル酸ジメチル 50部と N, N ジェチルー 1, 3 プロパンジアミ ン 130部を、弱く減圧しながら温度 80〜： LOO°Cで 4時間かけて反応させた。原料の 5 -トロイソフタル酸ジメチル及びモノアミド化合物の消失を確認したのち、過剰の N , N—ジェチル— 1, 3 プロパンジァミンを減圧除去し、 92部の 5 -トロイソフタル 酸ビス 3—ジェチルァミノプロピルアミドを得た。  (1) 50 parts of dimethyl 5-troisophthalate and 130 parts of N, N jetyl-1,3 propanediamine were reacted at a temperature of 80 to LOO ° C. over 4 hours with weak pressure reduction. After confirming the disappearance of dimethyl 5-troisophthalate and monoamide compound as raw materials, excess N, N-jetyl-1,3-propanediamine was removed under reduced pressure, and 92 parts of bis-3-jetylamino of 5-troisophthalate were removed. Propylamide was obtained.
[0174] (2)得られた 5 -トロイソフタル酸ビス 3 ジェチルァミノプロピルアミド 18. 5部、 及びトリェチルァミン 5. 1部を DMF60部に溶解して得られた溶液を氷冷した。この 溶液に 4 -トロベンゾイルク口ライド 9. 3部のアセトン 60部液を加えてアミド化を行 つた。この反応後、水 800部を反応系にカ卩えて結晶を濾取し、酢酸ェチルにより再結 晶して、 4— -トロベンゾィル—4— {3, 5—ビス（3—ジェチルァミノプロピルカルバモ ィル） }フヱ-ルアミド 14部を得た。  (2) A solution obtained by dissolving 18.5 parts of the obtained 5-troisophthalic acid bis 3 jetylaminopropylamide and 5.1 parts of triethylamine in 60 parts of DMF was ice-cooled. Amidation was performed by adding 9.3 parts of 60 parts of acetone to this solution. After this reaction, 800 parts of water was added to the reaction system, and the crystals were collected by filtration and recrystallized with ethyl acetate. 4-Trobenzoyl-4- {3,5-bis (3-jetylaminopropyl) Carbamoyl)} 14 parts of phenylamide were obtained.
[0175] (3)得られた 4 -トロベンゾィルー 4 {3, 5 ビス（3 ジェチルァミノプロピルカル バモイル）}フエ-ルアミド 14部を還元鉄及び塩化アンモ-ゥムと共にイソプロパノー ル 200部、水 35部中で還流し還元して、ァ-リン誘導体 13. 2部を得た。  [0175] (3) 14 parts of the obtained 4-trobenzoyl luo 4 {3,5 bis (3 jetylaminopropylcarbamoyl)} phenol amide with reduced iron and ammonium chloride, 200 parts isopropanol, water Refluxing in 35 parts and reduction afforded 13.2 parts of the arline derivative.
[0176] (4)得られたァ-リン誘導体 13. 2部をメタノール 120部に加え、氷冷下に塩酸 18部 を加えた。この混合液を更に温度 15°Cまで冷却した。これに NaNO 1. 8部の水  (4) 13.2 parts of the obtained aline derivative were added to 120 parts of methanol, and 18 parts of hydrochloric acid were added under ice cooling. The mixture was further cooled to a temperature of 15 ° C. This is NaNO 1. 8 parts of water
2  2
溶液 (水 20部）を滴下し、ジァゾィ匕した (ジァゾ溶液の調製)。別途、 5 ァセトァセチ ルァミノべンズイミダゾロン 5. 9部、メタノール 26部、水 530部、及び NaCO 10. 8部 The solution (20 parts of water) was added dropwise to dizzy (preparation of diazo solution). Separately, 5 options Luaminobens imidazolone 5.9 parts, methanol 26 parts, water 530 parts, and NaCO 10.8 parts
3 力もなるカップリング成分溶液を調製し、温度 10°Cに冷却した。これに上記で得られ たジァゾ液を温度 10°Cを超えない様に滴下し、反応させた。更に K COを加えて系  A coupling component solution having 3 strengths was prepared and cooled to a temperature of 10 ° C. The diazo solution obtained above was added dropwise to this so as not to exceed a temperature of 10 ° C., and reacted. Further, add K CO
2 3 を塩基性にし、析出した黄色生成物を濾取し、 DMFとァセトニトリルとによって再結 晶して、 目的の顔料分散物である下記化合物 [1]を得た。得られた化合物の最大吸 収波長は、 λ = 391nm (CHCl中）であった。  2 3 was made basic, and the precipitated yellow product was collected by filtration and recrystallized with DMF and acetonitrile to obtain the following compound [1] as the desired pigment dispersion. The maximum absorption wavelength of the obtained compound was λ = 391 nm (in CHCl).
max 3  max 3
[0177] [化 8]  [0177] [Chemical 8]
Figure imgf000038_0001
Figure imgf000038_0001
[0178] 黄色顔料分散液 PY— 139の調製 [0178] Preparation of yellow pigment dispersion PY-139
下記組成の黄色顔料組成物を調製した。  A yellow pigment composition having the following composition was prepared.
