WO2007046371A1 - Method for producing metal particle dispersion, metal particle dispersion, and colored composition, photosensitive transfer material, substrate with light-blocking image, color filter and liquid crystal display each using such metal particle dispersion - Google Patents

Method for producing metal particle dispersion, metal particle dispersion, and colored composition, photosensitive transfer material, substrate with light-blocking image, color filter and liquid crystal display each using such metal particle dispersion Download PDF

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Publication number
WO2007046371A1
WO2007046371A1 PCT/JP2006/320646 JP2006320646W WO2007046371A1 WO 2007046371 A1 WO2007046371 A1 WO 2007046371A1 JP 2006320646 W JP2006320646 W JP 2006320646W WO 2007046371 A1 WO2007046371 A1 WO 2007046371A1
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Prior art keywords
particle dispersion
metal fine
light
group
metal
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PCT/JP2006/320646
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French (fr)
Japanese (ja)
Inventor
Katsuyuki Takada
Kousaku Yoshimura
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Fujifilm Corporation
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Priority to CN2006800390843A priority Critical patent/CN101291763B/en
Publication of WO2007046371A1 publication Critical patent/WO2007046371A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

Definitions

  • the present invention relates to a method for producing a metal fine particle dispersion containing metal fine particles, and a metal fine particle dispersion.
  • the present invention also relates to a coloring composition, a photosensitive transfer material, a substrate with a light-shielding image, a color filter, and a liquid crystal display device using the same.
  • coloring compositions for black materials have been used for printing inks, inkjet inks, etching resists, solder resists, plasma display panel (PDP) partition walls, dielectric patterns, electrode (conductor circuit) patterns, and electronic components.
  • Widely used for shading images such as wiring patterns, conductive pastes, conductive films, and black matrices.
  • the shading image is a black edge provided around the periphery of a display device such as a liquid crystal display device, a plasma display device, an EL display device, a CRT display device, or a grid pattern between red, blue, and green pixels.
  • black matrix hereinafter sometimes referred to as “BM”
  • BM is generally used to improve display contrast.
  • BM is also used to prevent image degradation due to current leakage due to light in the case of active matrix liquid crystal display devices using thin film transistors (TFTs).
  • TFTs thin film transistors
  • An optical density of 3 or more) is required.
  • liquid crystal display devices have been applied to televisions (hereinafter sometimes referred to as “TV”).
  • TV televisions
  • power filters with low transmittance and high color purity are used, and the brightness of the backlight tends to increase in order to obtain high brightness.
  • BM is required to have a high light-shielding property in order to prevent a decrease in contrast and see-through of the peripheral frame portion.
  • TVs used for home use and installation are concerned about TFT deterioration due to sunlight, which is often installed in a room where sunlight enters for a long period of time.
  • BM requires a high level of light and light shielding.
  • Examples of BM include those having a metal film such as chromium as a light shielding layer.
  • a metal thin film is produced by vapor deposition or sputtering, a photoresist is applied on the metal thin film, and then BM is used. It is known to form a BM by exposing and developing a photoresist layer using a photomask with a pattern, etching the exposed metal thin film, and finally peeling the resist layer on the metal thin film. (For example, see Non-Patent Document 1).
  • this method of manufacturing BM using a photoresist uses a metal thin film, there is an advantage that a high light shielding effect can be obtained even if the film thickness is small.
  • the cost is increased because an evaporation method, a sputtering method, a vacuum film forming step and an etching step are required.
  • the light shielding layer is a metal film, there is a problem that the display contrast is low under strong external light with high reflectivity.
  • a method using a photosensitive resin composition containing a light-shielding pigment such as carbon black is also known.
  • a photosensitive resin composition containing a light-shielding pigment such as carbon black is also known.
  • a carbon black-containing photosensitive resin composition is applied on the pixels, and the R, G, B pixel non-formation surface of the transparent substrate is applied.
  • a self-alignment BM formation method is known in which the entire surface is exposed from the side (see, for example, Patent Document 1).
  • the method is lower in production cost than the method by etching the metal film, there is a problem that the film thickness is increased in order to obtain sufficient light shielding properties.
  • overlap (step) occurs between BM and R, G, and B pixels, and the flatness of the color filter deteriorates, resulting in cell gap unevenness in the liquid crystal display device, leading to display defects such as display unevenness.
  • Display unevenness is said to be a cause of display unevenness when the black matrix substrate surface is not smooth, which causes display unevenness.
  • a gray test signal is input to the liquid crystal display device, It is a faint unevenness observed.
  • the “straight stripes” that appear to be relatively sticky streaks are generated during the formation of alignment control protrusions, such as thickness unevenness, exposure unevenness, development processing unevenness, and heat treatment unevenness that occurred during the formation of the photosensitive resin layer.
  • the force mechanism that may cause unevenness between the alignment control protrusion and the liquid crystal when functioning as a liquid crystal display device is not clear.
  • a photosensitive resist layer containing a hydrophilic resin is formed on a transparent substrate, exposed through a photomask having a BM pattern, and developed to form a relief on the transparent substrate.
  • the transparent substrate is brought into contact with an aqueous solution of a metal compound serving as a catalyst for electroless plating, the metal compound is contained in the relief, dried, and then subjected to heat treatment, and then the relief on the transparent substrate is transferred to the electroless plating solution.
  • a method for producing a BM in which metal particles for light shielding having a particle size of 0.01-0.05 / im are uniformly dispersed therein has been proposed (see, for example, Patent Document 2). ).
  • the metal particles nickel, cobalt, iron, copper, and chromium are described, and nickel is shown as a specific example.
  • this method has many troublesome processing steps for handling water, such as application of relief forming electroless plating catalyst, heat treatment, and electroless plating including an exposure and development step. As a result, BM production at low cost cannot be expected.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 62-9301
  • Patent Document 2 Japanese Patent No. 3318353
  • Patent Document 3 Japanese Patent Laid-Open No. 2001-13678
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2004-334180
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2005-17322
  • Patent Document 6 Japanese Patent Laid-Open No. 2003-193118
  • Patent Document 7 Japanese Unexamined Patent Application Publication No. 2004-346429
  • Non-Patent Document 1 Kyoritsu Shuppan Co., Ltd. “Color TFT Liquid Crystal Display” pp. 218-220 (10 April, 1997)
  • the present invention relates to a method for producing a highly dispersed metal fine particle dispersion having stability over time, a metal fine particle dispersion, a coloring composition using the same, and a photosensitive transfer material.
  • the purpose is to provide.
  • the present invention has a light-shielded image including a high black film or a black matrix, or an image including a colored film having a high density with a thin film.
  • Another object of the present invention is to provide a substrate with a light-shielding image, a color filter excellent in flatness and low display unevenness, and a liquid crystal display device.
  • a method for producing a metal fine particle dispersion in which metal ions are reduced in the presence of an alkali-soluble polymer having one or more sulfur atoms and one or more Z or nitrogen atoms to form metal fine particles is a method for producing a metal fine particle dispersion in which metal ions are reduced in the presence of an alkali-soluble polymer having one or more sulfur atoms and one or more Z or nitrogen atoms to form metal fine particles.
  • ⁇ 2> The method for producing a metal fine particle dispersion according to ⁇ 1>, wherein the alkali-soluble polymer has an acidic group.
  • / O value is a metal fine particle dispersion according to the above ⁇ 6> to ⁇ 9>, which is 0.44 or more and 1.65 or less.
  • the metal fine particles are one type selected from Group 2 to Group 14 of the Periodic Table or
  • the ⁇ 6> to ⁇ 10> metal fine particle dispersion containing two or more metals [0026] ⁇ 12> A colored composition comprising the metal fine particle dispersion of ⁇ 6> to ⁇ 11>. [0027] ⁇ 13> The colored composition of ⁇ 12>, which is black.
  • a photosensitive transfer material in which at least one photosensitive light-shielding layer is provided on a support, wherein the photosensitive light-shielding layer uses the metal fine particle dispersion of ⁇ 6> to ⁇ 11>. It is a photosensitive transfer material that is formed.
  • a method for producing a dense metal fine particle dispersion having high temporal stability and stability over time, a metal fine particle dispersion, a coloring composition using the same, and a photosensitive transfer material Can provide you with power.
  • a color filter and a liquid crystal display device with low unevenness can be provided.
  • the method for producing a metal fine particle dispersion of the present invention comprises an alkali-soluble polymer having one or more sulfur atoms and / or nitrogen atoms (hereinafter sometimes referred to as "alkali-soluble polymer in the present invention").
  • the metal ions are reduced in the presence of to form metal fine particles.
  • the metal fine particle dispersion of the present invention contains an alkali-soluble polymer having at least one sulfur atom and / or nitrogen atom and metal fine particles.
  • the coloring composition of the present invention contains the metal fine particle dispersion of the present invention, and if necessary,
  • the coloring composition of the present invention may contain at least one kind of a resin or a precursor thereof, pigment fine particles, a polymer serving as a binder, a monomer, an initiator, a solvent, and the like.
  • a dense metal fine particle colored composition having high dispersion stability can be prepared, and since the coating solution has high stability with time and little stickiness, a thin film with a black density (light-shielding property) It is possible to stably produce a light-shielded image such as a black film or black matrix having a high performance or a colored film having a high density in a thin film.
  • the fine metal particle dispersion and the colored composition of the present invention include printing ink, inkjet ink, photomask preparation material, printing proof preparation material, etching resist, solder resist, plasma display panel (PDP) partition, dielectric It can be used for shading images of body patterns, electrode (conductor circuit) patterns, wiring patterns of electronic components, conductive pastes, conductive films, black matrices, and the like.
  • the metal fine particle dispersion and the colored composition of the present invention are shielded from the spacing between the colored pattern, the peripheral portion, and the outside light side of the TFT in order to improve the display characteristics of the color filter used in the color liquid crystal display device. It can be suitably used to provide an image.
  • the black edges provided around the periphery of display devices such as liquid crystal display devices, plasma display devices, EL display devices, and CRT display devices, as well as grids and stripes between red, blue, and green pixels. It is particularly preferably used as a black matrix such as a black part, more preferably a dot-like or linear black pattern for TFT light shielding.
  • the metal fine particle dispersion of the present invention contains an alkali-soluble polymer having one or more yellow atoms and / or nitrogen atoms and metal fine particles.
  • the metal of the metal fine particles in the present invention is not particularly limited, and any metal may be used. Further, the metal fine particles in the present invention can also be used as an alloy that can be used in combination of two or more metals. Furthermore, the metal fine particle in the present invention may be a metal compound or a composite fine particle of a metal compound and a metal. Among them, the metal fine particles in the present invention are particularly preferably those formed from a metal that is preferably formed from a metal and / or a metal compound.
  • a metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the long periodic table is included as a main component.
  • the metal fine particles in the present invention preferably contain a metal selected from the group consisting of Groups 2 to 14: Group 2, Group 8, Group 9, Group 10 and Group 11. More preferably, the main component is a metal selected from the group consisting of Group 12, Group 13, and Group 14.
  • Preferred examples of dispersed metal fine particles as the metal fine particles include, for example, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, Tungsten, niobium, tantalum, titanium, bismuth, antimony, lead, or an alloy thereof, and at least one of which power is also selected. More preferable metals are copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium or alloys thereof, and more preferable metals are selected from copper, silver, gold, platinum, tin or alloys thereof. At least one kind.
  • the metal fine particles in the present invention can be obtained by reducing metal ions in the presence of the alkali-soluble polymer in the present invention.
  • the metal particles in the present invention are obtained by adding a metal salt-containing solution and a reducing agent in the presence of the alkali-soluble polymer in the present invention, mixing them, and reducing the metal ions.
  • the metal salt can be used without particular limitation, and examples thereof include metal salts such as chloride, nitrate, nitrite, sulfate, ammonium salt, and acetate.
  • the reducing agent is not particularly limited as long as it is normally used.
  • metal borohydrides such as sodium borohydride and potassium borohydride; lithium aluminum hydride, hydrogenation Aluminum potassium, cesium hydride, aluminum beryllium hydride, magnesium aluminum hydride, aluminum hydride, aluminum hydride salts such as rum, hydrazine compounds, dextrin, hydroquinone, hydroxynoramine, citrate and its salts, succinic acid And its salt, ascorbic acid and its salt, and the like.
  • a method of adding a metal salt and a reducing agent is not particularly limited, and can be appropriately adjusted according to the conditions for producing fine metal particles to be prepared.
  • the “metal compound” in the present invention is a compound of a metal as described above and an element other than the metal.
  • Examples of the compound of the metal and other elements include metal oxides, sulfides, sulfates, carbonates and the like. Of these, sulfide is particularly preferable from the viewpoint of color tone and fine particle formation. Examples of these metal compounds include, for example, copper oxide (11), iron sulfide, silver sulfide, copper sulfide (11), titanium black, and the like, from the viewpoint of color tone, fine particle formation, and stability. Silver sulfide is particularly preferred.
  • composite fine particles of metal compound and metal refers to particles in which a metal and a metal compound are combined into one particle.
  • examples of such composite fine particles include those having different compositions between the inside and the surface of the particles, and those obtained by combining two kinds of particles.
  • the metal compound and the metal constituting the composite fine particles may be one kind or two kinds or more, respectively.
  • Specific examples of the composite fine particles of metal compound and metal 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 in the present invention may be core-shell type composite particles.
  • the core-shell type composite particle is obtained by coating the surface of a core material with a shell material.
  • shell materials used for core-shell type composite particles include Si, Ge, AlSb, InP, Ga, As, GaP, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, Pb Te, At least one semiconductor selected from Se, Te, CuCl, CuBr, Cul, T1C1, TlBr, Til and their solid solutions and solid solutions containing 90 mol% or more of these; or copper, silver, gold, platinum, palladium, eckenole , Tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantanore, titanium, bismuth, antimony, lead, or alloys
  • Preferred examples of the core material include, for example, copper, silver, gold, palladium, nickel, tin
  • the shell material is also preferably used as a refractive index adjusting agent for the purpose of reducing the reflectance.
  • a method for continuously forming a metal compound shell on the surface in the process of producing metal fine particles can be used.
  • a reducing agent is added to a metal salt solution, a part of metal ions is reduced to produce metal fine particles, and then a sulfide such as sodium sulfide or ammonium sulfide is added, There is a method of forming a metal sulfide around the produced metal fine particles.
  • the color of metal particles may change depending on the particle shape.
  • the shape of the metal fine particles in the present invention is not particularly limited and may be any shape, but it is preferable to include metal fine particles having different aspect ratios.
  • the main shapes of the metal fine particles in the present invention are ampang, potato, rod (needle, columnar, rectangular parallelepiped, rugby ball, etc.), flat plate (scale, ellipse plate, plate) It may be in the form of a fiber, a confetti, a coil, or the like, preferably a plate-like particle or a rod.
  • the “aspect ratio” of the metal fine particles means a value obtained by dividing the major axis length of the metal fine particles defined as described later by the minor axis length, and was measured for 100 metal fine particles. It is defined as the average value.
  • the projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification.
  • the diameter (major axis length, minor axis length) of the metal fine particles is a box (cuboid) in which one metal fine particle is exactly (contained) with the metal fine particle as a triaxial diameter. Box length L, width b, height or thickness t are defined as the dimensions of this metal fine particle.
  • the number average particle diameter of the metal fine particles in the present invention is not particularly limited as long as it does not exceed the film thickness to be formed, but the number average particle diameter of the metal fine particles is preferably in the range of 10 nm to 1000 nm. The range of ⁇ 500 nm is more preferred. The range of 10 nm to 200 nm is more preferred.
  • the number average particle size of the metal fine particles in the present invention is less than 10 nm, it is difficult to produce the color filter produced using the metal fine particles having the number average particle size. It may not be preferable in that it looks like Hananare.
  • the number average particle size of the metal fine particles in the present invention exceeds lOOOnm, the stability of the dispersed material in which the particles are dispersed may be lowered, and the light shielding property may be deteriorated.
  • particle diameter refers to the diameter when an electron micrograph image of a particle is a circle of the same area
  • number average particle diameter refers to the above-mentioned particle diameter for a number of particles. This means the average value of 100 pieces.
  • the metal fine particles in the present invention are not particularly restricted in the particle size distribution.
  • the metal fine particle dispersion according to the present invention reduces the metal ion in the presence of an alkali-soluble polymer having at least one sulfur atom and / or nitrogen atom to form metal fine particles, thereby stabilizing the dispersion of the metal fine particles.
  • reducing the metal ion in the “in the presence” of the alkali-soluble polymer in the present invention usually means reducing the metal-soluble salt and the metal-containing salt in a container in which the alkali-soluble polymer in the present invention has been previously dissolved.
  • the salt containing the noble and the reducing agent may be dissolved in separate containers, and these may be added simultaneously to separately prepared reaction containers. Since the alkali-soluble polymer in the present invention has the effect of improving the dispersion stability of the metal fine particles, it is preferably present in the reaction vessel before or just after the metal fine particles are formed.
  • the metal fine particles in the present invention are dispersed in the metal fine particle dispersion of the present invention.
  • the state of the presence of the metal fine particles during dispersion is not particularly limited, but it is preferable that the metal fine particles exist in a stable dispersed state. A force beam is preferred.
  • the metal fine particle dispersion of the present invention can be subjected to solvent substitution after the preparation of the metal fine particles.
  • solvent replacement an acid is added to the metal fine particle dispersion, the pH is adjusted to 7.5 or less, and the aggregated nanoparticles by soft aggregation of the metal fine particles are precipitated. Next, the supernatant is removed, this is washed several times with water, and a nonpolar solvent is gradually added from the water, and the solvent is successively replaced.
  • redispersion is performed after solvent replacement, it is preferable to perform mechanical dispersion using ultrasonic waves, a bead mill disperser, or the like. By performing such redispersion, impurities such as the remaining reducing agent can be removed and solvent replacement can be performed. Further, instead of decantation, means such as suction filtration and centrifugation may be used.
  • the solvent used for the solvent substitution is not particularly limited, and among them, those having an SP value of 9.0 or more are preferable.
  • the “SP value” is also called a solubility parameter, and is expressed by the square root of the cohesive energy density.
  • the SP value means that described on page 838 of “Adhesion Handbook” (edited by the Japan Adhesive Society, published by Nikkan Kogyo Shimbun, published in 1971, first edition).
  • the above SP values are, for example, n-xan / 7.3, toluene / 8.9, ethyl acetate / 9.1 methylinetenoregigen / 9.3, sensane / 100.0, ethinore / renore / 12.7, Metinore finished Lucor / 14.5, water / 23.4, etc.
  • the unit of the SP value is “(cal / cm 3 ) 1/2 ”.
  • the dispersibility is particularly good, and methylethylketone, 2-propanol, 1 propanol, 1-methoxy-2-propylacetate, cyclohexanone, acetone, N —Methylpyrrolidone or a mixture thereof is preferably raised.
  • the content of the metal fine particles in the metal fine particle dispersion of the present invention is such that the metal solid mass in the dispersion is 70 mass relative to the total solid content from the viewpoint of more effectively exerting the effects of the present invention. It is particularly preferable that it is 80% by mass or more, more preferably 85% by mass or more.
  • the alkali-soluble polymer in the present invention may be a polymer containing both a sulfur atom and a nitrogen atom, or may be a polymer having either one of a sulfur atom or a nitrogen atom.
  • the effects of the present invention can be obtained.
  • polymer having a sulfur atom a polymer having a thioether group, a mercapto group, a sulfide group, or a thixo group is preferred.
  • polymer having a nitrogen atom a polymer having an amino group or an imino group, or a nitrogen-containing complex is preferred. Ring compounds are preferred.
  • nitrogen-containing heterocycle examples include 2_mercaptobenzimidazole, pyrrole, pyrrolidine, oxazole, thiazole, imidazole, pyrazole, pyridine, piperidine, pyridazine, pyrimidine, pyrazine, indole, quinoline, and benzimidazole. These groups may be unsubstituted or substituted.
  • the alkali-soluble polymer in the present invention may have the above-described group containing a sulfur atom or nitrogen atom as a polymer (including a copolymer) described later or a side chain terminal group of a polymerizable compound. Moreover, although it may have other than the side chain terminal, what has as a side chain terminal group is preferable.
  • a polymer (including a copolymer) or a polymerizable compound is also simply referred to as a polymer.
  • alkali solubility means insoluble in distilled water (H0) and pHIO.
  • a water-soluble polymer compound is soluble in an alkaline aqueous solution, but is similarly soluble in distilled water, and is therefore excluded from the polymer in the present invention.
  • alkali solubility in the present invention can be determined, for example, by the following evaluation method.
  • Preferred examples of the alkali-soluble polymer in the present invention include those having an acidic group.
  • the acidic group is not particularly limited and can be appropriately selected according to the purpose.
  • Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a boronic acid, a phenol, a sulfoamide, and the like. Among these, a carboxynole group is preferable.
  • the amount of the structural unit having an alkali-soluble group in the alkali-soluble polymer in the present invention is determined by the presence of the alkali-soluble group, so that the alkali-soluble polymer in the present invention has an pH of 10 to 13: If it can melt
  • the acid value of the alkali polymer in the present invention is not particularly limited, and can be appropriately selected according to the purpose.