•C. I.ビグメントイエロー 139 8g  • C. I. Pigment Yellow 139 8g
•上記化合物 [1]の顔料分散物 0. 8g  • Pigment dispersion of above compound [1] 0.8g
'メタクリル酸 Zメタクリル酸ベンジル共重合体 20g  'Methacrylic acid Z benzyl methacrylate copolymer 20g
(モル比 28Z72、重量平均分子量 3万、濃度 40%の 1ーメトキシー 2 プロピルァセ テート溶液、酸価 105)  (Molar ratio 28Z72, weight-average molecular weight 30,000, 1-methoxy-2-propyl phosphate solution with a concentration of 40%, acid value 105)
•1ーメトキシ 2 プロピルアセテート 51. 2g  1-methoxy 2-propyl acetate 51.2 g
[0179] 上記組成の黄色顔料組成物をモーターミル「M— 50」（アイガー社製）で、径 0. 65 mm φのジルコユアビーズを用いて、周速 9mZ秒で 16時間かけて攪拌して、 目的と する黄色顔料分散液 (PY— 139)を調製した。 [0179] The yellow pigment composition having the above composition was stirred with a motor mill “M-50” (manufactured by Eiger) for 16 hours at a peripheral speed of 9 mZ seconds using 0.65 mm diameter Zircoyu beads. The purpose and A yellow pigment dispersion (PY-139) was prepared.
[0180] カラーフィルターの作製  [0180] Fabrication of color filter
下記の表 1に示したカラーフィルター用の赤色画素形成用塗布液 (R1)を調製し、 この塗布液をソーダライムガラス基板（100mm X 100mm、厚み 1. 1mm)上にスピ ンコーター「1H— DX」（ミカサ社製）を用いて 180rpmにて塗布した後、オーブンに 基板を入れ温度 100°Cで 2分間加熱して、得られた塗膜を乾燥した。  Prepare the red pixel forming coating solution (R1) for color filters shown in Table 1 below, and apply this coating solution on a soda lime glass substrate (100 mm x 100 mm, thickness 1.1 mm) on the spin coater “1H-DX”. (Mikasa Co., Ltd.) was applied at 180 rpm, and then the substrate was placed in an oven and heated at a temperature of 100 ° C. for 2 minutes to dry the resulting coating film.
[0181] 次いで、パターン作製用クロームマスクを介してマスクァライナー「M— 2L」（ミカサ 社製）により 200mjZcm2の露光を行った後、基板を温度 33°Cの 1%炭酸ナトリウム 水溶液中に 60秒間浸漬した後、水洗して未露光部分を除去し、更に基板をオーブ ンに入れて温度 220°Cで 30分間かけて加熱し、基板上に赤色 (R)画素パターンを 形成した。 [0181] Next, after exposure of 200 mjZcm 2 with a mask aligner “M-2L” (Mikasa) through a chrome mask for pattern preparation, the substrate was placed in a 1% aqueous sodium carbonate solution at a temperature of 33 ° C. After immersion for 60 seconds, the unexposed portion was removed by washing with water, and the substrate was placed in an oven and heated at 220 ° C. for 30 minutes to form a red (R) pixel pattern on the substrate.
[0182] 次に、上記で得た PY139分散液を用いて、下記表 1に示したカラーフィルター用の 緑色画素形成用塗布液 (G1)を調製して、この塗布液を上記の赤色画素パターンが 形成された基板上にスピンコーターを用いて 230rpmにて塗布した後、上記の赤色 画素パターン形成の場合と同様にして、緑色 (G)画素パターンを形成した。  [0182] Next, using the PY139 dispersion obtained above, a green pixel forming coating solution (G1) shown in Table 1 below was prepared, and this coating solution was used as the red pixel pattern described above. After coating at 230 rpm on a substrate with a spin coater, a green (G) pixel pattern was formed in the same manner as in the red pixel pattern formation described above.
[0183] 更に、下記表 1に示したカラーフィルター用の青色画素形成用塗布液 (B1)を調製 し、この塗布液を上記の赤色画素パターンと青色画素パターンが形成された基板上 にスピンコ一ターを用いて 180rpmにて塗布した後、上記赤色画素パターン形成と 同様にして青色 (B)画素パターンを形成し、本発明に従う (R)画素パターン、 （G)画 素パターン、及び (B)画素パターンが積層された基板 (カラーフィルター）を得た。  [0183] Further, a blue pixel forming coating solution (B1) for a color filter shown in Table 1 below was prepared, and this coating solution was spin-coated on the substrate on which the red pixel pattern and the blue pixel pattern were formed. After applying at 180 rpm using a filter, a blue (B) pixel pattern is formed in the same manner as the above red pixel pattern formation, and the (R) pixel pattern, (G) pixel pattern, and (B) according to the present invention are formed. A substrate (color filter) on which a pixel pattern was laminated was obtained.