  • 70 to 300 (mgKOH / g) is preferable 90 to 250 (mgK 100 to 200 (mgKH / g) is particularly preferable from the viewpoint of dispersion stability.
  • Examples of the polymer having a carboxyl group as the acidic group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, a modified epoxy resin, and the like.
  • a vinyl copolymer having a carboxynole group is preferred from the standpoints of solubility in water, solubility in an alkali developer, synthesis suitability, ease of adjustment of film properties, and the like.
  • a copolymer of at least one of styrene and a styrene derivative is also preferable.
  • the bull copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a bull monomer having a carboxyl group and (2) a monomer copolymerizable with the bull monomer of (1). it can.
  • butyl monomer having a carboxyl group examples include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and hydroxyl group.
  • Monomer having (for example, 2-hydro Xetyl (meth) acrylate, etc.) and cyclic anhydrides eg maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ⁇ -carboxypoly polyprolatathone mono (meth) Atallate and the like are listed.
  • (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost and solubility.
  • (meth) acrylic acid is a generic term for acrylic acid and methacrylic acid, and the same applies to derivatives thereof.
  • monomers having anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. may be used as the precursor of the carboxyl group.
  • the monomer (1) copolymerizable with the bull monomer is not particularly limited and can be appropriately selected according to the purpose.
  • Examples of the (meth) acrylic acid esters include methyl (meth) acrylate and ethyl.
  • crotonic acid esters examples include butyl crotonic acid and hexyl crotonic acid.
  • butyl esters examples include butyl acetate, bupropionate, butyl butyrate, vinyl methoxyacetate, and benzoic acid butyl.
  • maleic acid diesters examples include dimethyl maleate, diethyl maleate, and dibutyl maleate.
  • fumaric acid diesters examples include dimethyl fumarate, jetyl fumarate, and dibutyl fumarate.
  • Examples of the itaconic acid diesters include dimethyl itaconate, jetyl itaconate, and dibutyl itaconate.
  • the (meth) acrylamides include, for example, (meth) atalinoleamide, ⁇ -methinole (meth) acrylolamide, ⁇ ethyl (meth) acrylamide, ⁇ -propyl (meth) acrylamide, ⁇ -isopropyl (meth) ) Acrylamide, ⁇ _ ⁇ _Butyl Atalinole (meth) acrylamide, ⁇ -tert Butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (Meth) acrylamide, N, N-di Examples include ethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) atalyloylmorpholine, diacetone acrylamide and the like.
  • Examples of the butyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, and the like.
  • Examples of the esters of butyl alcohol include versato acid butyl, acetate butyl, formate butyl, propionate butyl, butyrate butyl.
  • styrenes examples include styrene, methyl styrene, dimethyl styrene, trimethylol styrene, ethynole styrene, isopropyleno styrene, butino styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, diethylene styrene.
  • Examples include styrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, tert-butyloxycarbonyl group), methyl vinyl benzoate, and monomethylstyrene. .
  • the molecular weight of the alkali-soluble polymer in the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of dispersion stability of the metal fine particles, for example, the weight average molecular weight is 2, 000-300,000 force S preferred, 4,000-: 150,000 force S more preferred, 6000-: 100,000 force S particularly preferred, 0
  • the organic / inorganic ratio (I / O value) in the organic conceptual diagram of the alkali-soluble polymer in the present invention is preferably 0.44 or more and 1.65 or less 0.5 or more and 0.6. The following are more preferred: If the I / O value is too low, it becomes soluble in water, and if the I / O value is high, it becomes insoluble in an alkaline aqueous solution.
  • the sulfur atom content in the polymer is preferably 0.5% by mass to 20% by mass from the viewpoint of dispersion stability of the metal fine particles. From 0% by mass to 10.0% by mass is more preferable.
  • the alkali-soluble polymer in the present invention has a nitrogen atom, the content of the nitrogen atom in the polymer is
  • the alkali-soluble polymer in the present invention has both a sulfur atom and a nitrogen atom
  • the mass ratio (sZn) of the sulfur atom (s) to the nitrogen atom (n) is determined from the viewpoint of dispersion stability of the metal fine particles. , 0.01-200 is preferred 0. :!-20 is more preferable.
  • alkali-soluble polymer in the present invention contains a sulfur atom
  • a polymer compound having at least one repeating unit represented by the following general formula (1) include, for example, a polymer compound having at least one repeating unit represented by the following general formula (1). It is done.
  • 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 include methinole group, ethyl group, nonolemanolepropyl group, isopropyl group, normal butyl group, sec butyl group, isobutyl group, tert-butyl group, etc. Groups are preferred.
  • R 2 represents a hydrogen atom, an alkyl group having a total carbon number of! To 18, an aryl group having a total carbon number of 6 to 14 or a aralkyl having a total carbon number of 7 to 16.
  • the alkyl group, aryl group, and aralkyl group each independently may be unsubstituted or substituted, and may form a saturated or unsaturated cyclic structure. ,.
  • the alkyl group having 1 to 18 carbon atoms in total represented by R 2 may be unsubstituted or substituted, and examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, Examples thereof include alkyl groups such as normal butyl group, sec butyl group, isobutyl group, tert-butyl group, hexyl group, octinole group, dodecyl group and stearyl group.
  • substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxynole group, an ester group, a sulfonyl group and the like are preferable.
  • an alkyl group having a total carbon number of! To 12 is preferable, and an alkyl group having a total carbon number of 1 to 8 is more preferable.
  • Normal propi Particularly preferred are a ru group, an isopropyl group, a normal butyl group and a tert-butyl group.
  • the aryl group represented by R 2 is preferably an aryl group having 6 to 14 carbon atoms which may be unsubstituted or substituted.
  • a substituent for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.
  • the aryl group represented by R 2 is preferably an aryl group having a total carbon number of 6 to 10 and particularly preferably a phenyl group.
  • the aralkyl group represented by R 2 is preferably an aralkyl group having a total carbon number of 7 to 16 which may be unsubstituted or substituted.
  • examples include aralkyl groups such as a til group and anthracenylmethyl group.
  • a substituent for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.
  • a benzyl group is particularly preferred, which is preferably an aralkyl group having 7 to 11 carbon atoms in total.
  • Z represents —O— or NH—.
  • Y represents a divalent linking group having a total carbon number of! ⁇ 8.
  • To 8 is an alkylene group (e.g., methylene, ethylene, propylene, butylene, pentylene), an alkenylene group (e.g., ethenylene, propenylene), Alkynylene group (eg, ethynylene, propynylene), arylene group (eg, phenylene), divalent heterocyclic group (eg, 6-chloro-1, 1,3-triazine 1, 2-4-zinole, pyrimidine 2, 4_ dinole group, quinoxaline 1, 2, 3 _ diinole group, pyridazine 1, 3, 6- diyl), _ ⁇ -, _CO_, -NR- (R is a hydrogen atom, an alkyl group or an aryl group), or these A combination (for example, one NHCH CH NH—, one NHCONH—, etc.) is preferred.
  • R is
  • the alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, R alkyl group or aryl group may have a substituent.
  • substituents are the same as those of the aryl group.
  • R alkyl and aryl groups Is as defined above.
  • divalent linking groups represented by Y:! ⁇ 8 the divalent linking groups having the total carbon number:! ⁇ 6 are preferred, especially ethylene groups, propylene groups, butylenes. Group, hexylene group, CH—
  • the polymer dispersant according to the present invention includes not only one type of repeating unit represented by the general formula (1) but also a polymer compound containing two or more sulfur atoms by copolymerizing two or more types. But
  • the thioether structure constituting the side chain has not only one sulfur atom but also a side chain having two or more sulfur atoms by constituting Z and R 2 with a group having a sulfur atom. be able to.
  • the polymer dispersant according to the present invention introduces a thioether structure into a desired polymer compound (preferably as a side chain) or is a single monomer having a thioether group (preferably in a side chain). It can be obtained by polymerization or copolymerization of a monomer having a thioether group (preferably in the side chain) with another monomer.
  • a thioether structure is introduced into the side chain of the ethylenically unsaturated monomer, or homopolymerization of an ethylenically unsaturated monomer having a thioether structure in the side chain, or an ethylenically unsaturated group having a thioether structure in the side chain. It can be obtained by copolymerization of a saturated monomer and another copolymer component.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a methyl group, an ethynole group, a normal propyl group, a normal butyl group, a tert-butyl group, a phenyl group
  • Z is _ ⁇ 1 and Y is an ethylene group
  • alkali-soluble polymer in the present invention contains a nitrogen atom
  • examples thereof include polymer compounds having at least one repeating unit represented by the following.
  • alkali-soluble polymer containing a sulfur atom or a nitrogen atom in the present invention will be given below, but the invention is not limited to these.
  • the following compounds PO— :! to P 0— are copolymers having repeating units represented by 34ttA, B, and C.
  • a, b, and c represent the mass% ratio of each of the repeating units A, B, and C.
  • a surfactant, preservative, or dispersion stabilizer may be appropriately blended in the metal fine particle dispersion of the present invention.
  • any of anionic, cationic, nonionic, and betaine surfactants can be used, and anionic and nonionic surfactants are particularly preferable.
  • the HLB value of the surfactant is preferably about 3 to 6, since the solvent of the coating solution is a nonpolar solvent.
  • the HLB value is described in, for example, "Surfactant Handbook" (Tokiyuki Yoshida, Shinichi Shindo, Yoshiyoshi Yamanaka, published by Engineering Book Co., Ltd. 1987).
  • Specific examples of the surfactant include propylene glycol monostearate, propylene glycol monolaurate, diethylene glycol monostearate, and solvent. There are bitane monolaurate and polyoxyethylene sorbitan monolaurate. Examples of surfactants are also described in the aforementioned “Surfactant Handbook”.
  • dispersion stabilizer for example, those described in “Pigment Dispersion Technology (issued by Technical Information Association Co., Ltd. 1999)” can be used.
  • the colored composition of the present invention contains at least the fine metal particle dispersion of the present invention described above, and also contains at least one resin or a precursor thereof, a photopolymerization initiator, a solvent, and the like. If necessary, pigment fine particles may be contained.
  • the metal fine particle dispersion of the present invention and the colored composition of the present invention are preferably a black black composition.
  • black composition and, when the total metal atom concentration contained in the metal fine particle dispersion of the present invention was distributed solution of 4. 0 X 10- 4 mol / L, at a wavelength of 450nm and 550nm Absorption ratio, ie
  • Examples of the resin that can be added to the coloring composition of the present invention include polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577.
  • Examples thereof include copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and cellulose derivatives having a carboxylic acid group in the side chain.
  • cyclic acid anhydride to the polymer which has a hydroxyl group
  • a copolymer can be mentioned preferably.
  • the above-mentioned tree)! Is preferably selected from those having an acid value in the range of 30 to 400 mg KOti / g and a weight average molecular weight in the range of 1000 to 300,000.
  • an alkali-soluble polymer may be added in a range that does not adversely affect developability and the like.
  • the alkali-soluble polymers in the present invention may be used, and other alcohol-soluble nylons and epoxy resins may be used.
  • the precursor of the resin has an ethylenically unsaturated double bond, undergoes addition polymerization by light irradiation (hereinafter sometimes referred to as “photopolymerizable monomer”), and cures to form a resin that becomes a resin.
  • photopolymerizable monomer examples include a polymerizable monomer.
  • Examples of the initiator added to the colored composition of the present invention include a photopolymerization initiator that generates radicals by light irradiation. This will be described later.
  • the solvent that can be added to the coloring composition of the present invention is not particularly limited, but the same solvent as that used for the metal fine particle solvent replacement has the viewpoint of dispersion stability of the fine metal particles. Among these, those having an SP value of 9.0 or more are preferable.
  • methyl ethyl ketone, 2-propanol, 1 propanol, 1-methoxy-2-propyl acetate, cyclohexanone, acetone, N-methylpyrrolidone, or a mixture thereof can be preferably mentioned.
  • the colored composition of the present invention can contain pigment fine particles to make the hue close to black.
  • Suitable examples of pigment fine particles that can be contained in the colored composition of the present invention include carbon black, titanium black, and graphite.
  • Pigment Black (Pigment Black) 7 (Strong Bon Black CI No. 77266) is preferred.
  • Commercial products include “Mitsubishi Carbon Black MA100” (Mitsubishi Chemical Corporation) and “Mitsubishi Carbon Black # 5” (Mitsubishi Chemical Corporation).
  • titanium black TiO, TiO, TiN, and mixtures thereof are preferable.
  • the particle size of titanium black used is preferably 40 to: OOnm.
  • the graphite those having a particle diameter of 3 am or less as a Stokes diameter are preferable. If graphite exceeding 3 zm is used, the contour shape of the light-shielding pattern becomes non-uniform and sharpness may deteriorate. In addition, it is desirable that most of the particle diameter (preferably 95% or more) is 0.1 ⁇ m or less.
  • pigment fine particles In addition to the pigment fine particles, other known pigment fine particles may be used in the colored composition of the present invention.
  • the pigments are roughly classified into organic pigments and inorganic pigments.
  • organic pigments are preferred.
  • examples of organic pigments preferably used include azo pigments, phthalocyanine pigments, anthraquinone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and nitro pigments.
  • the hue of the organic pigment is preferably, for example, a yellow pigment, an orange pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment, or a black pigment.
  • pigment fine particles include the color materials described in JP-A-2005-17716 [0038] to [0 040], and JP 2005-361447 No. [0068] to [0072].
  • the pigments described in this document and the colorants described in JP-A-2005-17521, [0080] to [0088] can be suitably used.
  • the present invention is not limited to these.
  • the pigment fine particles have a hue that is complementary to the hue of the metal fine particles in the present invention.
  • the pigment fine particles may be used alone or in combination of two or more.
  • Preferred pigment combinations include a combination of a red and blue pigment mixture complementary to each other and a yellow and purple pigment mixture complementary to each other, or a black pigment added to the above mixture. Additional combinations and combinations of blue, violet and black pigments can be mentioned.
  • the pigment fine particles are preferably dispersed uniformly in the composition.
  • the pigment The arithmetic average particle diameter of the fine particles is preferably 5 nm to 5 ⁇ m, particularly preferably 10 nm to 1 ⁇ m.
  • the arithmetic average particle size of the pigment fine particles is preferably 20 nm to 0.5 ⁇ m.
  • the colored composition of the present invention is used as a colored composition for producing a light-shielding image (hereinafter referred to as “colored composition for light shielding”), it will be described in detail below.
  • the optical density per film thickness l x m of the light shielding layer is preferably 1 or more.
  • the content of the metal fine particles in the light-shielding coloring composition is the light-shielding layer to be formed. It is preferable to adjust so that it may become 10-90 mass% with respect to the total solid content of this, Preferably it is about 10-80 mass%.
  • the content is preferably determined in consideration of variation in optical density due to the average particle diameter of the metal fine particles.
  • the “light-shielded image” is used to include a black matrix.
  • Black matrix means a black edge or a grid between red, blue, and green pixels on the periphery of display devices such as liquid crystal display devices, plasma display devices, EL display devices, and CRT display devices. This is a black part in the shape of a stripe or stripe, and also a dot-like or linear black pattern for TFT shading.
  • the definition of this black matrix is, for example, Taihei Kanno, “Liquid Crystal Display Device Dictionary” 2nd edition, Nikkan Kogyo Shimbun, 1996, p. 64.
  • Examples of light-shielded images include organic EL displays (for example, Japanese Patent Publication No. 2004-103507), PDP front non-nore (Nori Era, JP-A 2003-51261), and PALC for light shielding of the backlight. Etc.
  • the colored composition for producing a light-shielding image has photosensitivity.
  • the photosensitivity can be imparted by adding a photosensitive resin composition to the colored composition of the present invention.
  • a preferred embodiment of the photosensitive resin composition includes a binder polymer, a photopolymerization initiator, a photopolymerizable monomer, and the like.
  • the photosensitive resin composition includes those that can be developed with an alkaline aqueous solution and those that can be developed with an organic solvent. From the viewpoint of safety and the cost of the developer, those that can be developed with an aqueous alkaline solution are preferred. In order to give the photosensitive resin composition developability in an aqueous alkali solution, it is preferable that the polymer of the binder is an alkali-soluble polymer.
  • the photosensitive resin composition may be a negative composition in which a portion that receives radiation such as light or electron beam is cured as described above, or a positive composition in which a radiation non-receptive portion is cured. There may be.
  • Examples of the positive photosensitive resin composition include those using a novolac resin.
  • a novolac resin for example, an alkali-soluble novolac resin system described in JP-A-7-43899 can be used.
  • a positive photosensitive material described in JP-A-6-148888 that is, a mixture of an alkali-soluble resin described in the publication and 1,2 naphthoquinonediazide sulfonic acid ester as a photosensitive agent and a thermosetting agent described in the publication.
  • the positive type photosensitive material containing it can be used.
  • the composition described in JP-A-5-262850 can also be used.
  • the negative photosensitive resin composition includes a photosensitive resin composed of a negative diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition composed of an azide compound and a binder, and a cinnamic acid type.
  • a photosensitive resin composition examples thereof include a photosensitive resin composition.
  • a photopolymerizable composition containing a photopolymerization initiator, a photopolymerizable monomer, and a binder as basic constituent elements is particularly preferable.
  • the photopolymerizable composition “polymerizable compound B”, “polymerization initiator C”, “surfactant”, “adhesion aid” and other compositions described in JP-A-11-133600 are used.
  • a photosensitive resin composition that is a negative photosensitive resin composition and that can be developed with an aqueous alkali solution, includes a carboxylic acid group-containing binder (alkali-soluble binder) as a main component. 1), a photopolymerization initiator, and a photopolymerizable monomer.
  • alkali-soluble binder the above-described resins or resins exemplified as precursors thereof can be suitably used.
  • the alkali-soluble binder is usually contained in an amount of 10 to 95% by mass, more preferably 20 to 90% by mass, based on the total solid content of the photosensitive light-shielding coloring composition.
  • the content is in the range of 10 to 95% by mass, the adhesiveness of the photosensitive resin layer is not too high, and the strength and photosensitivity of the formed layer are not inferior.
  • Examples of the photopolymerization initiator include a vicinal polyketal dinitro compound disclosed in US Pat. No. 2,367,660 and a acyloin ether described in US Pat. No. 2448828.
  • Examples include trihalomethyl-s triazine compounds described in the specification, trihalomethyloxadiazole compounds described in US Pat. No. 4,212,976, and the like. It is. Particularly preferred are trihalomethyl-s-triazine, trihalomethyl oxadiazole, and triarylimidazole dimer.
  • polymerization initiator C described in JP-A-11 133600 can be cited as a suitable example.
  • photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture of two or more types. It is particularly preferable to use two or more types.
  • the content of the photopolymerization initiator based on the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.
  • Examples of combinations of photopolymerization initiators that are not yellowish and can be increased in exposure sensitivity and exhibit excellent display characteristics include a diazole photopolymerization initiator, The combination with a triazine type photoinitiator is mentioned. Among them, 2-trichloromethyl 5 _ (p-styrylstyryl) _ 1, 3, 4-oxadiazole and 2, 4- Bis (trichloromethyl) 6— [4 ′ — (N, N bisethoxycarbonylmethylamino) -3′-bromophenyl] —s-triazine is most preferred.
  • the ratio of these photopolymerization initiators is 95/5 to 20/80, more preferably f / 90/10 to 30/70, and particularly preferably f / 80, by mass ratio of diazole / triazine. / 20-60 / 40.
  • These photopolymerization initiators are described in JP-A-1-152449, JP-A-11-254918, and JP-A-2-153353.
  • benzophenone type can also be mentioned as a suitable example of the above-mentioned photopolymerization initiation time.
  • the ratio of the pigment to the entire solid content of the photosensitive light-shielding coloring composition is about 15 to 25% by mass, a coumarin compound is mixed with the photopolymerization initiator. Also, coloring such as yellowing can be suppressed and high sensitivity can be achieved.
  • the coumarin-based compound 7- [2- [4- (3-hydroxymethylbiperidino) -6-jetylamino] triazinylamino] -3-fuel coumarin is most preferred.
  • the ratio of these photopolymerization initiators and coumarin compounds is the mass ratio of photopolymerization initiators / coumarin compounds, 20/80 to 80/20, and more preferably 30/70 to 70/30. And most preferably 40/60 to 60/40.
  • the photopolymerizable composition that can be used in the present invention is not limited to these, and may be appropriately selected from known intermediate forces.
  • the photopolymerization initiator is generally from 0.5 to 20 mass%, preferably from! To 15 mass%, based on the total solid content of the photosensitive shading coloring composition. When the content is within the above range, a decrease in photosensitivity and image intensity can be prevented, and the performance can be sufficiently improved.
  • Examples of the photopolymerizable monomer include compounds having a boiling point of 100 ° C or higher at normal pressure.