[0184] [表 1] [0184] [Table 1]
JP2006/320755 JP2006 / 320755
Figure imgf000040_0001
Figure imgf000040_0001
注）顔料分散液中の顔料濃度  Note) Pigment concentration in the pigment dispersion
RT- 107 ： Β%  RT-107: Β%
MHIヴアイォレツ卜 7040Μ ： 8%  MHI Violet 7040: 8%
GT-2 ： 18%  GT-2: 18%
PY— 139分散液 ： 10%  PY—139 dispersion: 10%
MHけルー 7075M ： 14% <液晶表示素子及び液晶表示装置の作製〉  MH Keru 7075M: 14% <Production of liquid crystal display element and liquid crystal display device>
上記で得たカラーフィルタを用いて、以下のように、液晶表示素子を作製すると共 に、さらに液晶表示装置を作製した。  Using the color filter obtained above, a liquid crystal display device was produced as follows, and a liquid crystal display device was further produced.
まず、得られたカラーフィルタの RGBのパターンに対応させるようにして、別に用意 したガラス基板上に、薄膜トランジスタ (TFT)と画素電極とを形成すると共に、配向 膜を設けてアクティブマトリックス基板を作製した。次いで、上記で得たカラーフィルタ の上に更に ITO膜と配向膜とを形成し、対向基板とした。得られたアクティブマトリク ス基板と対向基板とを両者の間に所定の間隔（いわゆるセル厚）が形成されるよう対 向するよう配置し、両基板間の空間に TN液晶を封入して両基板をシール剤で貼り合 わせ、液晶表示素子を得た。そして、得られた液晶表示素子の両基板の表面に偏光 板をクロス-コルにて配置し、更にアクティブマトリックス基板側にノックライトを配設し て、液晶表示装置とした。 First, a thin film transistor (TFT) and a pixel electrode were formed on a separately prepared glass substrate so as to correspond to the RGB pattern of the obtained color filter, and an active matrix substrate was prepared by providing an alignment film. . Next, an ITO film and an alignment film were further formed on the color filter obtained above to obtain a counter substrate. The obtained active matrix substrate and the counter substrate are arranged so as to face each other so that a predetermined interval (so-called cell thickness) is formed between them, and TN liquid crystal is sealed in the space between the two substrates. Were bonded together with a sealing agent to obtain a liquid crystal display element. Then, polarized light is applied to the surfaces of both substrates of the obtained liquid crystal display element. A plate was placed in cross-col, and a knock light was further placed on the active matrix substrate side to obtain a liquid crystal display device.
[0186] 実施例 2  [0186] Example 2
実施例 1において、ポリマー 1の 20%溶液をポリマー 2の 20%溶液に代え、かつノ ルマルプロパノールをメチルェチルケトンに代えたこと以外、実施例 1と同じにして、 銀微粒子組成物を調製し、評価 1を行なうと共に、遮光画像、カラーフィルタ、液晶表 示素子、及び液晶表示装置を得た。評価 1の結果を表 2に示す。  In Example 1, a silver fine particle composition was prepared in the same manner as in Example 1, except that the 20% solution of polymer 1 was replaced with a 20% solution of polymer 2 and normal propanol was replaced with methyl ethyl ketone. Then, evaluation 1 was performed, and a light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were obtained. The results of Evaluation 1 are shown in Table 2.
[0187] 実施例 3 [0187] Example 3
実施例 1において、ポリマー 1の 20%溶液をポリマー 3の 20%溶液に代え、かつノ ルマルプロパノールをメチルェチルケトンに代えたこと以外、実施例 1と同じにして、 銀微粒子組成物を調製し、評価 1を行なうと共に、遮光画像、カラーフィルタ、液晶表 示素子、及び液晶表示装置を得た。評価 1の結果を表 2に示す。  A silver fine particle composition was prepared in the same manner as in Example 1, except that the 20% solution of polymer 1 was replaced with the 20% solution of polymer 3 and normal propanol was replaced with methyl ethyl ketone. Then, evaluation 1 was performed, and a light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were obtained. The results of Evaluation 1 are shown in Table 2.
[0188] 実施例 4 [0188] Example 4
実施例 1において、ポリマー 1の 20%溶液をポリマー 4の 20%溶液に代え、かつノ ルマルプロパノールをメチルェチルケトンに代えたこと以外、実施例 1と同じにして、 銀微粒子組成物を調製し、評価 1を行なうと共に、遮光画像、カラーフィルタ、液晶表 示素子、及び液晶表示装置を得た。評価 1の結果を表 2に示す。  A silver fine particle composition was prepared in the same manner as in Example 1, except that the 20% solution of polymer 1 was replaced with the 20% solution of polymer 4 and normal propanol was replaced with methyl ethyl ketone. Then, evaluation 1 was performed, and a light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were obtained. The results of Evaluation 1 are shown in Table 2.
[0189] 実施例 5〜8 [0189] Examples 5-8
実施例 1において、ロッド状銀微粒子の平均アスペクト比を 54. 7から 3. 2 (実施例 5)、 12. 2 (実施例 6)、 78. 4 (実施例 7)、又は 1. 3 (実施例 8)にそれぞれ代えたこ と以外、実施例 1と同じにして、銀微粒子組成物を調製し、評価 1を行なうと共に、遮 光画像、カラーフィルタ、液晶表示素子、及び液晶表示装置を得た。評価 1の結果を 表 2に示す。  In Example 1, the average aspect ratio of the rod-shaped silver fine particles is 54.7 to 3.2 (Example 5), 12.2 (Example 6), 78.4 (Example 7), or 1.3 ( A silver fine particle composition was prepared and evaluated 1 in the same manner as in Example 1 except that each of them was replaced with Example 8), and a light shielding image, a color filter, a liquid crystal display element, and a liquid crystal display device were obtained. It was. The results of Evaluation 1 are shown in Table 2.
[0190] 実施例 9 [0190] Example 9
<転写材料の作成 >  <Creation of transfer material>
厚さ 75 μ mのポリエチレンテレフタレート仮支持体 (PET仮支持体）の表面に、スリ ット状ノズルを用いて、下記の処方 HIで調製された熱可塑性榭脂層用塗布液を塗 布し、塗布膜を 100°Cで 3分間乾燥させ、乾燥厚みが 5 mの熱可塑性榭脂層を形 成した。この熱可塑性榭脂層上に、下記処方 P1で調製された中間層用塗布液をスリ ットコ一ターを用いて塗布し、塗布膜を lOO°Cで 3分間乾燥させて、乾燥厚みが 1. 5Use a slit nozzle on the surface of a 75 μm thick polyethylene terephthalate temporary support (PET temporary support) to apply the thermoplastic resin coating solution prepared with the following formulation HI. The coating film is dried at 100 ° C for 3 minutes to form a thermoplastic resin layer with a dry thickness of 5 m. Made. On this thermoplastic resin layer, an intermediate layer coating solution prepared by the following formulation P1 was applied using a slit coater, and the coating film was dried at lOO ° C for 3 minutes to obtain a dry thickness of 1. Five
/z mの中間層（酸素遮断膜)を積層した。この中間層上に、実施例 1で調製した遮光 画像形成用塗布液を、スリットコーターを用いて塗布し、塗布膜を 100°Cで 3分間乾 燥させて乾燥膜厚が 0. 5 μ mの感光性遮光層 (金属黒色層）を形成した。 An intermediate layer (oxygen barrier film) of / z m was laminated. On this intermediate layer, the light-shielding image-forming coating solution prepared in Example 1 was applied using a slit coater, and the coating film was dried at 100 ° C. for 3 minutes to obtain a dry film thickness of 0.5 μm. The photosensitive light-shielding layer (metal black layer) was formed.
以上のようにして、 PET仮支持体上に熱可塑性榭脂層、中間層、及び感光性遮光 層が順次積層されたフィルムを作製し、遮光層の上に保護フィルムとして、厚さ 12 mのポリプロピレンフィルムを圧着して、感光性転写材料を得た。  As described above, a film in which a thermoplastic resin layer, an intermediate layer, and a photosensitive light-shielding layer were sequentially laminated on a PET temporary support was prepared, and a protective film having a thickness of 12 m was formed on the light-shielding layer. A polypropylene film was pressure-bonded to obtain a photosensitive transfer material.