  • monofunctional (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoloxyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meta) )
  • Atalylate trimethylolethane tritalylate, trimethylolpropane triacrylate, trimethylolpropane ditalylate, neopentylglycol di (meth) atalylate, pentaerythritol tetra (meth) atalylate, pentaerythritol tri (meta) ) Relate, Dipentaerythritol Hexa (meth) acrylate, Dipentaerythritol Penta (meth) acrylate,
  • Atarirate can be mentioned.
  • the photopolymerizable monomers may be used alone or in combination of two or more.
  • the content of the photopolymerizable monomer with respect to the total solid content of the photosensitive coloring composition for light shielding is generally 5 to 50% by mass, and preferably 10 to 40% by mass. When the content is within the above range, the light sensitivity and the image strength are not lowered, and the adhesiveness of the photosensitive light-shielding layer is not excessive.
  • thermal polymerization inhibitor examples include, for example, aromatic hydroxy compounds such as hydroquinone, ⁇ -methoxyphenol, p_t-butylcatechol, 2, 6_di-tert-butynole p_taresol, ⁇ -naphthol, pyrogallol, etc.
  • Quinones such as benzoquinone, ⁇ -toluquinone, naphthylamine, pyridine, amines such as ⁇ -toluidine, phenothiazine, aluminum salt or ammonium salt of ⁇ ⁇ ⁇ -nitrosophenylhydroxylamine, chloranil, nitrobenzene, 4, 4 ' —Chobis (3-methyl-6_t_butylphenol), 2,2′-methylenebis (4-methyl_6_t_butylphenol), 2-mercaptobenzimidazole, and the like.
  • the photosensitive light-shielding coloring composition further contains known additives as necessary, for example, plasticizers, surfactants, adhesion promoters, dispersants, anti-sagging agents, leveling agents, antifoaming agents. Agents, flame retardants, brighteners, solvents, etc. can be added.
  • adhesion promoter examples include alkylphenol Z formaldehyde novolak resin, polybutyl ether, polybutyl isobutyl ether, polybutyl butyral, polyisobutylene, styrene monobutadiene copolymer rubber, butyl rubber, vinyl chloride.
  • examples include vinyl acetate copolymer, chlorinated rubber, acrylic resin-based adhesive, aromatic, aliphatic or alicyclic petroleum resin, and silane coupling agent.
  • the black matrix By forming the black matrix using the light-shielding coloring composition of the present invention (including the photosensitive composition), a thin black matrix having a high optical density can be produced.
  • a photosensitive light-shielding layer can be formed on a support using the metal fine particle dispersion of the present invention to provide the photosensitive transfer material of the present invention.
  • a light-shielded image such as a black matrix can be produced.
  • the photosensitive transfer material has at least one photosensitive light-shielding layer formed on the support using the above-described light-sensitive coloring composition for light shielding, etc., and if necessary, a thermoplastic resin layer, An intermediate layer, a protective layer, or the like can be provided.
  • the film thickness of the photosensitive light-shielding layer is preferably in the range of 0.:! To 4 / im, particularly in the range of 0.:! To 2. O ⁇ m, and more preferably 0.2 to: 1. O / im. I like it.
  • the support in the photosensitive transfer material a known support such as polyester or polystyrene can be used. Among these, biaxially stretched polyethylene terephthalate is preferable from the viewpoints of cost, heat resistance, and dimensional stability.
  • the thickness of the support is preferably about 15 to 200 xm, more preferably about 30 to about 150 zm. When the thickness of the support is within the above range, it is possible to effectively suppress generation of a wrinkle of a tin plate due to heat during the lamination process, which is advantageous in terms of cost.
  • the support may be provided with a conductive layer described in JP-A-11-149008 as required.
  • an alkali-soluble thermoplastic resin layer between the support and the photosensitive light-shielding layer or between the support and the intermediate layer.
  • the thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb unevenness (including unevenness due to an already formed image, etc.) on the base surface. It is preferable to have a property that can be deformed.
  • Resins contained in the alkali-soluble thermoplastic resin layer include saponified products of ethylene and acrylic acid ester copolymers, saponified products of styrene and (meth) acrylic acid ester copolymers, and bulls. Saponification products of toluene and (meth) acrylic acid ester copolymers, poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers of butyl (meth) acrylate and butyl acetate, etc. It is preferably at least one selected from Kenya, etc.
  • thermoplastic resins those having a softening point of 80 ° C. or less are preferable.
  • resins include JP-B 54-343, JP-B 55-31, JP-B ⁇ 8-12577, JP-B 54-, JP-A 61-134756, JP-B 59-44615.
  • a resin soluble in an alkaline aqueous solution can be mentioned.
  • methacrylic acid / 2_ethylhexyl acrylate, Z-benzyl methacrylate, and methyl methacrylate copolymer described in JP-A-63-147159 are used.
  • styrene Z (meth) acrylic acid copolymers described in Japanese Patent Publication Nos. 55-38961 and 5-241340 are used.
  • the thermoplastic resin layer includes various plasticizers, various polymers, supercooling substances, adhesion improvers, surfactants, It is also possible to arrange a release agent or the like.
  • preferable plasticizers include polypropylene glycolol, polyethylene glycolol, dioctino phthalate, diheptino phthalate.
  • thermoplastic resin layer Dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, polyethylene glycol mono (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) Atallate, polypropylene glycol di (meth) acrylate, addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, addition reaction product of organic diisocyanate and polyethylene glycol mono (meth) acrylate Examples include addition reaction products of organic diisocyanates and polypropylene (mono) (meth) acrylate, condensation reaction products of bisphenol A and poly (ethylene glycol) mono (meth) acrylate.
  • the plasticizer content of the thermoplastic resin layer which can, based on the total solid content of the thermoplastic resin layer, 200 mass% or less are common, preferably 20: 100% by weight.
  • the thickness of the thermoplastic resin layer is preferably 6 ⁇ m or more. If the thickness force of the thermoplastic resin is 3 ⁇ 4 x m or more, the unevenness of the base surface can be completely absorbed.
  • the upper limit is generally about 100 ⁇ m or less, preferably about 5 Ozm or less, from the viewpoint of developability and production suitability.
  • the solvent of the coating solution used for forming the thermoplastic resin layer can be used without particular limitation as long as it dissolves the resin constituting this layer.
  • the solvent examples thereof include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, i-propanol and the like.
  • an intermediate layer may be provided between the temporary support and the photosensitive light-shielding layer.
  • the resin constituting the intermediate layer is not particularly limited as long as it is alkali-soluble.
  • the resin include polybulal alcohol resins, polybulurpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, bulerite resins, polyamide resins, and copolymers thereof. be able to.
  • a resin obtained by copolymerizing a monomer having a carboxyl group or a sulfonic acid group with a resin that is not usually alkali-soluble, such as polyester, can also be used.
  • polybulal alcohol is preferable.
  • the polybulal alcohol preferably has a hatching degree of 80% or more, more preferably 83 to 98%.
  • an additive such as a surfactant can be added to the intermediate layer as necessary.
  • the thickness of the intermediate layer is preferably 0.1 to 5 x m, more preferably 0.5 to 3 ⁇ m. When the thickness of the intermediate layer is within the above range, it is possible to prevent an increase in the intermediate layer removal time during development without decreasing the oxygen barrier property.
  • the coating solvent for the intermediate layer there is no particular limitation as long as the resin is dissolved.
  • water is preferable, and a mixed solvent obtained by mixing the water-miscible organic solvent with water is also preferable.
  • the photosensitive transfer material of the present invention is prepared by applying a light-shielding coloring composition solution of the present invention to a support, such as a spinner, a wheeler, a roller coater, a curtain coater, a knife coater, or a wire bar coater. It can be prepared by forming a photosensitive light-shielding layer by applying and drying using an applicator such as Etastruder. It can also be formed in the same manner when an alkali-soluble thermoplastic resin layer is provided.
  • the photosensitive transfer material of the present invention is provided with the photosensitive light-shielding layer using the light-shielding coloring composition of the present invention as described above, a light-shielding layer having a thin film and a high optical density can be produced. it can.
  • the light-shielded image is produced by patterning a light-shielding layer formed using the metal fine particle dispersion of the present invention, a coloring composition containing the same, or a photosensitive transfer material.
  • the thickness of the light shielding layer is 0. 2 ⁇ 2. 0 / m or so, more preferably not more than 0. 9 u m. Since the light shielding layer is made by dispersing the metal fine particles in the present invention, even a thin film as described above can exert a sufficient optical density (O ⁇ D3.5 or more).
  • the method for producing (patterning) the light-shielded image using the metal fine particle dispersion of the present invention, the coloring composition containing the metal fine particle dispersion or the photosensitive transfer material is not particularly limited.
  • An example of a black matrix pattern forming method is given below.
  • the light-shielding coloring composition of the present invention containing the metal fine particles of the present invention and the alkali-soluble polymer of the present invention and having photosensitivity is applied to a substrate, and the metal fine particles and the present invention are applied.
  • a photosensitive light-shielding layer containing an alkali-soluble polymer is formed.
  • the first method is a method for obtaining a light-shielded image by performing pattern formation by removing the light-shielding layer other than the pattern by exposure and development thereafter.
  • the above A layer having the same composition as the intermediate layer may be formed on the photosensitive light-shielding layer to form a protective layer.
  • the coating solution can be applied by using the above-described coating machine, and it is particularly preferable to perform the coating by a spin coating method.
  • the fine metal particles according to the present invention and the alkali-soluble polymer according to the present invention are coated on the substrate with the non-photosensitive coloring composition of the present invention.
  • a light shielding layer containing an alkali-soluble polymer in the present invention is formed.
  • a photosensitive resist solution is applied on the light shielding layer to form a resist layer.
  • the resist layer is then exposed and developed by exposure to form a pattern in the resist layer, and then the non-patterned portion of the light shielding layer is dissolved according to this pattern to form a pattern in the light shielding layer. Finally, the resist layer is removed to produce a light-shielded image.
  • a coating layer is previously formed on a portion other than the pattern on the substrate, and the non-photosensitive light-shielding material of the present invention containing the metal fine particles and the alkali-soluble polymer of the present invention thereon.
  • the coating layer formed first is removed together with the upper light shielding layer to produce a light shielding image.
  • the photosensitive transfer material is placed on a light-transmitting substrate so that the photosensitive light-shielding layer of the photosensitive transfer material is in contact therewith. And stack. Next, the support is peeled off from the laminate of the photosensitive transfer material and the light transmissive substrate, and then the layer is exposed and developed to form a light-shielded image.
  • This method for producing a light-shielded image does not require a cumbersome process and is low in cost.
  • a predetermined mask is placed above the light-shielding layer formed on the substrate, then exposed from above the mask, then developed with a developing solution, and a patterned image is obtained, and subsequently washed with water as necessary.
  • the light-shielded image of the present invention can be obtained by performing the process.
  • the pattern image may be obtained by directly striking the exposure light based on the image data without using the mask.
  • the light source for the exposure light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.) can be appropriately selected and used.
  • a wavelength region capable of curing the photosensitive resin layer for example, 365 nm, 405 nm, etc.
  • Specific examples include ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, LDs, ultra-high pressure mercury lamps, YAG-SHG solid-state lasers, KrF lasers, and solid-state lasers.
  • the amount of exposure is usually about 5 to 200 mj / cm 2 , and preferably about 10 to 100 mj / cm 2 .
  • the exposure machine used in this case is not particularly limited, a scattered light exposure machine, a parallel light exposure machine, a stepper, and a laser exposure are used in addition to the proximity exposure machine that exposes through the mask. be able to.
  • the developer known developers such as those described in JP-A-5-72724, which are not particularly limited, can be used.
  • a dilute aqueous solution of an alkaline substance is used.
  • the developer is preferably one in which the photosensitive resin layer exhibits a dissolution type development behavior.
  • a small amount of an organic solvent miscible with water may be added.
  • pure water is sprayed with a shower nozzle or the like to make the surface of the photosensitive light-shielding layer uniform. It is preferable to moisten.
  • the alkaline substance includes alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal Carbonates (eg, sodium carbonate, lithium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate, potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali Metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg, tetramethylammonium hydroxy) D), trisodium phosphate, and the like.
  • the concentration of the alkaline substance is preferably 0.01 to 30% by mass.
  • the pH is preferably 8 to 14.
  • Examples of the organic miscibility miscible with water include, for example, methanolol, ethanol, 2_propanol, 1_propanol, butanol, diacetone ethanol, ethylene glycol monomethinoreateol, ethylene Glyconoremonoetinoreetheno Ethyleneglyco-reno N-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ⁇ -force prolatatone, ⁇ -butyroratatone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, lactate ethyl, methyl lactate, ⁇ -force Prolatatam, ⁇ _methylpyrrolidone and the like are preferable.
  • the concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass.
  • a known surfactant may be added, and the concentration of the surfactant is preferably
  • the developer may be used as a bath solution or a spray solution.
  • methods such as rubbing with a rotating brush or wet sponge in the developer can be combined.
  • the developer temperature is usually from about room temperature to 40 ° C.
  • the development time depends on the composition of the light-shielding layer, the alkalinity and temperature of the developer, and the type and concentration of the organic solvent when added, but is usually about 10 seconds to 2 minutes. If it is too short, the development of the unexposed area may be insufficient, and the absorbance of ultraviolet rays may be insufficient, and if it is too long, the exposed area may be etched. In either case, it is difficult to make the light-shielded image shape suitable. In this development step, a light-shielded image is formed.
  • the substrate with a light-shielding image of the present invention is a light-shielding formed by using the metal fine particle dispersion of the present invention or the coloring composition of the present invention containing the same, or the photosensitive transfer material of the present invention on a light-transmitting substrate. It is produced by patterning the layer as described above.
  • the film thickness of the light-shielded image on this substrate with a light-shielded image is preferably 0.2 to 2.0 / im, particularly 0.2 to 9 ⁇ 9 ⁇ . Since the light shielding layer in the black matrix substrate is obtained by dispersing the metal fine particles in the present invention, the thin film as described above has a sufficient optical density.
  • the substrate with a light-shielding image of the present invention can be applied to a TV, personal computer, liquid crystal projector, portable terminal such as a game machine or a mobile phone, a digital camera, a car navigation, and the like without any limitation. Further, it can be suitably used in the production of the following color filter.
  • the color filter of the present invention comprises a colored layer on a light-transmitting substrate and is different from each other. And each pixel constituting the pixel group is separated from each other by a light-shielding image (black matrix).
  • the black matrix is produced using the metal fine particle dispersion of the present invention, or the colored composition or photosensitive transfer material of the present invention using the same.
  • the number of pixel groups may be two, three, or four or more. For example, in the case of three, three hues of red (R), green (G) and blue (B) are preferably used. When three types of pixel groups of red, green, and blue are arranged, any arrangement may be used when four or more types of pixel groups are preferred, such as mosaic type and triangle type.
  • the light-transmitting substrate a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, or a plastic film is used.
  • two or more pixel groups may be formed on a light-transmitting substrate by a conventional method, and then a black matrix may be formed as described above.
  • a black matrix may be formed, and then two or more pixel groups may be formed. Since the color filter of the present invention is provided with a black matrix having a high density and a thin film as described above, it has a high display contrast and excellent flatness.
  • the metal fine particle dispersion of the present invention can be suitably used for a display element.
  • the display element include a plasma display device, an EL display device, a CRT display device, a liquid crystal display device, and the like, and particularly when used in a liquid crystal display device, the effect of the metal fine particle dispersion of the present invention is remarkable. To be demonstrated.
  • display elements and explanation of each display device refer to, for example, “Electronic Display Device (Akio Sasaki, published by Sumi Industrial Research Association 1990)”, “Display Device (written by Junyuki Ibuki, published in 1989 by Sangyo Tosho)” It is described in.
  • the liquid crystal display device of the present invention includes an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle compensation film, an antireflection film, a light diffusion film, an antiglare film, and the like. Generally composed of various members.
  • the light-shielded image in the present invention can be applied to a liquid crystal display device composed of these known members. it can.
  • LCD types include STN, TN, VA, IPS, OCS, and R_CB.
  • One of the liquid crystal display devices includes a power color filter, a liquid crystal layer, and liquid crystal driving means (including a simple matrix driving method and an active matrix driving method) between a pair of substrates that are at least one of light-transmitting substrates. ) At least.
  • the color filter preferably has a plurality of pixel groups as described above, and each pixel constituting the pixel group is preferably separated from each other by a light-shielded image according to the present invention. it can. Since the color filter has high flatness, the liquid crystal display device provided with the power filter does not generate cell gap unevenness between the color filter and the substrate, and the occurrence of display defects such as color unevenness is improved.
  • liquid crystal display device As another aspect of the liquid crystal display device, at least one of them is provided with a color filter, a liquid crystal layer, and a liquid crystal driving means between a pair of light-transmitting substrates, and the liquid crystal driving means is active.
  • a black matrix produced using the metal fine particle dispersion of the present invention, a coloring composition using the same, or a photosensitive transfer material is formed between the active elements. It is what.
  • the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Side Industry Research Committee, 1994)”.
  • the display device (liquid crystal display device) of the present invention is not particularly limited. For example, it can be applied to various types of liquid crystal display devices described in the above-mentioned “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device.
  • a color TFT liquid crystal display device is described in, for example, "Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)". Furthermore, the present invention can be applied to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field drive method such as IPS and a pixel division method such as MVA. For example, “EL, PDP, LCD display-latest trends in technology and market-(Toray Research Center Research Division 2001) Line) j, page 43.
  • the above-mentioned polymer compound PO-33 was soluble ( ⁇ ) in pH NaOH aqueous solution and insoluble (X) in distilled water.
  • polymer compound PO-33 is replaced with the polymer compounds PO-25, 7, 11, 20, 23, 19, 32, S-1 (Disperbyk-161, manufactured by Bicchemi), S-2 (Disperbyk-190 manufactured by Big Chemie Co., Ltd.), T— :!
  • S-1 Disbyk-161, manufactured by Bicchemi
  • S-2 Disbyk-190 manufactured by Big Chemie Co., Ltd.
  • T— T— :!
  • the obtained silver fine particles were amorphous potato-like particles having an arithmetic average particle diameter of 52 nm and an arithmetic standard deviation of 33 nm.
  • the prepared silver nanoparticle-containing liquid was centrifuged (12000 rpm '30 min), the supernatant liquid was discarded, distilled water was added, and washing was repeated three times. Further, acetone was added to the silver nanoparticle-containing solution, and the mixture was stirred with a stirrer and centrifuged (12000 rpm'30 min). Thereafter, the supernatant was removed, 1-methoxy-2-propyl acetate was prepared, and 20 kHz ultrasonic waves were irradiated for 5 minutes using a “Sonifier type II” ultrasonic homogenizer manufactured by Branson.
  • the silver nanoparticle dispersion thus obtained had the same shape and color as that after the formation of the particles. Moreover, as a result of measuring the Ag content of the obtained silver nanoparticle dispersion by atomic absorption, the Ag concentration was 8.0 mass%. The concentration of the polymer compound PO-33 obtained from loss on drying using TG-DTA (manufactured by Seiko Co., Ltd.) in the solvent dispersion was 1.1% by mass. This silver nanoparticle dispersion is designated as metal-containing dispersion A-1.
  • a metal particle-containing solution was prepared in the same manner as in the above (2) except that in the above (2), the polymer compound P01-33 was replaced with the polymer compounds described in Table 2 below.
  • the arithmetic average particle diameter, arithmetic standard deviation, and particle shape of the obtained silver fine particles are shown in Table 2 below.
  • 3 g of the polymer compound PO-20 was added to 2.5 L of an aqueous solution adjusted to pH 12.2 using 1N aqueous sodium hydroxide solution, and stirred at 45 ° C. for 30 minutes until it was completely dissolved.
  • the temperature of this solution is controlled at 50 ° C, and an aqueous solution containing 3 g of sodium borohydride, an aqueous solution containing 24 g of silver nitrate, and an aqueous solution containing 24.2 g of chloroauric acid are added at the same time to contain black-brown silver-gold alloy nanoparticles.
  • a liquid was prepared. Table 2 below shows the arithmetic mean particle diameter, arithmetic standard deviation, and particle shape of the obtained silver-gold alloy nanoparticles.
  • the silver-gold alloy nanoparticle-containing liquid obtained in the same manner as in (2) above was processed, and 1-methoxy_2-propyl acetate was added to add a silver concentration of 0.74 mol / L (total of silver and gold).
  • a particle dispersion was prepared, and this was designated as metal-containing dispersion A-15.
  • This solution was temperature-controlled at 50 ° C and an aqueous solution containing 2 g of sodium acetate (I) 23.6 g containing sodium borohydride 3 g and an aqueous solution 13.3 g hydrated salt (II) hydrate was added.
  • a liquid containing tin alloy nanoparticles was prepared. Table 2 shows the arithmetic average particle diameter, arithmetic standard deviation, and particle shape of the obtained silver fine particles.
  • the amount of dipentaerythritol hexatalylate added is the total mass of the amount of benzyl methacrylate / methacrylic acid copolymer and the amount of polymer compound PO-33 in the coating solution.
  • the mass ratio was 0.9. ]
  • compositions were mixed to prepare a protective layer coating solution.