[0191] 〈熱可塑性榭脂層用塗布液の処方 Hl〉 [0191] <Prescription of coating solution for thermoplastic resin layer Hl>
•メタノーノレ 1  • Methanore 1
'プロピレングリコールモノメチルエーテルアセテート … 6. 36部  'Propylene glycol monomethyl ether acetate… 6. 36 parts
•メチルェチルケトン · '·52. 4部  • Methyl ethyl ketone · '52. 4 parts
•メチルメタタリレート /2—ェチルへキシルアタリレート/ベンジルメタタリレート/メタ クリル酸共重合体 (共重合比 [モル比] = 55Zll. 7/4. 5/28. 8、重量平均分子 量 = 9万、 Tg 70。C) … 5. 83部 • Methyl methacrylate / 2—ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio [molar ratio] = 55 Zll. 7/4. 5/28. 8, weight average molecule Amount = 90,000, Tg 70. C)… 5. 83 parts
•スチレン Zアクリル酸共重合体 (共重合比 [モル比] = 63Z37、重量平均分子量 = 1万、 Tg 100。C) "· 13. 6部  • Styrene Z acrylic acid copolymer (copolymerization ratio [molar ratio] = 63Z37, weight average molecular weight = 10,000, Tg 100.C) "13.6 parts
•2, 2—ビス [4— (メタクリロキシポリエトキシ）フエ-ル]プロパン  • 2, 2-bis [4- (methacryloxypolyethoxy) phenol] propane
(新中村ィ匕学工業 (株)製;ビスフエノール Αにペンタエチレングリコールモノメタタリ ートを 2当量脱水縮合したィ匕合物） … 9. 1部  (Shin Nakamura Chemical Co., Ltd .; bisphenol kneaded with 2 equivalents of pentaethylene glycol monometatalite dehydrated)… 9.1 parts
'フッ素系界面活性剤 … 0. 54部  'Fluorosurfactant… 0. 54 parts
(大日本インキ化学工業 (株)製 F780F)  (F780F, manufactured by Dainippon Ink & Chemicals, Inc.)
[0192] 〈中間層用塗布液の処方 Pl〉 [0192] <Prescription Pl of intermediate layer coating solution>
•PVA- 205 … 32. 2部  • PVA- 205… 32. 2 copies
(ポリビュルアルコール、 （株)クラレ製、酸ィ匕度 = 88%、重合度 550)  (Polybulol alcohol, manufactured by Kuraray Co., Ltd., acidity = 88%, polymerization degree 550)
'ポリビュルピロリドン … 14. 9部  'Polybylpyrrolidone… 14. 9 parts
(アイ .エス .ピー .ジャパン (株)製、 K— 30)  (I.S.P. Japan Co., Ltd., K-30)
'蒸留水 一524部 •メタノーノレ - - -429 'Distilled water 524 parts • Methanore---429
[0193] <転写による遮光画像付き基板の作製 (転写法） >  [0193] <Production of substrate with shading image by transfer (transfer method)>
無アルカリガラス基板にガラス洗浄剤液をシャワーにより 20秒間吹き付けながらナ ィロン毛を有する回転ブラシで該無アルカリガラス基板を洗浄し、純水でシャワー洗 浄した後、シランカップリング液 (N— β (アミノエチル） γ—ァミノプロピルトリメトキシ シランの 0. 3%水溶液、信越ィ匕学工業 (株)製 ΚΒΜ603)をシャワーにより 20秒間吹 き付け、その後、純水でシャワー洗浄した。さらに、この基板を基板予備加熱装置を 用いて 100°Cで 2分間加熱した。  The alkali-free glass substrate is washed with a rotating brush having nylon hair while spraying a glass detergent solution on the alkali-free glass substrate for 20 seconds, shower-washed with pure water, and then a silane coupling solution (N-β (Aminoethyl) γ-aminopropyltrimethoxy silane 0.3% aqueous solution, Shin-Etsu Chemical Co., Ltd. ΚΒΜ603) was sprayed for 20 seconds with a shower, and then washed with pure water. Further, this substrate was heated at 100 ° C. for 2 minutes using a substrate preheating apparatus.
[0194] 続 、て、上記より得た感光性転写材料の保護フィルムを剥離後、露出した感光性 遮光層が、加熱後のガラス基板の表面と接するように重ね合わせ、ラミネーター Lami ell型〔(株）日立インダストリィズ製〕を用いて、ゴムローラ温度 130°C、線圧 lOON/c m2、搬送速度 2. 2mZ分の条件で感光性転写材料と基板を貼り合わせた (ラミネート )。次いで、獲られた積層体から PET仮支持体を剥離した (転写工程)。 [0194] Subsequently, after the protective film of the photosensitive transfer material obtained above was peeled off, the exposed photosensitive light-shielding layer was superposed so as to be in contact with the surface of the heated glass substrate, and a laminator Lamiell type [( Ltd.) using a Hitachi-in dust Ryizu], rubber roller temperature 130 ° C, linear pressure Loon / cm 2, bonding the photosensitive transfer material and the substrate under the condition of a conveying speed of 2. 2MZ minute (laminate). Next, the PET temporary support was peeled from the obtained laminate (transfer process).
[0195] 続、て、マスク（画像パターンを有する石英露光マスク）と、該マスクと熱可塑性榭 脂層とが向き合うように配置したガラス基板とを略平行に垂直に立てて、マスク面と感 光性榭脂層の中間層に接する側の表面との間の距離を 100 mに設定した。この状 態で、超高圧水銀灯を備えたプロキシミティー型露光機（日立電子エンジニアリング 社製)を用い、マスクを介して熱可塑性榭脂層側カゝら露光量 70mjZcm 2で感光性 遮光層をパターン露光した (露光工程)。 [0195] Subsequently, a mask (a quartz exposure mask having an image pattern) and a glass substrate disposed so that the mask and the thermoplastic resin layer face each other are set substantially parallel and perpendicular to each other, and the surface of the mask is sensed. The distance between the surface of the photosensitive resin layer on the side in contact with the intermediate layer was set to 100 m. In this state, using a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, pattern the photosensitive light-shielding layer with an exposure amount of 70 mjZcm 2 from the thermoplastic resin layer side through the mask. Exposed (exposure process).
[0196] 露光後、トリエタノールアミン系現像液 T— PD1 (2. 5%のトリエタノールァミン、ノ- オン界面活性剤、及びポリプロピレン系消泡剤含有、富士写真フィルム (株)製)をフ ラットノズルカゝら 30°C、ノズル圧力 0. 04MPa〖こて、熱可塑性榭脂層上から 50秒間 噴射してシャワー現像を行ない、熱可塑性榭脂層及び中間層を現像、除去した。引 き続き、純水をシャワーノズルにて感光性遮光層に噴霧して、感光性遮光層の表面 を均一に湿らせた後、 KOH系現像液 CDK— 1 (富士フィルムエレクト口-クスマテリ アルズ (株)製; KOH及びノ-オン界面活性剤含有アルカリ現像液)を純水で 100倍 に薄めたものを、フラットノズルから 23°C、ノズル圧力 0. 04MPa〖こて 80秒、間噴射し て感光性遮光層をシャワー現像し (現像工程)、パターン像を得た。続いて、超純水 を超高圧洗浄ノズルにて 9. 8MPaの圧力でパターン像に噴射して残渣除去を行な い、 220°Cで 40分間パターン像をベータし、遮光画像を得た。 [0196] After exposure, a triethanolamine developer T-PD1 (containing 2.5% triethanolamine, a nonionic surfactant, and a polypropylene antifoaming agent, manufactured by Fuji Photo Film Co., Ltd.) The flat nozzle cover was 30 ° C, the nozzle pressure was 0.04 MPa, sprayed from above the thermoplastic resin layer for 50 seconds to perform shower development, and the thermoplastic resin layer and the intermediate layer were developed and removed. Subsequently, after spraying pure water onto the photosensitive light-shielding layer with a shower nozzle to uniformly wet the surface of the photosensitive light-shielding layer, KOH developer CDK—1 (Fuji Film Elect Mouth-Cusmaterials ( Co., Ltd .; KOH and non-surfactant-containing alkaline developer) diluted 100 times with pure water, sprayed from flat nozzle at 23 ° C, nozzle pressure 0.04MPa iron for 80 seconds. The photosensitive light-shielding layer was shower-developed (development process) to obtain a pattern image. Next, ultrapure water The residue was removed by spraying onto the pattern image at a pressure of 9.8 MPa with an ultra-high pressure washing nozzle, and the pattern image was beta-treated at 220 ° C for 40 minutes to obtain a light-shielded image.
[0197] 比較例 1 [0197] Comparative Example 1
実施例 1にお 、て、ポリマー 1をべンジルメタタリレート Zメタクリル酸共重合体 (モル 比 = 73Z27、重量平均分子量： 3万）に代えたこと以外、実施例 1と同じにして、銀 微粒子組成物を調製し、評価 1を行なうと共に、遮光画像、カラーフィルタ、液晶表示 素子、及び液晶表示装置を得た。評価 1の結果は表 2に示す。  In Example 1, except that the polymer 1 was replaced with a benzyl metatalylate Z methacrylic acid copolymer (molar ratio = 73Z27, weight average molecular weight: 30,000), the same as in Example 1, A silver fine particle composition was prepared and evaluated 1, and a light-shielded image, a color filter, a liquid crystal display device, and a liquid crystal display device were obtained. The results of Evaluation 1 are shown in Table 2.
[0198] 評価 2 [0198] Rating 2
- 2.色相の評価  -2. Hue evaluation
各実施例及び比較例で得られた遮光画像の色度を、顕微分光光度計 OSP100 ( ォリンパス光学 (株)製を用いて、ピンホール径 5 mにて測定し、 F10光源視野 2度 の結果として計算した。そして、理想的な黒色を x=0. 33、 y=0. 33とし、得られた 値 (X, y値)との色差 Δ Εを算出して、色相を評価する指標とした。なお、色差 Δ Εの 値が小さい方が黒の色相が良好であることを示す。評価結果は下記表 2に示す。  The chromaticity of the light-shielded image obtained in each Example and Comparative Example was measured at a pinhole diameter of 5 m using a microspectrophotometer OSP100 (manufactured by Olympus Optical Co., Ltd.). The ideal black is x = 0.33 and y = 0.33, and the color difference Δ Ε from the obtained values (X, y values) is calculated to evaluate the hue. The smaller the color difference ΔΕ, the better the black hue, and the evaluation results are shown in Table 2 below.