  • the protective layer coating solution is applied onto the photosensitive light-shielding layer using a spin coater so that the dry film thickness is 1.5 ⁇ , and dried at 100 ° C. for 5 minutes to form a protective layer. Then, photosensitive material P-1 of the present invention was produced.
  • the photosensitive light-shielding layer coating solution B-1 that had passed 3 days after the preparation was coated on a glass substrate and processed in the same manner as described above to obtain a photosensitive material Z-1 having a protective layer.
  • the photosensitive material P-1 and the mask (quartz exposure mask with image pattern) are set upright Then, the distance between the exposure mask surface and the protective layer coating surface was set to 200 xm, and pattern exposure was performed with an exposure light amount of 70 mj / cm 2 . Subsequently, development processing (33 ° C. ⁇ 20 seconds) was performed using a development processing solution TCD (manufactured by Fuji Photo Film Co., Ltd., alkaline developer).
  • the black size has a screen size of 10 inches, a pixel power of S480 X 640, a black matrix width of 24 ⁇ m, and an aperture in the pixel area of 86 ⁇ ⁇ 304 ⁇ m. Obtained Trix P—1.
  • the obtained black matrix was evaluated as follows. The results are shown in Table 3 below.
  • the optical densities of the black matrices P-1 and Z-1 were measured.
  • the density fluctuation value was calculated by subtracting the absolute value of the optical density of the black matrix P_1 from the absolute value of the optical density of the black matrix Z_1.
  • the stability with time of the coating solution before and after the lapse of 3 days was evaluated from the absolute value of the concentration fluctuation value according to the following criteria. Each result is shown in Table 3 below.
  • Absolute value of OD change is 0.4 or more and less than 1.0
  • the optical density of the black matrix was measured by the following method.
  • the photosensitive light-shielding layer coated on the glass substrate before the black matrix was exposed to 500 mj / cm 2 from the coated surface side using the above-described ultrahigh pressure mercury lamp. Further, beta was performed at 240 ° C for 120 minutes, and then the optical density (OD) was measured using a Macbeth densitometer (trade name: T
  • the optical density (OD) of the glass substrate is measured in the same way, and the OD force OD is measured.
  • 0 1 is the bow I and the optical density of each black matrix.
  • a black image having a good hue is obtained, and the quality as a black matrix is excellent.
  • ⁇ Power to satisfy the black matrix's blackness is slightly yellowish.
  • the light-shielding coloring compositions of B_9 and B-10 in Comparative Examples have a small yellow color reduction due to deterioration over time, but have a yellowish color, and the resulting black matrix has a low O.D. The We were unable to demonstrate satisfactory performance as a rack matrix.
  • Comparative Examples B-11 to B-14 were the light-shielding coloring compositions before aging, and they were able to form a black matrix having a high performance of OD of 3.5 or more. The resulting black matrix was unable to exhibit satisfactory performance.
  • the liquid crystal display device using the metal fine particle dispersion of the present invention can provide a liquid crystal display device with high display quality without display unevenness and good display quality.
  • thermoplastic resin layer coating solution prepared as described below was applied to a thickness of 15 / m and dried at 100 ° C. for 5 minutes to form a thermoplastic resin layer.
  • an intermediate layer coating solution having the same composition as that of the protective layer coating solution in Example 1 (6) was applied on this so that the dry film thickness was 1.5 ⁇ . Dry for 5 minutes to form an intermediate layer did.
  • the photosensitive light-shielding layer coating solution B-1 of Example 1 (6) which was aged for 3 days from the preparation, was applied to a dry film thickness of 1.0 / m at 100 ° C. It was dried for 5 minutes to form a photosensitive light-shielding layer, and a photosensitive transfer material was produced.
  • the following composition was mixed to prepare a coating solution for a thermoplastic resin layer.
  • the glass substrate and the photosensitive transfer material obtained above are overlapped so that the photosensitive light-shielding layer is in contact with the glass substrate, and both are laminated using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)). Pasted together.
  • the lamination conditions were rubber roller temperature 130 ° C, linear pressure 100N / cm, and conveyance speed 2.2mZ. Thereafter, the support (polyethylene terephthalate film) was peeled from the photosensitive transfer material to prepare Photosensitive Material G-1.
  • Example 1 The exposure was performed under the same exposure machine and the same exposure conditions as those in Example 1 (9). Subsequently, the following three steps of development processing were performed to obtain a black matrix H-1.
  • Second step Development processing was performed using a developing solution (trade name: ⁇ CD1, manufactured by Fuji Photo Film Co., Ltd., alkaline developer) at a temperature of 33 ° C for 20 seconds.
  • a developing solution (trade name: ⁇ CD1, manufactured by Fuji Photo Film Co., Ltd., alkaline developer) at a temperature of 33 ° C for 20 seconds.
  • the grid-shaped light-shielded image (black matrix) obtained in the present invention and the comparative example is red.
  • a color filter having a predetermined size and shape of green and blue was formed to produce a color filter.
  • a liquid crystal display device was formed using the color filter of the present invention obtained above and the color filter of the comparative example.
  • an active matrix substrate in which a thin film transistor and a pixel electrode are formed on a glass substrate corresponding to an RGB pattern, and an alignment film is provided.
  • ITO and an alignment film were formed on the color filter to produce a counter substrate.
  • TN liquid crystal is sealed between this active matrix substrate and the counter electrode, and bonded via a sealant.
  • Polarizers are placed on both sides of each substrate in crossed Nicols, and a backlight is placed on the active matrix substrate side.
  • a liquid crystal display device was obtained.
  • the metal fine particle dispersion of the present invention includes, for example, paints, printing inks, inkjet inks, power color filters, shading image preparation coloring compositions, image preparation coloring compositions, substrates with black images, liquid crystal display devices, and the like. It can be mentioned as a use. Particularly, high performance is required, and particularly important in practical use include a coloring composition for producing a light-shielding image, a robust paint or coloring composition for ink-jet ink, and a coloring composition for a color filter.

Abstract

Disclosed is a method for producing a metal particle dispersion wherein metal particles are produced by reducing metal ions in the presence of an alkali-soluble polymer having one or more sulfur and/or nitrogen atoms. Also disclosed are a metal particle dispersion, and a colored composition, a photosensitive transfer material, a substrate with a light-blocking image, a color filter and a liquid crystal display, each using the metal particle dispersion.

Description

明 細 書  Specification
金属微粒子分散物の製造方法、金属微粒子分散物、並びに、これを用 いた着色組成物、感光性転写材料、遮光画像付き基板、カラーフィルターおよび 液晶表示装置  Method for producing metal fine particle dispersion, metal fine particle dispersion, and coloring composition, photosensitive transfer material, substrate with light-shielding image, color filter, and liquid crystal display device using the same
技術分野  Technical field
[0001] 本発明は、金属微粒子を含む金属微粒子分散物の製造方法、金属微粒子分散物 [0001] The present invention relates to a method for producing a metal fine particle dispersion containing metal fine particles, and a metal fine particle dispersion.
、並びに、これを用いた着色組成物、感光性転写材料、遮光画像付き基板、カラー フィルターおよび液晶表示装置に関する。 The present invention also relates to a coloring composition, a photosensitive transfer material, a substrate with a light-shielding image, a color filter, and a liquid crystal display device using the same.
背景技術  Background art
[0002] 従来から黒色材料用着色組成物は、印刷インク、インクジェットインク、エッチングレ ジスト、ソルダーレジスト、プラズマディスプレイパネル（PDP)の隔壁、誘電体パター ン、電極（導体回路)パターン、電子部品の配線パターン、導電ペースト、導電フィル ム、ブラックマトリックス等の遮光画像等に広く用いられている。前記遮光画像は、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、 CRT表示装置などの表 示装置の周辺部に設けられた黒色の縁や、赤、青、緑の画素間の格子状やストライ プ状の黒色部、さらに TFT遮光のためのドット状や線状の黒色パターン等、いわゆる ブラックマトリックス（以下、「BM」という場合がある。）の他に、各種遮光画像を含むも のである。  Conventionally, coloring compositions for black materials have been used for printing inks, inkjet inks, etching resists, solder resists, plasma display panel (PDP) partition walls, dielectric patterns, electrode (conductor circuit) patterns, and electronic components. Widely used for shading images such as wiring patterns, conductive pastes, conductive films, and black matrices. The shading image is a black edge provided around the periphery of a display device such as a liquid crystal display device, a plasma display device, an EL display device, a CRT display device, or a grid pattern between red, blue, and green pixels. In addition to the so-called black matrix (hereinafter sometimes referred to as “BM”) such as black and strip-shaped black portions, dot-shaped and linear black patterns for TFT shading, etc. is there.
BMは、一般に表示コントラストを向上させるために用いられる。さらに、 BMは、薄 膜トランジスター (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装置の 場合には光による電流リークによる画質低下を防止するためにも用いられており、高 レ、遮光性（光学濃度〇Dで 3以上）が求められてレ、る。  BM is generally used to improve display contrast. In addition, BM is also used to prevent image degradation due to current leakage due to light in the case of active matrix liquid crystal display devices using thin film transistors (TFTs). An optical density of 3 or more) is required.
[0003] 一方、近年、液晶表示装置がテレビジョン (以下、「TV」という場合がある。）へ応用 されるようになってきている。 TV用途では、透過率が低く且つ高い色純度を有する力 ラーフィルターが用いられており、また、高輝度を得るためにバックライトの輝度が高く なる傾向にある。このため、コントラストの低下や周辺額縁部分の透けを防止するため に、 BMには高い遮光性が要求されている。 [0004] また、家庭用や設置用等に用いられる TVは、太陽光が入射する部屋に長期間設 置されることが多ぐ太陽光に対する TFTの劣化が懸念されている。更に、 TV用途 では、（1)〇Dが高く画像の引締まり感がでること、即ち、コントラストが高いこと、およ び（2)外光での液晶の白さが目立たなくなること、が要求されるため、係る観点でも B Mには高レ、遮光性が要求されてレ、る。 On the other hand, in recent years, liquid crystal display devices have been applied to televisions (hereinafter sometimes referred to as “TV”). In TV applications, power filters with low transmittance and high color purity are used, and the brightness of the backlight tends to increase in order to obtain high brightness. For this reason, BM is required to have a high light-shielding property in order to prevent a decrease in contrast and see-through of the peripheral frame portion. [0004] In addition, TVs used for home use and installation are concerned about TFT deterioration due to sunlight, which is often installed in a room where sunlight enters for a long period of time. Furthermore, for TV applications, it is required that (1) OD is high and the image is tightened, that is, the contrast is high, and (2) the white color of the liquid crystal under external light is inconspicuous. Therefore, from this point of view, BM requires a high level of light and light shielding.
[0005] BMとしては、例えば、クロム等の金属膜を遮光層として有するものが挙げられる。ク ロム等の金属膜を遮光層とする BMの形成方法としては、例えば、金属薄膜を蒸着 法やスパッタリング法により作製して、該金属薄膜の上にフォトレジストを塗布し、次い で BM用パターンをもつフォトマスクを用いてフォトレジスト層を露光現像し、その後露 出した金属薄膜をエッチングし、最後に金属薄膜上のレジスト層を剥離することによ つて BMを形成する方法が知られている（例えば、非特許文献 1参照）。  [0005] Examples of BM include those having a metal film such as chromium as a light shielding layer. As a method for forming BM using a metal film such as chromium as a light shielding layer, for example, a metal thin film is produced by vapor deposition or sputtering, a photoresist is applied on the metal thin film, and then BM is used. It is known to form a BM by exposing and developing a photoresist layer using a photomask with a pattern, etching the exposed metal thin film, and finally peeling the resist layer on the metal thin film. (For example, see Non-Patent Document 1).
[0006] このフォトレジストを用いた BMの製造方法は、金属薄膜を用いるため、膜厚が小さ くても高い遮光効果が得られるという利点がある。しかし、蒸着法やスパッタリング法と レ、う真空成膜工程やエッチング工程が必要となり、コストが高くなるという問題がある。 また、遮光層が金属膜であるため、反射率が高ぐ強い外光の下では表示コントラス トが低いという問題もある。  [0006] Since this method of manufacturing BM using a photoresist uses a metal thin film, there is an advantage that a high light shielding effect can be obtained even if the film thickness is small. However, there is a problem that the cost is increased because an evaporation method, a sputtering method, a vacuum film forming step and an etching step are required. In addition, since the light shielding layer is a metal film, there is a problem that the display contrast is low under strong external light with high reflectivity.
これに対し、前記金属薄膜として、低反射クロム膜 (金属クロムと酸化クロムとの 2層 力 なるもの等）を用いるといった手段がある力 更なるコストアップとなることは否め なレ、。また、エッチング工程では金属イオンを含有した廃液が排出されるため、環境 負荷が大きいという大きな欠点も有している。特に、上述の方法に最もよく用いられる クロムは、有害で環境負荷が非常に大きぐ昨今は EUの ELV指令、 RoHS指令に 代表されるように環境負荷低減への社会的な関心が高まっており、クロムを代替した 材料の提案が行われてレ、る。  On the other hand, it is undeniable that the cost is further increased by using a low-reflective chromium film (such as metal chromium and chromium oxide having a two-layer force) as the metal thin film. In addition, since the waste liquid containing metal ions is discharged in the etching process, there is a great disadvantage that the environmental load is large. In particular, chromium, which is most commonly used in the above-mentioned methods, is harmful and has a very large environmental impact. Recently, as shown by the EU ELV Directive and RoHS Directive, there is an increasing social interest in reducing the environmental impact. Proposals for materials that replace chrome have been made.
[0007] 他の BM形成方法としては、遮光性顔料、例えばカーボンブラックを含有する感光 性樹脂組成物を用いる方法も知られている。該方法としては、例えば、透明基板に R 、 G、 B画素を形成した後、この画素の上にカーボンブラック含有感光性樹脂組成物 を塗布し、透明基板の R、 G、 B画素非形成面側から全面に露光する、セルファライメ ント方式の BM形成方法が知られている（例えば、特許文献 1参照。）。 前記方法は、前記金属膜のエッチングによる方法に比較して製造コストは低くなる ものの、十分な遮光性を得るためには膜厚が厚くなるという問題がある。その結果、 B Mと R、 G、 B画素との重なり（段差）が生じ、カラーフィルターの平坦性が悪くなつて 液晶表示装置のセルギャップムラが発生し、表示ムラ等の表示不良につながることに なる。 [0007] As another BM forming method, a method using a photosensitive resin composition containing a light-shielding pigment such as carbon black is also known. As the method, for example, after forming R, G, B pixels on a transparent substrate, a carbon black-containing photosensitive resin composition is applied on the pixels, and the R, G, B pixel non-formation surface of the transparent substrate is applied. A self-alignment BM formation method is known in which the entire surface is exposed from the side (see, for example, Patent Document 1). Although the method is lower in production cost than the method by etching the metal film, there is a problem that the film thickness is increased in order to obtain sufficient light shielding properties. As a result, overlap (step) occurs between BM and R, G, and B pixels, and the flatness of the color filter deteriorates, resulting in cell gap unevenness in the liquid crystal display device, leading to display defects such as display unevenness. Become.
[0008] 表示ムラとは、ブラックマトリックス基板表面が平滑でない場合に、液晶の配向が乱 れ、表示ムラの原因となると言われており、液晶表示装置にグレイのテスト信号を入 力させた時に観察される淡いムラである。比較的くつきりした筋状に見える「スジムラ」 は感光性樹脂層の形成時に生じた厚みムラ、露光のムラ、現像処理のムラ、熱処理 のムラなど、配向制御用突起の形成時に発生しているものと、液晶表示装置として機 能する際に、配向制御用突起と液晶の間のインターラタシヨンにより発生するムラとが 考えられる力 機構は定かではない。  [0008] Display unevenness is said to be a cause of display unevenness when the black matrix substrate surface is not smooth, which causes display unevenness. When a gray test signal is input to the liquid crystal display device, It is a faint unevenness observed. The “straight stripes” that appear to be relatively sticky streaks are generated during the formation of alignment control protrusions, such as thickness unevenness, exposure unevenness, development processing unevenness, and heat treatment unevenness that occurred during the formation of the photosensitive resin layer. However, the force mechanism that may cause unevenness between the alignment control protrusion and the liquid crystal when functioning as a liquid crystal display device is not clear.
[0009] 一方、透明基板上に親水性樹脂を含有する感光性レジスト層を形成し、 BM用パタ ーンを有するフォトマスクを介して露光 '現像して透明基板上にレリーフを形成し、こ の透明基板を無電解メツキの触媒となる金属化合物の水溶液に接触させ、金属化合 物をレリーフ中に含有させ乾燥した後、熱処理を施し、その後、前記透明基板上のレ リーフを無電解メツキ液に接触させることにより、粒径 0. 01-0. 05 /i mの遮光用の 金属粒子がその内部に均一に分散された BMを作製する方法が提案されている（例 えば、特許文献 2参照）。前記金属粒子としてはニッケル、コバルト、鉄、銅、クロムが 記載され、具体例としては唯一ニッケルが示されている。  On the other hand, a photosensitive resist layer containing a hydrophilic resin is formed on a transparent substrate, exposed through a photomask having a BM pattern, and developed to form a relief on the transparent substrate. The transparent substrate is brought into contact with an aqueous solution of a metal compound serving as a catalyst for electroless plating, the metal compound is contained in the relief, dried, and then subjected to heat treatment, and then the relief on the transparent substrate is transferred to the electroless plating solution. A method for producing a BM in which metal particles for light shielding having a particle size of 0.01-0.05 / im are uniformly dispersed therein has been proposed (see, for example, Patent Document 2). ). As the metal particles, nickel, cobalt, iron, copper, and chromium are described, and nickel is shown as a specific example.
し力しながら、この方法は、露光現像工程を含むレリーフ形成 無電解メツキ触媒 の付与—熱処理—無電解メツキという、水を扱う煩瑣な処理工程が多レ、。そのため、 低コストでの BM製造を大きくは期待できなレ、。  However, this method has many troublesome processing steps for handling water, such as application of relief forming electroless plating catalyst, heat treatment, and electroless plating including an exposure and development step. As a result, BM production at low cost cannot be expected.
[0010] また、黒色パターンを作製する着色組成物に磁性フィラーを使った例が提案されて レ、るが（例えば、特許文献 3参照。）、これらの例は 10ミクロン以上の厚膜であり、単位 膜厚辺りの濃度が低ぐ薄膜で遮光性能が高い遮光画像を低コストで作製することが できない。  [0010] In addition, examples using a magnetic filler in a colored composition for producing a black pattern have been proposed (see, for example, Patent Document 3), but these examples are thick films of 10 microns or more. Therefore, it is impossible to produce a light-shielded image having a low density around the unit film thickness and having a high light-shielding performance at a low cost.
[0011] 前記以外に、環境負荷が小さく薄膜で光学濃度の高いブラックマトリックスを得る方 法として金属微粒子を用いる方法が知られている（例えば、特許文献 4および 5参照[0011] In addition to the above, a method of obtaining a black matrix with a low environmental load and a high optical density with a thin film As a method, a method using metal fine particles is known (for example, see Patent Documents 4 and 5).
。）。これらの方法によると、環境負荷が小さぐ薄膜で光学濃度の高いブラックマトリ ックスを得ることができるとされている。 . ). According to these methods, it is said that a black matrix having a high optical density can be obtained with a thin film having a small environmental load.
しかし、前記金属微粒子を含む着色組成物を用い遮光膜を作製し、パターユング 露光、現像処理によって高精細のマトリックスを形成した際に、金属微粒子の凝集物 による凹凸や、遮光膜作製時に調液した着色組成物の経時安定が悪ぐ安定に製 造できない問題があり、技術改良が望まれていた。  However, when a light-shielding film is prepared using the colored composition containing the metal fine particles and a high-definition matrix is formed by patterning exposure and development processing, irregularities due to aggregates of metal fine particles and liquid preparation at the time of preparing the light-shielding film are prepared. The colored composition thus obtained has poor stability over time and cannot be stably produced, and technical improvement has been desired.
[0012] 一方、金属微粒子を安定に分散する方法が提案されている（例えば、特許文献 6お よび 7参照。）。係る方法では、分散剤として、塗料などに使用する高分子顔料分散 剤や、非水系のチオール化合物を用いた金属微粒子分散物の製造方法が開示され ているが、前記の分散剤では粒子の形成時の単分散は向上して分散安定性が向上 するものの、遮光膜としての遮光能力が低ぐ遮光膜を作製した場合に満足できる性 能を発揮できなかった。 On the other hand, methods for stably dispersing metal fine particles have been proposed (see, for example, Patent Documents 6 and 7). In this method, as a dispersant, a polymer pigment dispersant used for paints and the like, and a method for producing a metal fine particle dispersion using a non-aqueous thiol compound are disclosed. Although monodispersion at the time was improved and dispersion stability was improved, satisfactory performance could not be exhibited when a light shielding film having a low light shielding ability as a light shielding film was produced.
[0013] 特許文献 1 :特開昭 62— 9301号公報 Patent Document 1: Japanese Patent Application Laid-Open No. 62-9301
特許文献 2 :特許第 3318353号公報  Patent Document 2: Japanese Patent No. 3318353
特許文献 3：特開 2001— 13678号公報  Patent Document 3: Japanese Patent Laid-Open No. 2001-13678
特許文献 4 :特開 2004— 334180号公報  Patent Document 4: Japanese Patent Application Laid-Open No. 2004-334180
特許文献 5 :特開 2005— 17322号公報  Patent Document 5: Japanese Unexamined Patent Application Publication No. 2005-17322
特許文献 6 :特開 2003— 193118号公報  Patent Document 6: Japanese Patent Laid-Open No. 2003-193118
特許文献 7：特開 2004— 346429号公報  Patent Document 7: Japanese Unexamined Patent Application Publication No. 2004-346429
非特許文献 1：共立出版 (株)発行「カラー TFT液晶ディスプレイ」第 218〜220頁（1 997年 4月 10曰）  Non-Patent Document 1: Kyoritsu Shuppan Co., Ltd. “Color TFT Liquid Crystal Display” pp. 218-220 (10 April, 1997)
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
[0014] 本発明は、経時安定性を有した分散安定性の高い濃厚な金属微粒子分散物の製 造方法、金属微粒子分散物、並びに、これを用いた着色組成物、感光性転写材料、 を提供することを目的とする。また、本発明は、高い黒色の膜またはブラックマトリック スを初めとする遮光画像若しくは薄膜で濃度の高い着色膜をはじめとする画像を有 する遮光画像付き基板、また、平坦性に優れ、表示ムラが低いカラーフィルターおよ び液晶表示装置を提供することを目的とする。 [0014] The present invention relates to a method for producing a highly dispersed metal fine particle dispersion having stability over time, a metal fine particle dispersion, a coloring composition using the same, and a photosensitive transfer material. The purpose is to provide. In addition, the present invention has a light-shielded image including a high black film or a black matrix, or an image including a colored film having a high density with a thin film. Another object of the present invention is to provide a substrate with a light-shielding image, a color filter excellent in flatness and low display unevenness, and a liquid crystal display device.
課題を解決するための手段  Means for solving the problem
[0015] <1> 硫黄原子および Zまたは窒素原子を 1個以上有するアルカリ溶解性ポリマ 一の存在下で金属イオンを還元し、金属微粒子を形成する金属微粒子分散物の製 造方法である。  <1> A method for producing a metal fine particle dispersion in which metal ions are reduced in the presence of an alkali-soluble polymer having one or more sulfur atoms and one or more Z or nitrogen atoms to form metal fine particles.
[0016] <2> 前記アルカリ溶解性ポリマーが、酸性基を有することを特徴する前記 <1> の金属微粒子分散物の製造方法である。  <2> The method for producing a metal fine particle dispersion according to <1>, wherein the alkali-soluble polymer has an acidic group.
[0017] <3> 前記アルカリ溶解性ポリマーの酸性基力 カルボキシル基である前記 < 2 <3> Acidic power of the alkali-soluble polymer <2 which is a carboxyl group
>の金属微粒子分散物の製造方法である。  This is a method for producing a metal fine particle dispersion.
[0018] <4> 前記アルカリ溶解性ポリマーの有機概念図における有機性/無機性比（I<0018> <4> Organic / inorganic ratio in the organic conceptual diagram of the alkali-soluble polymer (I
/O値）が、 0.44以上 1.65以下である前記く 1>〜<3>の金属微粒子分散物の 製造方法である。 / O value) is a method for producing a metal fine particle dispersion according to the above <1> to <3>, which is 0.44 to 1.65.
[0019] <5> 前記金属微粒子が、周期律表の第 2族〜第 14族から選ばれる 1種または 2 種以上の金属を含有する前記 < 1 >〜 < 4 >の金属微粒子分散物の製造方法であ る。  [0019] <5> The metal fine particle dispersion according to <1> to <4>, wherein the metal fine particles contain one or more metals selected from Group 2 to Group 14 of the Periodic Table. It is a manufacturing method.
[0020] <6> 硫黄原子および Zまたは窒素原子を 1個以上有するアルカリ溶解性ポリマ 一と、金属微粒子と、を含有する金属微粒子分散物である。  [0020] <6> A metal fine particle dispersion containing an alkali-soluble polymer having at least one sulfur atom and one or more Z or nitrogen atoms, and metal fine particles.
[0021] <7> 黒色である前記 < 6 >の金属微粒子分散物である。 <7> The fine metal particle dispersion of <6>, which is black.
[0022] <8> 前記アルカリ溶解性ポリマー力 酸性基を有することを特徴する前記 < 6 > または < 7 >の金属微粒子分散物である。  <0022> <8> The metal fine particle dispersion of <6> or <7>, which has an acidic group.
[0023] <9> 前記アルカリ溶解性ポリマーの酸性基力 S、カルボキシル基である前記 < 8 <9> Acidic basic force S of the alkali-soluble polymer, <8
>の金属微粒子分散物である。  > Metal fine particle dispersion.
[0024] <10> 前記アルカリ溶解性ポリマーの有機概念図における有機性 Z無機性比（I[0024] <10> Organic Z-inorganic ratio (I
/O値）が、 0.44以上 1.65以下である前記く 6>〜<9>の金属微粒子分散物で ある。 / O value) is a metal fine particle dispersion according to the above <6> to <9>, which is 0.44 or more and 1.65 or less.
[0025] <11> 前記金属微粒子が、周期律表の第 2族〜第 14族から選ばれる 1種または  [0025] <11> The metal fine particles are one type selected from Group 2 to Group 14 of the Periodic Table or
2種以上の金属を含有する前記 < 6 >〜 < 10 >の金属微粒子分散物である。 [0026] < 12 > 前記く 6 >〜< 11 >の金属微粒子分散物を含有する着色組成物である [0027] < 13 > 黒色である前記く 12 >の着色組成物である。 The <6> to <10> metal fine particle dispersion containing two or more metals. [0026] <12> A colored composition comprising the metal fine particle dispersion of <6> to <11>. [0027] <13> The colored composition of <12>, which is black.
[0028] < 14 > 支持体上に少なくとも一層の感光性遮光層を設けた感光性転写材料で あって、前記感光性遮光層が前記 < 6 >〜 < 11 >の金属微粒子分散物を用いて形 成される感光性転写材料である。  [0028] <14> A photosensitive transfer material in which at least one photosensitive light-shielding layer is provided on a support, wherein the photosensitive light-shielding layer uses the metal fine particle dispersion of <6> to <11>. It is a photosensitive transfer material that is formed.
[0029] < 15 > 前記く 6 >〜く 11 >の金属微粒子分散物を用いて形成される遮光画像 を有する遮光画像付き基板である。 [0029] <15> A substrate with a light-shielding image having a light-shielding image formed using the metal fine particle dispersion of <6> to <11>.
[0030] < 16 > 前記 < 14 >の感光性転写材料を用いて作製される遮光画像を有する遮 光画像付き基板である。 [0030] <16> A substrate with a light shielding image having a light shielding image produced using the photosensitive transfer material according to <14>.
[0031] < 17 > 前記く 6 >〜く 11 >の金属微粒子分散物を用いて形成されるカラーフィ ノレターである。 [0031] <17> A color finolet formed using the metal fine particle dispersion of <6> to <11>.
[0032] < 18 > 前記く 6 >〜く 11 >の金属微粒子分散物を用いて形成される液晶表示 装置である。  [0032] <18> A liquid crystal display device formed using the metal fine particle dispersion of <6> to <11>.
発明の効果  The invention's effect
[0033] 本発明によれば、経時安定性を有した分散安定性の高い濃厚な金属微粒子分散 物の製造方法、金属微粒子分散物、並びに、これを用いた着色組成物、感光性転 写材料、を提供すること力できる。また、本発明によれば、高い黒色の膜またはブラッ クマトリックスを初めとする遮光画像若しくは薄膜で濃度の高い着色膜をはじめとする 画像を有する遮光画像付き基板、また、平坦性に優れ、表示ムラが低いカラーフィル ターおよび液晶表示装置を提供することができる。  [0033] According to the present invention, a method for producing a dense metal fine particle dispersion having high temporal stability and stability over time, a metal fine particle dispersion, a coloring composition using the same, and a photosensitive transfer material Can provide you with power. In addition, according to the present invention, a substrate with a light-shielding image having a light-shielding image including a high black film or a black matrix or an image including a thin colored film having a high density, and having excellent flatness and display. A color filter and a liquid crystal display device with low unevenness can be provided.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0034] 本発明の金属微粒子分散物の製造方法は、硫黄原子および/または窒素原子を 1個以上有するアルカリ溶解性ポリマー（以下、「本発明におけるアルカリ溶解性ポリ マー」という場合がある。）の存在下で金属イオンを還元し、金属微粒子を形成する。 また、本発明の金属微粒子分散物は、硫黄原子および/または窒素原子を 1個以 上有するアルカリ溶解性ポリマーと、金属微粒子と、を含有する。 [0034] The method for producing a metal fine particle dispersion of the present invention comprises an alkali-soluble polymer having one or more sulfur atoms and / or nitrogen atoms (hereinafter sometimes referred to as "alkali-soluble polymer in the present invention"). The metal ions are reduced in the presence of to form metal fine particles. The metal fine particle dispersion of the present invention contains an alkali-soluble polymer having at least one sulfur atom and / or nitrogen atom and metal fine particles.
更に、本発明の着色組成物は、本発明の金属微粒子分散物を含有し、必要に応じ て、本発明の着色組成物は、樹脂またはその前駆体の少なくとも 1種、顔料微粒子、 バインダーとなるポリマー、モノマー、開始剤、溶媒等を含有してもよい。 Furthermore, the coloring composition of the present invention contains the metal fine particle dispersion of the present invention, and if necessary, In addition, the coloring composition of the present invention may contain at least one kind of a resin or a precursor thereof, pigment fine particles, a polymer serving as a binder, a monomer, an initiator, a solvent, and the like.
本発明の微粒子分散物および着色組成物によれば、分散安定性の高い濃厚な金 属微粒子着色組成物を調製でき、塗布液経時安定性が高くブッが少ないことから、 薄膜で黒色濃度（遮光性能）が高い黒色の膜またはブラックマトリックスを初めとする 遮光画像、あるいは、薄膜で濃度の高い着色膜をはじめとする画像を、安定に作製 すること力 sできる。  According to the fine particle dispersion and the colored composition of the present invention, a dense metal fine particle colored composition having high dispersion stability can be prepared, and since the coating solution has high stability with time and little stickiness, a thin film with a black density (light-shielding property) It is possible to stably produce a light-shielded image such as a black film or black matrix having a high performance or a colored film having a high density in a thin film.
[0035] 本発明の金属微粒子分散物および着色組成物は、印刷インク、インクジェットインク 、フォトマスク作製材料、印刷用プルーフ作製用材料、エッチングレジスト、ソルダー レジスト、プラズマディスプレイパネル（PDP)の隔壁、誘電体パターン、電極（導体回 路)パターン、電子部品の配線パターン、導電ペースト、導電フィルム、ブラックマトリ ックス等の遮光画像等に用いることができる。例えば、本発明の金属微粒子分散物 および着色組成物は、カラー液晶表示装置等に用いるカラーフィルターの表示特性 向上のために、着色パターンの間隔部、周辺部分、および TFTの外光側等に遮光 画像を設けるために好適に用いることができる。また、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、 CRT表示装置などの表示装置の周辺部に設けられ た黒色の縁や、赤、青、緑の画素間の格子状やストライプ状の黒色の部分、更に好 ましくは TFT遮光のためのドット状や線状の黒色パターン等のブラックマトリックスとし て特に好適に用いられる。  [0035] The fine metal particle dispersion and the colored composition of the present invention include printing ink, inkjet ink, photomask preparation material, printing proof preparation material, etching resist, solder resist, plasma display panel (PDP) partition, dielectric It can be used for shading images of body patterns, electrode (conductor circuit) patterns, wiring patterns of electronic components, conductive pastes, conductive films, black matrices, and the like. For example, the metal fine particle dispersion and the colored composition of the present invention are shielded from the spacing between the colored pattern, the peripheral portion, and the outside light side of the TFT in order to improve the display characteristics of the color filter used in the color liquid crystal display device. It can be suitably used to provide an image. In addition, the black edges provided around the periphery of display devices such as liquid crystal display devices, plasma display devices, EL display devices, and CRT display devices, as well as grids and stripes between red, blue, and green pixels. It is particularly preferably used as a black matrix such as a black part, more preferably a dot-like or linear black pattern for TFT light shielding.
[0036] 《本発明の金属微粒子分散物》  << Metal Fine Particle Dispersion of the Present Invention >>
以下、本発明を詳細に説明するにあたり、まず本発明の金属微粒子分散物につい て詳述する。本発明の金属微粒子分散物は、黄原子および/または窒素原子を 1個 以上有するアルカリ溶解性ポリマーと、金属微粒子と、を含有する。  In the following detailed description of the present invention, the metal fine particle dispersion of the present invention will be described in detail. The metal fine particle dispersion of the present invention contains an alkali-soluble polymer having one or more yellow atoms and / or nitrogen atoms and metal fine particles.
[0037] (金属微粒子の組成）  [0037] (Composition of metal fine particles)
本発明における金属微粒子の金属は、特に限定されず、いかなる金属であっても よい。また、本発明における金属微粒子は、 2種以上の金属を組み合わせて用いて もよぐ合金として用いることも可能である。更に、本発明における金属微粒子は金属 化合物でもよいし、金属化合物と金属との複合微粒子でもよい。 その中でも、本発明における金属微粒子としては、金属および/または金属化合 物から形成されるものが好ましぐ金属から形成されるものが特に好ましい。 The metal of the metal fine particles in the present invention is not particularly limited, and any metal may be used. Further, the metal fine particles in the present invention can also be used as an alloy that can be used in combination of two or more metals. Furthermore, the metal fine particle in the present invention may be a metal compound or a composite fine particle of a metal compound and a metal. Among them, the metal fine particles in the present invention are particularly preferably those formed from a metal that is preferably formed from a metal and / or a metal compound.
特に本発明においては、長周期律表（IUPAC1991)の第 4周期、第 5周期、およ び第 6周期からなる群から選ばれる金属を主成分として含むことが好ましい。また、本 発明における金属微粒子は、第 2〜： 14族からなる群から選ばれる金属を含有するこ とが好ましぐ第 2族、第 8族、第 9族、第 10族、第 11族、第 12族、第 13族、および第 14族からなる群から選ばれる金属を主成分として含むことがより好ましい。  In particular, in the present invention, it is preferable that a metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the long periodic table (IUPAC1991) is included as a main component. In addition, the metal fine particles in the present invention preferably contain a metal selected from the group consisting of Groups 2 to 14: Group 2, Group 8, Group 9, Group 10 and Group 11. More preferably, the main component is a metal selected from the group consisting of Group 12, Group 13, and Group 14.
[0038] 前記金属微粒子として分散金属微粒子の好ましレ、例は、例えば、銅、銀、金、白金 、パラジウム、ニッケル、錫、コバルト、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、またはこれらの合金、力も選ばれる少なくとも 1種を挙げることができる。更に 好ましい金属は、銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウム、ィ リジゥムまたはこれらの合金、より好ましい金属は、銅、銀、金、白金、錫またはこれら の合金から選ばれる少なくとも 1種である。  [0038] Preferred examples of dispersed metal fine particles as the metal fine particles include, for example, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, Tungsten, niobium, tantalum, titanium, bismuth, antimony, lead, or an alloy thereof, and at least one of which power is also selected. More preferable metals are copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium or alloys thereof, and more preferable metals are selected from copper, silver, gold, platinum, tin or alloys thereof. At least one kind.
[0039] 本発明における金属微粒子は、本発明におけるアルカリ溶解性ポリマーの存在下 で、金属イオンを還元することによって得られる。具体的に、本発明における金属粒 子は、本発明におけるアルカリ溶解性ポリマーの存在下に金属塩を含む溶液と還元 剤とを添加し、混合して、金属イオンを還元することによって得られる。前記金属塩は 、特に制限無く用いることができ、例えば、塩化物、硝酸塩、亜硝酸塩、硫酸塩、アン モニゥム塩、酢酸塩等の金属塩が挙げられる。  [0039] The metal fine particles in the present invention can be obtained by reducing metal ions in the presence of the alkali-soluble polymer in the present invention. Specifically, the metal particles in the present invention are obtained by adding a metal salt-containing solution and a reducing agent in the presence of the alkali-soluble polymer in the present invention, mixing them, and reducing the metal ions. The metal salt can be used without particular limitation, and examples thereof include metal salts such as chloride, nitrate, nitrite, sulfate, ammonium salt, and acetate.
[0040] また、前記還元剤としては、通常使用されるものであれば特に限定されず、例えば 、水素化ホウ素ナトリウム、水素化ホウ素カリウムなどの水素化ホウ素金属塩;水素化 アルミニウムリチウム、水素化アルミニウムカリウム、水素化アルミニウムセシウム、水 素化アルミニウムベリリウム、水素化アルミニウムマグネシウム、水素化アルミニウム力 ルシゥム等の水素化アルミニウム塩、ヒドラジン化合物、デキストリン、ハイドロキノン、 ヒドロキシノレアミン、クェン酸およびその塩、コハク酸およびその塩、ァスコルビン酸お よびその塩等が挙げられる。  [0040] The reducing agent is not particularly limited as long as it is normally used. Examples thereof include metal borohydrides such as sodium borohydride and potassium borohydride; lithium aluminum hydride, hydrogenation Aluminum potassium, cesium hydride, aluminum beryllium hydride, magnesium aluminum hydride, aluminum hydride, aluminum hydride salts such as rum, hydrazine compounds, dextrin, hydroquinone, hydroxynoramine, citrate and its salts, succinic acid And its salt, ascorbic acid and its salt, and the like.
[0041] 本発明の金属微粒子分散物の製造方法において、金属塩および還元剤の添加方 法や反応温度等は特に制限は無ぐ調製する目的の金属微粒子生成条件に合わせ て、適宜調整することが出来る。 [0041] In the method for producing a metal fine particle dispersion of the present invention, a method of adding a metal salt and a reducing agent The method, reaction temperature, etc. are not particularly limited, and can be appropriately adjusted according to the conditions for producing fine metal particles to be prepared.
[0042] 金属化合物  [0042] Metal compounds
本発明でいう「金属化合物」とは上述のごとき金属と、金属以外の元素と、の化合物 である。  The “metal compound” in the present invention is a compound of a metal as described above and an element other than the metal.
金属と他の元素との化合物としては、金属の酸化物、硫化物、硫酸塩、炭酸塩など が挙げられる。このうち硫化物が色調や微粒子形成のしゃすさから特に好ましい。こ れら金属化合物の例としては、例えば、酸化銅（11)、硫化鉄、硫化銀、硫化銅 (11)、 チタンブラックなどが挙げられるが、色調や微粒子形成のしゃすさや安定性の観点 から、硫化銀が特に好ましい。  Examples of the compound of the metal and other elements include metal oxides, sulfides, sulfates, carbonates and the like. Of these, sulfide is particularly preferable from the viewpoint of color tone and fine particle formation. Examples of these metal compounds include, for example, copper oxide (11), iron sulfide, silver sulfide, copper sulfide (11), titanium black, and the like, from the viewpoint of color tone, fine particle formation, and stability. Silver sulfide is particularly preferred.
[0043] —複合微粒子— [0043] —Composite fine particles—
本発明でいう「金属化合物と金属との複合微粒子」とは、金属と金属化合物とが結 合して 1つの粒子になったものをいう。例えば、このような複合微粒子としては、粒子 の内部と表面とで組成の異なるもの、 2種類の粒子が合一したもの等を挙げることが できる。また、複合微粒子を構成する金属化合物および金属は、それぞれ 1種あって もよレ、し、 2種以上であってもよい。前記金属化合物と金属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。  The “composite fine particles of metal compound and metal” as used in the present invention refers to particles in which a metal and a metal compound are combined into one particle. For example, examples of such composite fine particles include those having different compositions between the inside and the surface of the particles, and those obtained by combining two kinds of particles. In addition, the metal compound and the metal constituting the composite fine particles may be one kind or two kinds or more, respectively. Specific examples of the composite fine particles of metal compound and metal include composite fine particles of silver and silver sulfide, composite fine particles of silver and copper (II) oxide, and the like.