[0199] 3.透過濃度の評価  [0199] 3. Evaluation of transmission density
各実施例及び比較例で得られた遮光画像 (膜)の透過濃度 (OD)を、マクベス濃度 計 (マクベス社製 TD— 904)を用いて測定した。その際、測定された濃度をガラス基 板の光学濃度分、補正した。評価結果は下記表 2に示す。  The transmission density (OD) of the light-shielded image (film) obtained in each Example and Comparative Example was measured using a Macbeth densitometer (TD-904 manufactured by Macbeth). At that time, the measured density was corrected by the optical density of the glass substrate. The evaluation results are shown in Table 2 below.
[0200] [表 2] [0200] [Table 2]
Figure imgf000045_0001
Figure imgf000045_0001
*1： 銀微粒子組成物中における銀粒子の凝集のだめ、遮光画像を得ることはできなかった。  * 1: Aggregation of silver particles in the silver fine particle composition was not possible, and a light-shielded image could not be obtained.
[0201] 前記表 2に示すように、チォエーテル基を有する高分子化合物を用いた実施例で は、金属微粒子の分散安定性が優れており、形成された遮光画像は透過濃度が高く 、加熱された後でも色差が小さく抑えられ、良好な色相の黒色像を得ることができた。 特にアスペクト比が 2〜： L00の銀微粒子を用いて膜を形成した場合に、透過濃度が 高ぐ加熱された後の色差が小さぐ色相に優れていた。 [0201] As shown in Table 2, in Examples using a polymer compound having a thioether group, the dispersion stability of metal fine particles is excellent, and the formed light-shielded image has a high transmission density and is heated. Even after this, the color difference was kept small, and a black image with a good hue could be obtained. In particular, when a film was formed using silver fine particles having an aspect ratio of 2 to L00, it was excellent in hue with small color difference after heating with high transmission density.
これに対し、チォエーテル基を有する高分子化合物を用いない比較例 1では、分 散安定性が不充分であり、銀粒子が凝集を起こして遮光画像を得ることはできなかつ た。  On the other hand, in Comparative Example 1 in which a polymer compound having a thioether group was not used, the dispersion stability was insufficient, and silver particles were aggregated and a light-shielded image could not be obtained.
[0202] 評価 3  [0202] Rating 3
4.着色画素の評価  4. Evaluation of colored pixels
実施例 1〜9及び比較例 1で得られたカラーフィルタの各々の着色パターンを顕微 鏡観察により評価した。その結果、実施例のカラーフィルタはいずれも、比較例の力 ラーフィルタに比し、欠陥がない着色画素と、精細なパターンを有していた。  The coloring patterns of the color filters obtained in Examples 1 to 9 and Comparative Example 1 were evaluated by microscopic observation. As a result, all of the color filters of the examples had colored pixels having no defect and a fine pattern as compared with the power filter of the comparative example.
[0203] 評価 4 [0203] Rating 4
5.画質の評価  5. Image quality evaluation
実施例 1〜9及び比較例 1で得られた液晶表示装置の各々を用いて画像を表示し 、表示画像の品質を目視により評価した。その結果、実施例の液晶表示装置はいず れも、比較例の液晶表示装置に比し、高コントラストで鮮ゃ力な画像表示が可能であ り、良好な表示特性を示すことを確認した。 Images were displayed using each of the liquid crystal display devices obtained in Examples 1 to 9 and Comparative Example 1, and the quality of the displayed images was visually evaluated. As a result, all of the liquid crystal display devices of the examples are capable of displaying images with high contrast and a clear power compared to the liquid crystal display devices of the comparative examples. As a result, it was confirmed that good display characteristics were exhibited.

Claims

請求の範囲 The scope of the claims
[1] 少なくとも、金属微粒子及び Z又は金属化合物微粒子と、少なくとも 1つのチォェ 一テル基を有する高分子化合物と、熱もしくは光で硬化する化合物とを含有する微 粒子含有組成物。  [1] A fine particle-containing composition comprising at least metal fine particles and Z or metal compound fine particles, a polymer compound having at least one thiol group, and a compound that is cured by heat or light.
[2] 前記高分子化合物が、少なくとも一種のチォエーテル構造を側鎖に含むエチレン 性不飽和単量体から誘導される繰り返し単位を有する請求項 1の微粒子含有組成物  2. The fine particle-containing composition according to claim 1, wherein the polymer compound has a repeating unit derived from an ethylenically unsaturated monomer containing at least one thioether structure in the side chain.
[3] 前記高分子化合物が、下記一般式 (1)で表される繰り返し単位を少なくとも有する 請求項 1の微粒子含有組成物。 [3] The fine particle-containing composition according to claim 1, wherein the polymer compound has at least a repeating unit represented by the following general formula (1).