[0044] コア 'シェル  [0044] Core 'shell
更に、本発明における金属微粒子は、コア 'シェル型の複合粒子であってもよい。コ ァ'シェル型の複合粒子とは、コア材料の表面をシェル材料でコートしたものである。 コア.シェル型の複合粒子に用いられる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、 Pb Te、 Se、 Te、 CuCl、 CuBr、 Cul、 T1C1、 TlBr、 Tilや、これらの固溶体およびこれら を 90mol%以上含む固溶体から選ばれる少なくとも 1種の半導体；或いは、銅、銀、 金、 白金、パラジウム、エッケノレ、錫、コバルト、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、タンタノレ、チタン、ビスマス、 アンチモン、鉛、またはこれらの合金、力 選ばれる少なくとも 1種の金属が挙げられ る。 Furthermore, the metal fine particles in the present invention may be core-shell type composite particles. The core-shell type composite particle is obtained by coating the surface of a core material with a shell material. Examples of shell materials used for core-shell type composite particles include Si, Ge, AlSb, InP, Ga, As, GaP, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, Pb Te, At least one semiconductor selected from Se, Te, CuCl, CuBr, Cul, T1C1, TlBr, Til and their solid solutions and solid solutions containing 90 mol% or more of these; or copper, silver, gold, platinum, palladium, eckenole , Tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantanore, titanium, bismuth, antimony, lead, or alloys thereof, force at least one selected metal The
前記コア材料の好ましい例としては、例えば、銅、銀、金、パラジウム、ニッケル、錫 Preferred examples of the core material include, for example, copper, silver, gold, palladium, nickel, tin
、ビスマス、アンモチン、鉛、またはこれらの合金から選ばれる少なくとも 1種を挙げる こと力 sできる。 It is possible to list at least one selected from bismuth, ammotine, lead, and 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 preferably used as a refractive index adjusting agent for the purpose of reducing the reflectance.
[0045] コア'シェル構造を有する複合微粒子の作製方法に特に制限はなぐ例えば、金属 微粒子を作製する過程で連続的に表面に金属化合物のシェルを形成する方法等を 用いることができる。このような方法としては、例えば、金属塩溶液に還元剤を添加し て、金属イオンの一部を還元して金属微粒子を作製し、次いで硫化ナトリウムや硫化 アンモニゥム等の硫化物を添加して、作製した金属微粒子の周囲に金属硫化物を形 成する方法がある。  [0045] There are no particular restrictions on the method for producing composite fine particles having a core-shell structure. For example, a method of continuously forming a metal compound shell on the surface in the process of producing metal fine particles can be used. As such a method, for example, a reducing agent is added to a metal salt solution, a part of metal ions is reduced to produce metal fine particles, and then a sulfide such as sodium sulfide or ammonium sulfide is added, There is a method of forming a metal sulfide around the produced metal fine particles.
[0046] 金属微粒子の形状  [0046] Shape of metal fine particles
「Advanced MaterialsJ 2002, 14, 80〜82や「J. Phys. Chem. B.」2003. 107, 2466〜2470等に記載されているように、金属粒子は粒子形状によって色味 が変化することが知られている。本発明における金属微粒子の形状は、特に制限無 ぐレ、かなる形状の物であってもよいが、アスペクト比の異なる金属微粒子を含むこと が好ましい。本発明における金属微粒子の主な形状は、アンパン状、ジャガイモ状、 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、金平糖状、コイル状等であってもよぐ好ましくは、板状 粒子、棒状（ロッド）である。  As described in "Advanced Materials J 2002, 14, 80-82" and "J. Phys. Chem. B." 2003. 107, 2466-2470, etc., the color of metal particles may change depending on the particle shape. Are known. The shape of the metal fine particles in the present invention is not particularly limited and may be any shape, but it is preferable to include metal fine particles having different aspect ratios. The main shapes of the metal fine particles in the present invention are ampang, potato, rod (needle, columnar, rectangular parallelepiped, rugby ball, etc.), flat plate (scale, ellipse plate, plate) It may be in the form of a fiber, a confetti, a coil, or the like, preferably a plate-like particle or a rod.
[0047] 本発明において、金属微粒子の「アスペクト比」とは、後述のごとく定義した金属微 粒子の長軸長を短軸長で割った値を意味し、 100個の金属微粒子について測定し た値の平均値と定義する。  In the present invention, the “aspect ratio” of the metal fine particles means a value obtained by dividing the major axis length of the metal fine particles defined as described later by the minor axis length, and was measured for 100 metal fine particles. It is defined as the average value.
尚、粒子の投影面積は電子顕微鏡写真上での面積を測定し、撮影倍率を補正す ることにより得られる。  The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification.
[0048] 前記金属微粒子における径 (長軸長、短軸長）とは、金属微粒子を三軸径として、 1 個の金属微粒子がちょうど（きっちりと）収まるような箱（直方体）を考え、この箱の長さ L、幅 b、高さまたは厚み tをもってこの金属微粒子の寸法と定義する。 [0048] The diameter (major axis length, minor axis length) of the metal fine particles is a box (cuboid) in which one metal fine particle is exactly (contained) with the metal fine particle as a triaxial diameter. Box length L, width b, height or thickness t are defined as the dimensions of this metal fine particle.
[0049] 本発明における金属微粒子の数平均粒径は、形成する膜厚を超えない限り特に制 限はないが、該金属微粒子の数平均粒径は、 10nm〜1000nmの範囲が好ましぐ 10nm〜500nmの範囲がより好ましぐ 10nm〜200nmの範囲が更に好ましい。 本発明における金属微粒子の数平均粒径が 10nm未満であると、生成が難しぐ 該数平均粒径の金属微粒子を用いて作製されたカラーフィルタ一は、その特性上、 目視で茶褐色（黒色にはならなレ、）に見える点で、好ましくない場合がある。また、本 発明における金属微粒子の数平均粒径が lOOOnmを超えると、粒子を分散した分 散物の安定性が低下して、遮光性が悪化する場合がある。 [0049] The number average particle diameter of the metal fine particles in the present invention is not particularly limited as long as it does not exceed the film thickness to be formed, but the number average particle diameter of the metal fine particles is preferably in the range of 10 nm to 1000 nm. The range of ˜500 nm is more preferred. The range of 10 nm to 200 nm is more preferred. When the number average particle size of the metal fine particles in the present invention is less than 10 nm, it is difficult to produce the color filter produced using the metal fine particles having the number average particle size. It may not be preferable in that it looks like Hananare. In addition, when the number average particle size of the metal fine particles in the present invention exceeds lOOOnm, the stability of the dispersed material in which the particles are dispersed may be lowered, and the light shielding property may be deteriorated.
尚、ここでいう「粒径」とは粒子の電子顕微鏡写真画像を同面積の円とした時の直 径を言い、また「数平均粒径」とは多数の粒子について前記の粒径を求め、この 100 個平均値をいう。また、本発明における金属微粒子は、粒径分布についても特に制 約はない。  As used herein, “particle diameter” refers to the diameter when an electron micrograph image of a particle is a circle of the same area, and “number average particle diameter” refers to the above-mentioned particle diameter for a number of particles. This means the average value of 100 pieces. Further, the metal fine particles in the present invention are not particularly restricted in the particle size distribution.
[0050] (本発明の金属微粒子分散物の製造方法）  [0050] (Method for producing metal fine particle dispersion of the present invention)
以下に本発明の金属微粒子分散物の製造方法について説明する。  The method for producing the metal fine particle dispersion of the present invention will be described below.
本発明の金属微粒子分散物は、硫黄原子および/または窒素原子を 1個以上有 するアルカリ溶解性ポリマーの存在下で金属イオンを還元し、金属微粒子を形成す ることにより、金属微粒子の分散安定性を改良できる。ここで、本発明におけるアル力 リ溶解性ポリマーの「存在下」で金属イオンを還元するとは、通常、本発明におけるァ ルカリ溶解性ポリマーを、予め溶解した容器中に、金属を含む塩と還元剤とを添加す ることを示すが、前記貴族を含む塩と還元剤とをそれぞれ別の容器で溶解し、これら を別途用意した反応容器にそれぞれ同時に添加してもよい。本発明におけるアル力 リ溶解性ポリマーは金属微粒子の分散安定性を向上させる効果があるので、金属微 粒子が形成される前または形成直後に反応容器中に存在することが好ましい。  The metal fine particle dispersion according to the present invention reduces the metal ion in the presence of an alkali-soluble polymer having at least one sulfur atom and / or nitrogen atom to form metal fine particles, thereby stabilizing the dispersion of the metal fine particles. Can be improved. Here, reducing the metal ion in the “in the presence” of the alkali-soluble polymer in the present invention usually means reducing the metal-soluble salt and the metal-containing salt in a container in which the alkali-soluble polymer in the present invention has been previously dissolved. The salt containing the noble and the reducing agent may be dissolved in separate containers, and these may be added simultaneously to separately prepared reaction containers. Since the alkali-soluble polymer in the present invention has the effect of improving the dispersion stability of the metal fine particles, it is preferably present in the reaction vessel before or just after the metal fine particles are formed.
[0051] 一金属微粒子の分散一  [0051] Dispersion of monometallic fine particles
本発明における金属微粒子は、本発明の金属微粒子分散物中におレ、て分散され ている。分散時における金属微粒子の存在状態は特に限定されないが、金属微粒 子が安定な分散状態で存在していることが好ましぐ例えば、コロイド状態であること 力はり好ましい。 The metal fine particles in the present invention are dispersed in the metal fine particle dispersion of the present invention. The state of the presence of the metal fine particles during dispersion is not particularly limited, but it is preferable that the metal fine particles exist in a stable dispersed state. A force beam is preferred.
[0052] 金属微粒子の溶媒置換  [0052] Solvent substitution of fine metal particles
また、本発明の金属微粒子分散物は、金属微粒子調製後に溶媒置換を行うことも できる。溶剤置換は、金属微粒子分散液中に酸をカ卩え、 pHを 7. 5以下にして、金属 微粒子の軟凝集による凝集ナノ粒子を沈降させる。次いで上澄みを取り除き、これを 数回繰り返し水洗し、水から徐々に非極性溶媒を添加し、順次溶媒を置換する。溶 媒置換後に、再分散を行う際には、超音波、ビーズミル分散機等を利用して機械的 な分散を行うことが好ましい。このような再分散を行うことにより、残留した還元剤等の 不純物を除去や溶媒置換をおこなうことができる。また、デカンテーシヨンの代わりに 、吸引ろ過、遠心分離等の手段を用レ、てもよい。  Further, the metal fine particle dispersion of the present invention can be subjected to solvent substitution after the preparation of the metal fine particles. In the solvent replacement, an acid is added to the metal fine particle dispersion, the pH is adjusted to 7.5 or less, and the aggregated nanoparticles by soft aggregation of the metal fine particles are precipitated. Next, the supernatant is removed, this is washed several times with water, and a nonpolar solvent is gradually added from the water, and the solvent is successively replaced. When redispersion is performed after solvent replacement, it is preferable to perform mechanical dispersion using ultrasonic waves, a bead mill disperser, or the like. By performing such redispersion, impurities such as the remaining reducing agent can be removed and solvent replacement can be performed. Further, instead of decantation, means such as suction filtration and centrifugation may be used.
[0053] 前記溶媒置換の際に用いる溶媒は特に制限なく用レ、られるが、中でも SP値が 9. 0 以上のものが好ましい。 「SP値」は溶解性パラメーターともいわれるもので、凝集エネ ルギー密度の平方根で表される。本発明においては、 SP値とは、「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頁記載のもの を意味する。  [0053] The solvent used for the solvent substitution is not particularly limited, and among them, those having an SP value of 9.0 or more are preferable. The “SP value” is also called a solubility parameter, and is expressed by the square root of the cohesive energy density. In the present invention, the SP value means that described on page 838 of “Adhesion Handbook” (edited by the Japan Adhesive Society, published by Nikkan Kogyo Shimbun, published in 1971, first edition).
上記 SP値は、例えば、 n キサン/ 7. 3、トルエン /8. 9、酢酸ェチル /9. 1 メチノレエチノレゲ卜ン /9. 3、了セ卜ン /10. 0、ェチノレ レ ーノレ / 12. 7、メチノレ了 ルコール /14. 5、水 /23. 4等である。ここで前記 SP値の単位は「（cal/cm3) 1/2」 である。 The above SP values are, for example, n-xan / 7.3, toluene / 8.9, ethyl acetate / 9.1 methylinetenoregigen / 9.3, sensane / 100.0, ethinore / renore / 12.7, Metinore finished Lucor / 14.5, water / 23.4, etc. Here, the unit of the SP value is “(cal / cm 3 ) 1/2 ”.
溶剤再分散の際に SP値が 9. 0以上のものを用いると、分散性が特に良好となり、メ チルェチルケトン、 2—プロパノール、 1 プロパノール、 1ーメトキシー 2—プロピルァ セテート、シクロへキサノン、アセトン、 N—メチルピロリドン、あるいはそれらの混合物 などが好適に上げられる。  When the solvent redispersion has an SP value of 9.0 or more, the dispersibility is particularly good, and methylethylketone, 2-propanol, 1 propanol, 1-methoxy-2-propylacetate, cyclohexanone, acetone, N —Methylpyrrolidone or a mixture thereof is preferably raised.
[0054] 本発明の金属微粒子分散物中における金属微粒子の含有量は、本発明の効果を より効果的に発揮させる観点から、分散物中の金属固形分質量が全固形分に対して 70質量％以上であることが好ましぐ 80質量％以上であることがさらに好ましぐ 85 質量％以上が特に好ましい。  [0054] The content of the metal fine particles in the metal fine particle dispersion of the present invention is such that the metal solid mass in the dispersion is 70 mass relative to the total solid content from the viewpoint of more effectively exerting the effects of the present invention. It is particularly preferable that it is 80% by mass or more, more preferably 85% by mass or more.
[0055] (硫黄原子および/または窒素原子を 1個以上有するアルカリ溶解性ポリマー） 次に、本発明における硫黄原子および/または窒素原子を 1個以上有するアル力 リ溶解性ポリマーについて説明する。本発明の金属微粒子分散物の製造方法によれ ば、本発明におけるアルカリ溶解性ポリマーの存在下で金属微粒子を調製すること により、金属微粒子の分散安定性を更に改良できる。 [0055] (Alkali-soluble polymer having at least one sulfur atom and / or nitrogen atom) Next, the alkali-soluble polymer having one or more sulfur atoms and / or nitrogen atoms in the present invention will be described. According to the method for producing a metal fine particle dispersion of the present invention, the dispersion stability of the metal fine particles can be further improved by preparing the metal fine particles in the presence of the alkali-soluble polymer in the present invention.
[0056] 本発明におけるアルカリ溶解性ポリマーには、硫黄原子、窒素原子の両方を含む ポリマーであってもよいし、硫黄原子または窒素原子のいずれか一方を有するポリマ 一であってよぐ両者ともに本発明の効果を得ることができる。  [0056] The alkali-soluble polymer in the present invention may be a polymer containing both a sulfur atom and a nitrogen atom, or may be a polymer having either one of a sulfur atom or a nitrogen atom. The effects of the present invention can be obtained.
硫黄原子をもつポリマーとしては、チォエーテル基、メルカプト基、スルフイド基、チ ォキソ基を有するものが好ましぐまた、窒素原子をもつポリマーとしては、アミノ基、ィ ミノ基を有するものや含窒素複素環化合物が好ましレ、。  As the polymer having a sulfur atom, a polymer having a thioether group, a mercapto group, a sulfide group, or a thixo group is preferred. As the polymer having a nitrogen atom, a polymer having an amino group or an imino group, or a nitrogen-containing complex is preferred. Ring compounds are preferred.
前記含窒素複素環としては、例えば、 2 _メルカプトべンズイミダゾール、ピロール、 ピロリジン、ォキサゾール、チアゾール、イミダゾール、ピラゾール、ピリジン、ピぺリジ ン、ピリダジン、ピリミジン、ピラジン、インドール、キノリン、ベンズイミダゾールが挙げ られ、これらの基は未置換でもよいし、置換された形でもよい。  Examples of the nitrogen-containing heterocycle include 2_mercaptobenzimidazole, pyrrole, pyrrolidine, oxazole, thiazole, imidazole, pyrazole, pyridine, piperidine, pyridazine, pyrimidine, pyrazine, indole, quinoline, and benzimidazole. These groups may be unsubstituted or substituted.
[0057] 本発明におけるアルカリ溶解性ポリマーは、上述した硫黄原子または窒素原子を 含む基を後述する重合体 (共重合体を含む。）或いは重合性化合物の側鎖末端基と して有するものでも、また、その側鎖末端以外に有していてもよいが、側鎖末端基とし て有するものが好ましい。以下、重合体（共重合体を含む。）または重合性化合物を 単に重合体ともいう。  [0057] The alkali-soluble polymer in the present invention may have the above-described group containing a sulfur atom or nitrogen atom as a polymer (including a copolymer) described later or a side chain terminal group of a polymerizable compound. Moreover, although it may have other than the side chain terminal, what has as a side chain terminal group is preferable. Hereinafter, a polymer (including a copolymer) or a polymerizable compound is also simply referred to as a polymer.
[0058] 本発明において「アルカリ溶解性」とは、蒸留水（H〇）に不溶であり、且つ、 pHIO In the present invention, “alkali solubility” means insoluble in distilled water (H0) and pHIO.
〜 13のアルカリ水溶液に溶解しうるものを意味する。 Means those that can be dissolved in an aqueous alkali solution of ~ 13.
例えば、水溶性高分子化合物はアルカリ水溶液に対して可溶性を示すが、蒸留水 に対しても同様に可溶性を示すので、本発明におけるポリマーからは除外される。  For example, a water-soluble polymer compound is soluble in an alkaline aqueous solution, but is similarly soluble in distilled water, and is therefore excluded from the polymer in the present invention.
[0059] 本発明における「アルカリ溶解性」の判定は、例えば、以下の評価法で決定すること ができる。 The determination of “alkali solubility” in the present invention can be determined, for example, by the following evaluation method.
まず、 pH12. 0に調整した Na〇H水溶液 20mlに評価対象の化合物 0. 2gを添加 し、激しく攪拌する。次いで、 25°Cの恒温層中に 6時間放置し、溶解性を確認する。 同時に蒸留水 20mlに評価対象の化合物 0. 2gを添加し、激しく攪拌する。 25°Cの 恒温層中に 6時間放置後に溶解性を確認する。この際、白濁、沈降物が確認されれ ば「不溶」、白濁、沈降物が確認されなければ「可溶」と判定する。このような評価法に よって、 pH12. 0に調整した NaOH水溶液に可溶で、蒸留水に不溶の物を選択する ことにより、本発明における「アルカリ溶解性」を確認することができる。 First, add 0.2 g of the target compound to 20 ml of NaOH aqueous solution adjusted to pH 12.0, and stir vigorously. Next, leave it in a constant temperature layer at 25 ° C for 6 hours to check the solubility. At the same time, add 0.2 g of the compound to be evaluated to 20 ml of distilled water and stir vigorously. 25 ° C Check the solubility after 6 hours in the thermostatic chamber. At this time, it is judged as “insoluble” if white turbidity and sediment are confirmed, and “soluble” if no white turbidity and sediment are confirmed. By such an evaluation method, the “alkali solubility” in the present invention can be confirmed by selecting a substance that is soluble in NaOH aqueous solution adjusted to pH 12.0 and insoluble in distilled water.
[0060] 本発明におけるアルカリ溶解性ポリマーとしては、例えば、酸性基を有するものが 好適に挙げられる。前記酸性基としては、特に制限は無ぐ 目的に応じて適宜選択 すること力 sできる。前記酸性基としては、例えば、カルボキシル基、スルホン酸基、リン 酸基、ボロン酸、フヱノール類、スルホアミドなどが挙げられ、これらの中でもカルボキ シノレ基が好ましい。また、本発明におけるアルカリ溶解性ポリマー中の前記アルカリ 可溶性基を有する構造単位の導入量は、該アルカリ可溶性基の存在によって、本発 明におけるアルカリ溶解性ポリマーが pH 10〜： 13のアル力リ水溶液に溶解しうるもの であれば特に限定はされない。 [0060] Preferred examples of the alkali-soluble polymer in the present invention include those having an acidic group. The acidic group is not particularly limited and can be appropriately selected according to the purpose. Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a boronic acid, a phenol, a sulfoamide, and the like. Among these, a carboxynole group is preferable. Further, the amount of the structural unit having an alkali-soluble group in the alkali-soluble polymer in the present invention is determined by the presence of the alkali-soluble group, so that the alkali-soluble polymer in the present invention has an pH of 10 to 13: If it can melt | dissolve in aqueous solution, it will not specifically limit.
[0061] 本発明におけるアルカリポリマーの酸価としては、特に制限は無ぐ 目的に応じて適 宜選択することができる力 例えば、 70〜300 (mgKOH/g)が好ましぐ 90〜250 ( mgK〇H/g)がより好ましぐ 100〜200 (mgK〇H/g)が分散安定性の観点から 特に好ましい。 [0061] The acid value of the alkali polymer in the present invention is not particularly limited, and can be appropriately selected according to the purpose. For example, 70 to 300 (mgKOH / g) is preferable 90 to 250 (mgK 100 to 200 (mgKH / g) is particularly preferable from the viewpoint of dispersion stability.
[0062] 前記酸性基としてカルボキシル基を有する重合体としては、例えば、カルボキシノレ 基を有するビニル共重合体、ポリウレタン樹脂、ポリアミド酸樹脂、変性エポキシ樹脂 などが挙げられ、これらの中でも、塗布溶媒への溶解性、アルカリ現像液への溶解性 、合成適性、膜物性の調整の容易さ等の観点からカルボキシノレ基を有するビニル共 重合体が好ましい。また、スチレンおよびスチレン誘導体の少なくともいずれかの共 重合体も好ましい。  [0062] Examples of the polymer having a carboxyl group as the acidic group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, a modified epoxy resin, and the like. A vinyl copolymer having a carboxynole group is preferred from the standpoints of solubility in water, solubility in an alkali developer, synthesis suitability, ease of adjustment of film properties, and the like. A copolymer of at least one of styrene and a styrene derivative is also preferable.
[0063] 前記カルボキシル基を有するビュル共重合体は、少なくとも（1)カルボキシル基を 有するビュルモノマーと、 (2)前記（1)のビュルモノマーと共重合可能なモノマーとの 共重合により得ることができる。  [0063] The bull copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a bull monomer having a carboxyl group and (2) a monomer copolymerizable with the bull monomer of (1). it can.
前記カルボキシル基を有するビュルモノマーとしては、例えば、（メタ）アクリル酸、ビ ニル安息香酸、マレイン酸、マレイン酸モノアルキルエステル、フマル酸、ィタコン酸 、クロトン酸、桂皮酸、アクリル酸ダイマー、水酸基を有する単量体 (例えば、 2—ヒドロ キシェチル (メタ）アタリレート等）と環状無水物（例えば、無水マレイン酸や無水フタ ル酸、シクロへキサンジカルボン酸無水物）との付加反応物、 ω—カルボキシーポリ 力プロラタトンモノ (メタ）アタリレートなどが挙げられる。これらの中でも、共重合性、コ ストおよび溶解性などの観点から (メタ）アクリル酸が特に好ましい。尚、本願明細書 において、「（メタ）アクリル酸」とは、アクリル酸およびメタクリル酸を総称し、その誘導 体の場合も同様である。 Examples of the butyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and hydroxyl group. Monomer having (for example, 2-hydro Xetyl (meth) acrylate, etc.) and cyclic anhydrides (eg maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxypoly polyprolatathone mono (meth) Atallate and the like are listed. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost and solubility. In the present specification, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, and the same applies to derivatives thereof.
また、カルボキシル基の前駆体として無水マレイン酸、無水ィタコン酸、無水シトラコ ン酸等の無水物を有するモノマーを用いてもょレ、。  In addition, monomers having anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. may be used as the precursor of the carboxyl group.
[0064] 前記（1)のビュルモノマーと共重合可能なモノマーとしては、特に制限は無く目的 に応じて適宜選択することができる力 例えば、（メタ）アクリル酸エステル類、クロトン 酸エステル類、ビュルエステル類、マレイン酸ジエステル類、フマル酸ジエステル類、 ィタコン酸ジエステル類、（メタ）アクリルアミド類、ビュルエーテル類、ビュルアルコー ルのエステル類、スチレン類（例えば、スチレン、スチレン誘導体等）、（メタ）アタリ口 二トリル、ビニル基が置換した複素環式基（例えば、ビエルピリジン、ビニルピロリドン 、ビニルカルバゾール等）、 Ν—ビニルホルムアミド、 Ν—ビエルァセトアミド、 Ν—ビニ ノレイミダゾール、ビニルカプロラタトン、 2—アクリルアミドー 2—メチルプロパンスルホ ン酸、リン酸モノ（2—アタリロイルォキシェチルエステル）、リン酸モノ（1ーメチルーァ クリロイルォキシェチルエステル）、官能基（例えば、ウレタン基、ウレァ基、スルホンァ ミド基、フエノール基、イミド基）を有するビニルモノマーなどが挙げられ、これらの中 でもスチレン類が好ましい。  [0064] The monomer (1) copolymerizable with the bull monomer is not particularly limited and can be appropriately selected according to the purpose. For example, (meth) acrylic acid esters, crotonic acid esters, bulle Esters, maleic diesters, fumaric diesters, itaconic diesters, (meth) acrylamides, butyl ethers, butyl alcohol esters, styrenes (eg, styrene, styrene derivatives, etc.), (meth) Atari mouth Nitryl, heterocyclic groups substituted with vinyl groups (eg, birpyridine, vinylpyrrolidone, vinylcarbazole, etc.), Ν-vinylformamide, Ν-biacetoamide, Ν-vininoleimidazole, vinyl caprolatatone 2-acrylamide-2-methylpropane sulfonic acid, phosphoric acid mono (2-Ataryllooxychetyl ester), phosphoric acid mono (1-methyl-acryloyloxychetyl ester), functional group (for example, urethane group, urea group, sulfonamide group, phenol group, imide group) Examples thereof include vinyl monomers, and among these, styrenes are preferable.
[0065] 前記 (メタ）アクリル酸エステル類としては、例えば、メチル (メタ）アタリレート、ェチル  [0065] Examples of the (meth) acrylic acid esters include methyl (meth) acrylate and ethyl.
(メタ）アタリレート、 η—プロピル（メタ）アタリレート、イソプロピル（メタ）アタリレート、 η —ブチル (メタ）アタリレート、イソブチル (メタ）アタリレート、 tert—ブチル (メタ）アタリ レート、 n キシル（メタ）アタリレート、シクロへキシル（メタ）アタリレート、 tert—ブチ ルシクロへキシル（メタ）アタリレート、 2 _ェチル（メタ）アタリレート、 tert—ォクチル（メ タ）アタリレート、ドデシル (メタ）アタリレート、ォクタデシル (メタ）アタリレート、ァセトキ シェチル (メタ）アタリレート、フエニル (メタ）アタリレート、 2—ヒドロキシェチル (メタ）ァ タリレート、 2—メトキシェチル (メタ）アタリレート、 2 _エトキシェチル (メタ）アタリレート 、 2— (2—メトキシェトキシ）ェチル（メタ）アタリレート、 3 フエノキシ 2 ヒドロキシ プロピル（メタ）アタリレート、ベンジル（メタ）アタリレート、ジエチレングリコールモノメチ ルエーテル（メタ）アタリレート、ジエチレングリコールモノェチルエーテル（メタ）アタリ レート、ジエチレングリコーノレモノフヱニノレエーテノレ（メタ）アタリレート、トリエチレングリ コーノレモノメチノレエーテノレ（メタ）アタリレート、トリエチレングリコーノレモノェチノレエー テル（メタ）アタリレート、ポリエチレングリコールモノメチルエーテル（メタ）アタリレート、 ポリエチレングリコールモノェチルエーテル（メタ）アタリレート、 β—フエノキシェトキ シェチル（メタ）アタリレート、ノユルフェノキシポリエチレングリコール（メタ）アタリレート 、ジシクロペンタニル（メタ）アタリレート、ジシクロペンテュル（メタ）アタリレート、ジシク タフロロペンチル（メタ）アタリレート、パーフロロクチルェチル（メタ）アタリレート、トリブ ロモフエニル（メタ）アタリレート、トリブロモフエニルォキシェチル（メタ）アタリレートなど が挙げられる。 (Meth) acrylate, η-propyl (meth) acrylate, isopropyl (meth) acrylate, η-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n xyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, tert-butyl cyclohexyl (meth) acrylate, 2_ethyl (meth) acrylate, tert-octyl (meth) acrylate, dodecyl (meth) ate Rate, Octadecyl (meth) acrylate, Acetoxy Shetyl (meth) acrylate, Phenyl (meth) acrylate, 2-Hydroxyethyl (meth) acrylate, 2-Methoxy ethyl (meth) acrylate, 2_Ethoxyethyl (meth) Atarirate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3 phenoxy 2 hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (Meth) Atallate, Diethylene Glycolanol Monophenol Ninore Etherenore (Meth) Atalylate, Triethylene Glycole Monomethino Methylenoatenore (Meth) Atallate, Triethylene Glyconore Monomethinoreate Ter (Meth) Atari , Polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β-phenoloxy chelyl (meth) acrylate, nourphenoxypolyethylene Glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclofluoropentyl (meth) acrylate, perfluorooctyl cetyl (meth) acrylate, tribromophenyl (Meth) acrylate, tribromophenyloxychetyl (meth) acrylate, and the like.
[0066] 前記クロトン酸エステル類としては、例えば、クロトン酸ブチル、クロトン酸へキシル などが挙げられる。  [0066] Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.
前記ビュルエステル類としては、例えば、ビュルアセテート、ビュルプロピオネート、 ビュルブチレート、ビニルメトキシアセテート、安息香酸ビュルなどが挙げられる。 前記マレイン酸ジエステル類としては、例えば、マレイン酸ジメチル、マレイン酸ジ ェチル、マレイン酸ジブチルなどが挙げられる。  Examples of the butyl esters include butyl acetate, bupropionate, butyl butyrate, vinyl methoxyacetate, and benzoic acid butyl. Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
前記フマル酸ジエステル類としては、フマル酸ジメチル、フマル酸ジェチル、フマル 酸ジブチルなどが挙げられる。  Examples of the fumaric acid diesters include dimethyl fumarate, jetyl fumarate, and dibutyl fumarate.
前記ィタコン酸ジエステル類としては、ィタコン酸ジメチル、ィタコン酸ジェチル、ィ タコン酸ジブチルなどが挙げられる。  Examples of the itaconic acid diesters include dimethyl itaconate, jetyl itaconate, and dibutyl itaconate.
[0067] 前記 (メタ）アクリルアミド類としては、例えば、 （メタ）アタリリノレアミド、 Ν—メチノレ (メタ )ァクリノレアミド、 Ν ェチル (メタ）アクリルアミド、 Ν—プロピル (メタ）アクリルアミド、 Ν —イソプロピル（メタ）アクリルアミド、 Ν _η_ブチルアタリノレ（メタ）アクリルアミド、 Ν— tert ブチル（メタ）アクリルアミド、 N—シクロへキシル（メタ）アクリルアミド、 N— (2— メトキシェチル）（メタ）アクリルアミド、 N, N—ジメチル（メタ）アクリルアミド、 N， N—ジ ェチル（メタ）アクリルアミド、 N—フエニル（メタ）アクリルアミド、 N—べンジル（メタ）ァ クリルアミド、 （メタ）アタリロイルモルホリン、ジアセトンアクリルアミドなどが挙げられる。 [0067] The (meth) acrylamides include, for example, (meth) atalinoleamide, Ν-methinole (meth) acrylolamide, ェ ethyl (meth) acrylamide, Ν-propyl (meth) acrylamide, 、 -isopropyl (meth) ) Acrylamide, Ν_η_Butyl Atalinole (meth) acrylamide, Ν-tert Butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (Meth) acrylamide, N, N-di Examples include ethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) atalyloylmorpholine, diacetone acrylamide and the like.
[0068] 前記ビュルエーテル類としては、例えば、メチルビニルエーテル、ブチルビニルェ 一テル、へキシルビニルエーテル、メトキシェチルビニルエーテルなどが挙げられる。 前記ビュルアルコールのエステル類としては、ベルサト酸ビュル、酢酸ビュル、ギ酸 ビュル、プロピオン酸ビュル、酪酸ビュルなどが挙げられる。  [0068] Examples of the butyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, and the like. Examples of the esters of butyl alcohol include versato acid butyl, acetate butyl, formate butyl, propionate butyl, butyrate butyl.
前記スチレン類としては、例えば、スチレン、メチルスチレン、ジメチルスチレン、トリ メチノレスチレン、ェチノレスチレン、イソプロピノレスチレン、ブチノレスチレン、ヒドロキシス チレン、メトキシスチレン、ブトキシスチレン、ァセトキシスチレン、クロロスチレン、ジク ロロスチレン、ブロモスチレン、クロロメチルスチレン、酸性物質により脱保護可能な基 (例えば、 tert—ブチルォキシカルボニル基等）で保護されたヒドロキシスチレン、ビ ニル安息香酸メチル、 ひ一メチルスチレンなどが挙げられる。  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethylol styrene, ethynole styrene, isopropyleno styrene, butino styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, diethylene styrene. Examples include styrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, tert-butyloxycarbonyl group), methyl vinyl benzoate, and monomethylstyrene. .
[0069] 本発明におけるアルカリ溶解性ポリマーの分子量としては、特に制限は無く目的に 応じて適宜選択することができるが、金属微粒子の分散安定性の観点から、例えば、 重量平均分子量として、 2, 000〜300, 000力 S好ましく、 4, 000〜： 150, 000力 Sより 好ましく、 6000〜： 100, 000力 S特に好ましレ、0 [0069] The molecular weight of the alkali-soluble polymer in the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of dispersion stability of the metal fine particles, for example, the weight average molecular weight is 2, 000-300,000 force S preferred, 4,000-: 150,000 force S more preferred, 6000-: 100,000 force S particularly preferred, 0
[0070] また、本発明におけるアルカリ溶解性ポリマーの有機概念図における有機性/無 機性比（I/O値）は 0. 44以上 1. 65以下が好ましぐ 0. 5以上 0. 6以下が更に好ま しい。前記 I/O値が低すぎると水に可溶となってしまい、また、前記 I/O値が高くな ると、アルカリ水溶液にも不溶となってしまう。  [0070] Further, the organic / inorganic ratio (I / O value) in the organic conceptual diagram of the alkali-soluble polymer in the present invention is preferably 0.44 or more and 1.65 or less 0.5 or more and 0.6. The following are more preferred: If the I / O value is too low, it becomes soluble in water, and if the I / O value is high, it becomes insoluble in an alkaline aqueous solution.
本発明におけるアルカリ溶解性ポリマーが硫黄原子を有する場合、ポリマー中の硫 黄原子の含有量は、金属微粒子の分散安定性の観点から、 0. 5質量％〜20質量 %が好ましぐ 1. 0質量％〜： 10. 0質量％が更に好ましい。また、本発明におけるァ ルカリ溶解性ポリマーが窒素原子を有する場合、ポリマー中の窒素原子の含有量は When the alkali-soluble polymer in the present invention has a sulfur atom, the sulfur atom content in the polymer is preferably 0.5% by mass to 20% by mass from the viewpoint of dispersion stability of the metal fine particles. From 0% by mass to 10.0% by mass is more preferable. In addition, when the alkali-soluble polymer in the present invention has a nitrogen atom, the content of the nitrogen atom in the polymer is
、金属微粒子の分散安定性の観点から、 0. 5質量％〜20質量％が好ましぐ 1. 0質 量％〜10. 0質量％が更に好ましい。更に、本発明におけるアルカリ溶解性ポリマー が硫黄原子および窒素原子の両者を有する場合、硫黄原子（s)と窒素原子 (n)との 質量比（sZn)は、金属微粒子の分散安定性の観点から、 0. 01〜200好ましぐ 0. ：!〜 20が更に好ましい。 From the viewpoint of dispersion stability of the metal fine particles, 0.5% by mass to 20% by mass is preferable, and 1.0% by mass to 10.0% by mass is more preferable. Furthermore, when the alkali-soluble polymer in the present invention has both a sulfur atom and a nitrogen atom, the mass ratio (sZn) of the sulfur atom (s) to the nitrogen atom (n) is determined from the viewpoint of dispersion stability of the metal fine particles. , 0.01-200 is preferred 0. :!-20 is more preferable.
[0071] 本発明におけるアルカリ溶解性ポリマーが硫黄原子を含有する場合の具体例とし ては、例えば、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 子化合物が挙げられる。 [0071] Specific examples of the case where the alkali-soluble polymer in the present invention contains a sulfur atom include, for example, a polymer compound having at least one repeating unit represented by the following general formula (1). It is done.
[0072] [化 1] [0072] [Chemical 1]
Figure imgf000019_0001
Figure imgf000019_0001
[0073] 前記一般式（1)において、 R1は、水素原子、または総炭素数 1〜4のアルキル基を 表す。総炭素数 1〜4のアルキル基としては、例えば、メチノレ基、ェチル基、ノノレマノレ 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。 In the general formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms in total. Examples of the alkyl group having 1 to 4 carbon atoms include methinole group, ethyl group, nonolemanolepropyl group, isopropyl group, normal butyl group, sec butyl group, isobutyl group, tert-butyl group, etc. Groups are preferred.
[0074] 前記一般式（1)において、 R2は、水素原子、総炭素数:!〜 18のアルキル基、総炭 素数 6〜： 14のァリール基、または総炭素数 7〜： 16のァラルキル基を表し、このアルキ ル基、ァリール基、およびァラルキル基は各々独立に、無置換でも置換基を有してい てもよく、飽和または不飽和の環状構造を形成してレ、てもよレ、。 In the general formula (1), R 2 represents a hydrogen atom, an alkyl group having a total carbon number of! To 18, an aryl group having a total carbon number of 6 to 14 or a aralkyl having a total carbon number of 7 to 16. The alkyl group, aryl group, and aralkyl group each independently may be unsubstituted or substituted, and may form a saturated or unsaturated cyclic structure. ,.
[0075] 前記 R2で表される総炭素数 1〜： 18のアルキル基は、無置換でも置換基を有してい てもよく、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、ォクチノレ 基、ドデシル基、ステアリル基等のアルキル基が挙げられる。置換基を有する場合の 置換基としては、例えば、ハロゲン原子、水酸基、アミノ基、アミド基、カルボキシノレ基 、エステル基、スルホニル基等が好適である。 [0075] The alkyl group having 1 to 18 carbon atoms in total represented by R 2 may be unsubstituted or substituted, and examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, Examples thereof include alkyl groups such as normal butyl group, sec butyl group, isobutyl group, tert-butyl group, hexyl group, octinole group, dodecyl group and stearyl group. As the substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxynole group, an ester group, a sulfonyl group and the like are preferable.
[0076] 上記のうち、 R2の表すアルキル基としては、総炭素数:!〜 12のアルキル基が好まし く、総炭素数 1〜8のアルキル基がより好ましぐメチノレ基、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、 tert—ブチル基は特に好ましい。 Of the above, as the alkyl group represented by R 2 , an alkyl group having a total carbon number of! To 12 is preferable, and an alkyl group having a total carbon number of 1 to 8 is more preferable. Normal propi Particularly preferred are a ru group, an isopropyl group, a normal butyl group and a tert-butyl group.
[0077] 前記 R2で表されるァリール基は、無置換でも置換基を有していてもよぐ総炭素数 6 〜 14のァリール基が好ましぐ例えば、フエニル基、トルィル基、キシリル基、ナフチ ル基、アントラセニル等のァリール基が挙げられる。置換基を有する場合の置換基と しては、例えば、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、スルホニル基等が好適である。 [0077] The aryl group represented by R 2 is preferably an aryl group having 6 to 14 carbon atoms which may be unsubstituted or substituted. For example, a phenyl group, a tolyl group, a xylyl group And aryl groups such as naphthyl and anthracenyl. As the substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.
[0078] 上記のうち、 R2の表すァリール基としては、総炭素数 6〜： 10のァリール基が好ましく 、フエ二ル基は特に好ましい。 Of the above, the aryl group represented by R 2 is preferably an aryl group having a total carbon number of 6 to 10 and particularly preferably a phenyl group.
[0079] 前記 R2で表されるァラルキル基は、無置換でも置換基を有していてもよぐ総炭素 数 7〜： 16のァラルキル基が好ましぐ例えば、ベンジル基、フエネチル基、ナフチルメ チル基、アントラセニルメチル基等のァラルキル基が挙げられる。置換基を有する場 合の置換基としては、例えば、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、スルホニル基等が好適である。 [0079] The aralkyl group represented by R 2 is preferably an aralkyl group having a total carbon number of 7 to 16 which may be unsubstituted or substituted. For example, a benzyl group, a phenethyl group, a naphthyl group. Examples include aralkyl groups such as a til group and anthracenylmethyl group. As the substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.
[0080] 上記のうち、 R2の表すァラルキル基としては、総炭素数 7〜： 11のァラルキル基が好 ましぐベンジル基は特に好ましい。 Among the above, as the aralkyl group represented by R 2 , a benzyl group is particularly preferred, which is preferably an aralkyl group having 7 to 11 carbon atoms in total.
[0081] 前記一般式（1)において、 Zは、—O—または NH—を表す。また、 Yは、総炭素数 ：!〜 8の 2価の連結基を表す。  In the general formula (1), Z represents —O— or NH—. Y represents a divalent linking group having a total carbon number of! ~ 8.
Yで表される総炭素数：!〜 8の 2価の連結基は、アルキレン基（例、メチレン、ェチレ ン、プロピレン、ブチレン、ペンチレン）、アルケニレン基（例、ェテニレン、プロぺニレ ン）、アルキニレン基（例、ェチニレン、プロピニレン）、ァリーレン基（例、フエ二レン）、 二価のへテロ環基（例、 6—クロ口一 1、 3、 5—トリアジン一 2、 4ージィノレ基、ピリミジン 2、 4_ジィノレ基、キノキサリン一 2、 3 _ジイノレ基、ピリダジン一 3, 6—ジィル）、 _〇 ―、 _CO_、 -NR- (Rは水素原子、アルキル基またはァリール基）、またはこれら の組み合わせ（例えば一 NHCH CH NH―、一NHCONH—等）であることが好ま しい。  The divalent linking group having a total carbon number represented by Y:! To 8 is an alkylene group (e.g., methylene, ethylene, propylene, butylene, pentylene), an alkenylene group (e.g., ethenylene, propenylene), Alkynylene group (eg, ethynylene, propynylene), arylene group (eg, phenylene), divalent heterocyclic group (eg, 6-chloro-1, 1,3-triazine 1, 2-4-zinole, pyrimidine 2, 4_ dinole group, quinoxaline 1, 2, 3 _ diinole group, pyridazine 1, 3, 6- diyl), _ ○-, _CO_, -NR- (R is a hydrogen atom, an alkyl group or an aryl group), or these A combination (for example, one NHCH CH NH—, one NHCONH—, etc.) is preferred.