[化 1]  [Chemical 1]
一般式。）General formula. )
Figure imgf000047_0001
Figure imgf000047_0001
〔式中、 R1は、水素原子又は総炭素数 1〜4のアルキル基を表し、 R2は水素原子、 総炭素数 1〜18のアルキル基、総炭素数 6〜14のァリール基、又は総炭素数 7〜1 6のァラルキル基を表す。 Zは、—O—又は—NH—を表し、 Yは総炭素数 1〜8の 2 価の連結基を表す。〕 [Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms in total, R 2 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms in total, an aryl group having 6 to 14 carbon atoms in total, or This represents an aralkyl group having a total carbon number of 7 to 16. Z represents —O— or —NH—, and Y represents a divalent linking group having 1 to 8 carbon atoms in total. ]
[4] 前記高分子化合物が酸基を更に有する請求項 1の微粒子含有組成物。 4. The fine particle-containing composition according to claim 1, wherein the polymer compound further has an acid group.
[5] 前記酸基がカルボン酸基である請求項 4の微粒子含有組成物。 5. The fine particle-containing composition according to claim 4, wherein the acid group is a carboxylic acid group.
[6] 前記金属微粒子及び Z又は金属化合物微粒子は 2〜： L00のアスペクト比を有する 請求項 1の微粒子含有組成物。 6. The fine particle-containing composition according to claim 1, wherein the metal fine particles and the Z or metal compound fine particles have an aspect ratio of 2 to L00.
[7] 多官能モノマーを更に含有する請求項 1の微粒子含有組成物。 7. The fine particle-containing composition according to claim 1, further comprising a polyfunctional monomer.
[8] 光重合開始剤を更に含有する請求項 1の微粒子含有組成物。 8. The fine particle-containing composition according to claim 1, further comprising a photopolymerization initiator.
[9] 請求項 1の微粒子含有組成物を含む表示装置用着色膜形成用インク。 [9] A colored film forming ink for a display device, comprising the fine particle-containing composition according to claim 1.
[10] 請求項 1の微粒子含有組成物又は請求項 9の表示装置用着色膜形成用インクを 用いて形成された表示装置用遮光膜。 [10] A light-shielding film for a display device, which is formed using the fine particle-containing composition according to claim 1 or the colored film-forming ink for display device according to claim 9.
[11] 表示装置用遮光膜の形成に用いられる遮光材料であって、 [11] A light shielding material used for forming a light shielding film for a display device,
支持体上に、アスペクト比が 2〜： LOOの金属微粒子及び Z又は金属化合物微粒子 と、少なくとも 1つのチォエーテル基を有する高分子化合物と、熱もしくは光で硬化す る化合物とを少なくとも含有する微粒子含有層を少なくとも 1層有する遮光材料。  On a support, fine particles containing at least an LOO metal fine particle and a Z or metal compound fine particle, a polymer compound having at least one thioether group, and a compound curable by heat or light A light shielding material having at least one layer.
[12] 多官能モノマーを更に含有する請求項 11の遮光材料。  12. The light shielding material according to claim 11, further comprising a polyfunctional monomer.
[13] 光重合開始剤を更に含有する請求項 11の遮光材料。  [13] The light-shielding material according to claim 11, further comprising a photopolymerization initiator.
[14] 前記微粒子含有層が被転写体への転写が可能な層である請求項 11の遮光材料。  14. The light-shielding material according to claim 11, wherein the fine particle-containing layer is a layer that can be transferred to a transfer target.
[15] 請求項 1の微粒子含有組成物、請求項 9の表示装置用着色膜形成用インク、又は 請求項 11の遮光材料を用いて形成された遮光膜を有する遮光膜付き基板。 [15] A substrate with a light-shielding film having a light-shielding film formed using the fine particle-containing composition according to claim 1, the ink for forming a colored film for a display device according to claim 9, or the light-shielding material according to claim 11.
[16] 光透過性の基板上に、異なる色相を呈する複数の画素と、前記複数の画素の各々 を離隔する遮光画像とを有するカラーフィルタにおいて、前記遮光画像が請求項 10 の表示装置用遮光膜であるカラーフィルタ。 [16] In the color filter having a plurality of pixels exhibiting different hues and a light-shielding image separating each of the plurality of pixels on a light-transmitting substrate, the light-shielding image is a light-shielding device for a display device according to claim 10. A color filter that is a film.
[17] 請求項 15の遮光膜付き基板を備えたカラーフィルタ。 [17] A color filter comprising the substrate with a light-shielding film according to claim 15.
[18] 請求項 15の遮光膜付き基板を備えた液晶表示素子。 18. A liquid crystal display device comprising the substrate with a light shielding film according to claim 15.
[19] 請求項 18の液晶表示素子を備えた液晶表示装置。 19. A liquid crystal display device comprising the liquid crystal display element according to claim 18.
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