上記のうちアルキレン基、アルケニレン基、アルキニレン基、ァリーレン基、二価の ヘテロ環基、 Rのアルキル基またはァリール基は、置換基を有していてもよい。置換 基の例としては、ァリール基の置換基と同じである。 Rのアルキル基およびァリール基 は前述と同義である。 Among the above, the alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, R alkyl group or aryl group may have a substituent. Examples of the substituent are the same as those of the aryl group. R alkyl and aryl groups Is as defined above.
[0082] Yで表される総炭素数：!〜 8の 2価の連結基のうち、総炭素数:!〜 6の 2価の連結基 が好ましぐ中でも、エチレン基、プロピレン基、ブチレン基、へキシレン基、 CH—  [0082] Of the divalent linking groups represented by Y:! ~ 8, the divalent linking groups having the total carbon number:! ~ 6 are preferred, especially ethylene groups, propylene groups, butylenes. Group, hexylene group, CH—
2 2
CH (OH) - CH―、一 C H -O-C H—は特に好ましい。 CH 2 (OH) 2 —CH— and 1 C 3 H 2 —O—C 3 H— are particularly preferred.
2 2 4 2 4  2 2 4 2 4
[0083] 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 みならず、 2種以上を共重合して硫黄原子を 2以上含む高分子化合物であってもよ レ、。また、側鎖を構成するチォエーテル構造は、硫黄原子を 1つのみならず、前記 Z 、 R2を、硫黄原子を有する基で構成することにより、 2つ以上の硫黄原子を有する側 鎖とすることができる。 [0083] The polymer dispersant according to the present invention includes not only one type of repeating unit represented by the general formula (1) but also a polymer compound containing two or more sulfur atoms by copolymerizing two or more types. But yeah, In addition, the thioether structure constituting the side chain has not only one sulfur atom but also a side chain having two or more sulfur atoms by constituting Z and R 2 with a group having a sulfur atom. be able to.
[0084] 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、あるいはチォエーテル基を (好ましくは側鎖に）持つ単 量体の単独重合、また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、エチレン性不飽和単量体の側鎖 にチォエーテル構造を導入する、あるい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、また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。  [0084] The polymer dispersant according to the present invention introduces a thioether structure into a desired polymer compound (preferably as a side chain) or is a single monomer having a thioether group (preferably in a side chain). It can be obtained by polymerization or copolymerization of a monomer having a thioether group (preferably in the side chain) with another monomer. Preferably, a thioether structure is introduced into the side chain of the ethylenically unsaturated monomer, or homopolymerization of an ethylenically unsaturated monomer having a thioether structure in the side chain, or an ethylenically unsaturated group having a thioether structure in the side chain. It can be obtained by copolymerization of a saturated monomer and another copolymer component.
[0085] 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、 これらに制限されるものではない。  [0085] Specific examples of the repeating unit represented by the general formula (1) are shown below. However, the present invention is not limited to these.
[0086] [化 2] [0086] [Chemical 2]
Figure imgf000022_0001
Figure imgf000022_0001
[0087] 上述の中でも、特に R1が水素原子あるいはメチル基であって、 R2がメチル基、ェチ ノレ基、ノルマルプロピル基、ノルマルブチル基、 tert—ブチル基、フヱニル基であつ て、 Zが _〇一であって、 Yがエチレン基、である化合物が好ましい。 [0087] Among the above, in particular, R 1 is a hydrogen atom or a methyl group, and R 2 is a methyl group, an ethynole group, a normal propyl group, a normal butyl group, a tert-butyl group, a phenyl group, A compound in which Z is _〇1 and Y is an ethylene group is preferable.
[0088] 本発明におけるアルカリ溶解性ポリマーが窒素原子を含有する場合の具体例とし ては、例えば、下記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 が挙げられる。 [0088] As a specific example when the alkali-soluble polymer in the present invention contains a nitrogen atom, Examples thereof include polymer compounds having at least one repeating unit represented by the following.
[0089] [化 3]  [0089] [Chemical 3]
Figure imgf000023_0001
Figure imgf000023_0001
[0090] 以下に本発明における硫黄原子あるいは窒素原子を含有するアルカリ可溶解性ポ リマーの具体例をあげるが、これらに限定される物ではなレ、。下記化合物 PO— :!〜 P 0— 34ttA、 B、 Cで表される繰り返し単位を有した共重合体である。また a、 b、 c、は 繰り返し単位 A, B, Cそれぞれの質量％の比を表す。 [0090] Specific examples of the alkali-soluble polymer containing a sulfur atom or a nitrogen atom in the present invention will be given below, but the invention is not limited to these. The following compounds PO— :! to P 0— are copolymers having repeating units represented by 34ttA, B, and C. Moreover, a, b, and c represent the mass% ratio of each of the repeating units A, B, and C.
[0091] [化 4] [0091] [Chemical 4]
[S^] [2600] [S ^] [2600]
Figure imgf000024_0001
Figure imgf000024_0001
9 90ZC/900Zdf/X3d 滅 OOZ OAV
Figure imgf000025_0001
9 90ZC / 900Zdf / X3d OOZ OAV
Figure imgf000025_0001
[0093] また、本発明の金属微粒子分散物には、界面活性剤、防腐剤、または分散安定剤 などを適宜配合してもよい。 [0093] In addition, a surfactant, preservative, or dispersion stabilizer may be appropriately blended in the metal fine particle dispersion of the present invention.
[0094] 前記界面活性剤としては、ァニオン系、カチオン系、ノニオン系、ベタイン系界面活 性剤のいずれも使用でき、ァニオン系およびノニオン系界面活性剤が特に好ましい。 界面活性剤の HLB値は塗布液の溶媒が非極性溶剤であるため、 3〜6程度のもの が好ましい。 As the surfactant, any of anionic, cationic, nonionic, and betaine surfactants can be used, and anionic and nonionic surfactants are particularly preferable. The HLB value of the surfactant is preferably about 3 to 6, since the solvent of the coating solution is a nonpolar solvent.
[0095] 尚、前記 HLB値については、例えば「界面活性剤ハンドブック」（吉田時行、進藤 信一、山中樹好編、工学図書 (株)発行昭和 62年）に記載されている。前記界面活 性剤の具体例としては、プロピレングリコールモノステアリン酸エステル、プロピレング リコールモノラウリン酸エステル、ジエチレングリコールモノステアリン酸エステル、ソル ビタンモノラウリル酸エステル、ポリオキシエチレンソルビタンモノラウリル酸エステル などがある。界面活性剤の例についても前述の「界面活性剤ハンドブック」に記載さ れている。 [0095] The HLB value is described in, for example, "Surfactant Handbook" (Tokiyuki Yoshida, Shinichi Shindo, Yoshiyoshi Yamanaka, published by Engineering Book Co., Ltd. 1987). Specific examples of the surfactant include propylene glycol monostearate, propylene glycol monolaurate, diethylene glycol monostearate, and solvent. There are bitane monolaurate and polyoxyethylene sorbitan monolaurate. Examples of surfactants are also described in the aforementioned “Surfactant Handbook”.
[0096] 前記分散安定剤については、例えば「顔料分散技術 (技術情報協会 (株） 1999年 発行）」に記載されているものを用いることができる。  As the dispersion stabilizer, for example, those described in “Pigment Dispersion Technology (issued by Technical Information Association Co., Ltd. 1999)” can be used.
[0097] 《本発明の着色組成物》 [0097] <Coloring composition of the present invention>
本発明の着色組成物は、少なくとも上述の本発明の金属微粒子分散物を含有し、 また樹脂またはその前駆体の少なくとも 1種、光重合開始剤、溶媒等を含有する。必 要に応じて、顔料微粒子を含有してもよい。  The colored composition of the present invention contains at least the fine metal particle dispersion of the present invention described above, and also contains at least one resin or a precursor thereof, a photopolymerization initiator, a solvent, and the like. If necessary, pigment fine particles may be contained.
また、本発明の金属微粒子分散物および本発明の着色組成物は、黒色の黒色組 成物であることが好ましレ、。ここで、「黒色」とは、無彩色点（x = 0. 333, y = 0. 333, Y=0)からの色度のズレが Δ Εで 100以内である色をいう。また、「黒色組成物」とは 、本発明の金属微粒子分散物に含まれる全金属原子濃度を 4. 0 X 10— 4モル/ Lの分 散溶液とした場合に、波長 450nmと 550nmでの吸収の比、すなわち、 Further, the metal fine particle dispersion of the present invention and the colored composition of the present invention are preferably a black black composition. Here, “black” refers to a color having a deviation of chromaticity from an achromatic point (x = 0.333, y = 0.333, Y = 0) within Δ100. Also, "black composition" and, when the total metal atom concentration contained in the metal fine particle dispersion of the present invention was distributed solution of 4. 0 X 10- 4 mol / L, at a wavelength of 450nm and 550nm Absorption ratio, ie
黒色度 =八 3 (450應） /八 3 (550應）カ、0. 5〜2· 0の範囲である組成物を 意味する。前記黒色組成物の吸収は、 日立社製 U— 3410形自記分光光度形を用 いて測定することができる。  This means a composition having a blackness of 8 3 (450 °) / 8 3 (550 °) and a range of 0.5 to 2.0. Absorption of the black composition can be measured using Hitachi U3410 model autospectrophotometer.
[0098] (樹脂またはその前駆体） [0098] (Resin or its precursor)
本発明の着色組成物に添加することのできる樹脂としては、側鎖にカルボン酸基を 有するポリマー、例えば、特開昭 59— 44615号公報、特公昭 54— 34327号公報、 特公昭 58— 12577号公報、特公昭 54— 25957号公報、特開昭 59— 53836号公 報、および特開昭 59— 71048号公報に記載されているメタクリル酸共重合体、アタリ ル酸共重合体、ィタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部 分エステル化マレイン酸共重合体、また側鎖にカルボン酸基を有するセルロース誘 導体が挙げられる。更に、水酸基を有するポリマーに環状酸無水物を付加したものも 好ましく使用することができる。特に、米国特許第 4139391号明細書に記載のベン ジル (メタ）アタリレートと（メタ）アクリル酸の共重合体やべンジル (メタ）アタリレートと（ メタ）アクリル酸と他のモノマーとの多元共重合体を好適に挙げることができる。 [0099] 前記樹)!旨としては、 30〜400mgKOti/gの範囲の酸価と 1000〜300000の範 囲の重量平均分子量を有するものを選択して使用するのが好ましい。その他、種々 の性能、例えば、硬化膜の強度を改良するために、現像性等に悪影響を与えない範 囲で、アルカリ可溶性ポリマーを添カ卩してもよい。これらのアルカリ可溶性ポリマーとし ては、本発明におけるアルカリ溶解性ポリマーを用いてもよいし、その他アルコール 可溶性ナイロンやエポキシ樹脂を挙げることができる。 Examples of the resin that can be added to the coloring composition of the present invention include polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577. Methacrylic acid copolymer, tallic acid copolymer, itaconic acid described in Japanese Patent Publication No. SHO 54-25957, Japanese Patent Publication SHO 59-53836, and Japanese Patent Publication SHO 59-71048. Examples thereof include copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and cellulose derivatives having a carboxylic acid group in the side chain. Furthermore, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. In particular, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid or benzyl (meth) acrylate and (meth) acrylic acid and other monomers described in US Pat. No. 4,139,391. A copolymer can be mentioned preferably. [0099] The above-mentioned tree)! Is preferably selected from those having an acid value in the range of 30 to 400 mg KOti / g and a weight average molecular weight in the range of 1000 to 300,000. In addition, in order to improve various performances, for example, the strength of the cured film, an alkali-soluble polymer may be added in a range that does not adversely affect developability and the like. As these alkali-soluble polymers, the alkali-soluble polymers in the present invention may be used, and other alcohol-soluble nylons and epoxy resins may be used.
前記樹脂の前駆体としてはエチレン性不飽和二重結合を有し、光照射によって付 加重合 (以下「光重合性モノマー」とレ、う場合がある）し、硬化することで樹脂となる光 重合性モノマー等が挙げられる。これらにっレ、ては後述する。  The precursor of the resin has an ethylenically unsaturated double bond, undergoes addition polymerization by light irradiation (hereinafter sometimes referred to as “photopolymerizable monomer”), and cures to form a resin that becomes a resin. Examples thereof include a polymerizable monomer. These will be described later.
[0100] (開始剤）  [0100] (Initiator)
本発明の着色組成物に添加する開始剤は、光照射によってラジカルが発生する光 重合開始剤等が挙げられる。これについては後述する。  Examples of the initiator added to the colored composition of the present invention include a photopolymerization initiator that generates radicals by light irradiation. This will be described later.
[0101] (溶媒）  [0101] (Solvent)
本発明の着色組成物に添加することのできる溶剤としては、特に制限なく用いられ るが、前記金属微粒子溶媒置換の際に用いた溶媒と同様な物が、金属微粒子分散 安定性の観点力もも好ましぐ中でも SP値が 9. 0以上のものが好ましい。  The solvent that can be added to the coloring composition of the present invention is not particularly limited, but the same solvent as that used for the metal fine particle solvent replacement has the viewpoint of dispersion stability of the fine metal particles. Among these, those having an SP value of 9.0 or more are preferable.
例えば、メチルェチルケトン、 2—プロパノール、 1 プロパノール、 1ーメトキシー2 プロピルアセテート、シクロへキサノン、アセトン、 N—メチルピロリドン、あるいはそ れらの混合物などが好適に挙げられる。  For example, methyl ethyl ketone, 2-propanol, 1 propanol, 1-methoxy-2-propyl acetate, cyclohexanone, acetone, N-methylpyrrolidone, or a mixture thereof can be preferably mentioned.
[0102] (顔料微粒子） [0102] (Pigment fine particles)
本発明の着色組成物には、金属微粒子分散物の他に、顔料微粒子を含有せしめ ることにより、色相を黒色に近づけることも可能となる。  In addition to the metal fine particle dispersion, the colored composition of the present invention can contain pigment fine particles to make the hue close to black.
本発明の着色組成物に含有させることのできる顔料微粒子としては、カーボンブラ ック、チタンブラック、または黒鉛が好適なものとして挙げられる。  Suitable examples of pigment fine particles that can be contained in the colored composition of the present invention include carbon black, titanium black, and graphite.
前記カーボンブラックの例としては、 Pigment Black (ピグメント 'ブラック） 7 (力 一ボンブラック C. I. No. 77266)力好ましレ、。市販品としては、「三菱カーボンブラ ック MA100」（三菱化学 (株)製)、「三菱カーボンブラック # 5」（三菱化学 (株)製)が 挙げられる。 [0103] 前記チタンブラックの例としては、 TiO、 Ti〇、 TiNやこれらの混合物が好ましレ、。 As an example of the carbon black, Pigment Black (Pigment Black) 7 (Strong Bon Black CI No. 77266) is preferred. Commercial products include “Mitsubishi Carbon Black MA100” (Mitsubishi Chemical Corporation) and “Mitsubishi Carbon Black # 5” (Mitsubishi Chemical Corporation). [0103] As examples of the titanium black, TiO, TiO, TiN, and mixtures thereof are preferable.
2  2
市販品として、三菱マテリアルズ (株)製の商品名「12S」や「13M」が挙げられる。ま た用いられるチタンブラックの粒子径は 40〜： !OOnmが好ましい。  Commercially available products include “12S” and “13M” trade names manufactured by Mitsubishi Materials Corporation. The particle size of titanium black used is preferably 40 to: OOnm.
[0104] 前記黒鉛の例としては、粒子径がストークス径として 3 a m以下のものが好ましい。 3 z mを超えた黒鉛を用いると、遮光パターンの輪郭形状が不均一になり、シャープネ スが悪くなる場合がある。また、粒子径の大部分 (好ましくは 95%以上）が 0. 1 μ m以 下であることが望ましい。  [0104] As an example of the graphite, those having a particle diameter of 3 am or less as a Stokes diameter are preferable. If graphite exceeding 3 zm is used, the contour shape of the light-shielding pattern becomes non-uniform and sharpness may deteriorate. In addition, it is desirable that most of the particle diameter (preferably 95% or more) is 0.1 μm or less.
[0105] 本発明の着色組成物は、前記顔料微粒子の他に、他の公知の顔料微粒子を用い ることもできる。顔料は一般に有機顔料と無機顔料とに大別されるが、本発明におい ては有機顔料が好ましい。好適に使用される有機顔料の例としては、ァゾ系顔料、フ タロシアニン系顔料、アントラキノン系顔料、ジォキサジン系顔料、キナクリドン系顔料 、イソインドリノン系顔料、ニトロ系顔料を挙げることができる。前記有機顔料の色相は 、例えば黄色顔料、オレンジ顔料、赤色顔料、バイオレット顔料、青色顔料、緑色顔 料、ブラウン顔料、黒色顔料等が好ましい。  [0105] In addition to the pigment fine particles, other known pigment fine particles may be used in the colored composition of the present invention. In general, the pigments are roughly classified into organic pigments and inorganic pigments. In the present invention, organic pigments are preferred. Examples of organic pigments preferably used include azo pigments, phthalocyanine pigments, anthraquinone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and nitro pigments. The hue of the organic pigment is preferably, for example, a yellow pigment, an orange pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment, or a black pigment.
[0106] 前記顔料微粒子としては、具体的には、特開 2005— 17716号公報 [0038]〜[0 040] ίこ記載の色材や、特開 2005— 361447号公幸 [0068]〜[0072] ίこ記載の 顔料や、特開 2005— 17521号公報 [0080]〜[0088]に記載の着色剤を好適に用 レ、ることができる。但し、本発明はこれらに限定されるものではない。  [0106] Specific examples of the pigment fine particles include the color materials described in JP-A-2005-17716 [0038] to [0 040], and JP 2005-361447 No. [0068] to [0072]. The pigments described in this document and the colorants described in JP-A-2005-17521, [0080] to [0088] can be suitably used. However, the present invention is not limited to these.
[0107] また、前記着色剤の他、「顔料便覧、 日本顔料技術協会編、誠文堂新光社、 1989 」、「COL〇UR INDEX, THE SOCIETY OF DYES & COL〇URIST、 T HIRD EDITION, 1987」に記載のものを参照して適宜用いることもできる。  [0107] In addition to the above colorants, "Pigment Handbook, edited by Japan Pigment Technology Association, Seikodo Shinkosha, 1989", "COLUR INDEX, THE SOCIETY OF DYES & COL URIST, T HIRD EDITION, 1987 Can be used as appropriate with reference to those described in the above.
[0108] また、前記顔料微粒子は、色相が上述の本発明における金属微粒子の色相と補色 関係にあるものを用いることが望ましい。また、顔料微粒子は 1種で用いてもよいし、 2 種以上を組み合せて用いてもよい。好ましい顔料の組み合わせとしては、赤色系お よび青色系の互いに補色関係にある顔料混合物と黄色系および紫色系の互いに補 色関係にある顔料混合物との組み合せや、前記の混合物に更に黒色の顔料を加え た組み合わせや、青色系と紫色系と黒色系との顔料の組合せを挙げることができる。  [0108] Further, it is desirable that the pigment fine particles have a hue that is complementary to the hue of the metal fine particles in the present invention. Also, the pigment fine particles may be used alone or in combination of two or more. Preferred pigment combinations include a combination of a red and blue pigment mixture complementary to each other and a yellow and purple pigment mixture complementary to each other, or a black pigment added to the above mixture. Additional combinations and combinations of blue, violet and black pigments can be mentioned.
[0109] 前記顔料微粒子は、組成物中に均一に分散されていることが好ましい。前記顔料 微粒子の算術平均粒径は、 5nm〜5 μ mが好ましぐ特に 10nm〜l μ mが好ましい 。本発明の着色組成物をカラーフィルター用途として用いる場合には、前記顔料微 粒子の算術平均粒径は 20nm〜0. 5 μ mが好ましい。 [0109] The pigment fine particles are preferably dispersed uniformly in the composition. The pigment The arithmetic average particle diameter of the fine particles is preferably 5 nm to 5 μm, particularly preferably 10 nm to 1 μm. When the colored composition of the present invention is used as a color filter, the arithmetic average particle size of the pigment fine particles is preferably 20 nm to 0.5 μm.
[0110] ぐ遮光画像作製用着色組成物 > [0110] Color shading image preparation coloring composition>
前記本発明の着色組成物を、特に遮光画像作製用の着色組成物（以下、「遮光用 着色組成物」ともレ、う。）として用いる場合にっレ、て以下に詳述する。  In particular, when the colored composition of the present invention is used as a colored composition for producing a light-shielding image (hereinafter referred to as “colored composition for light shielding”), it will be described in detail below.
前記遮光用着色組成物を用いて遮光層（パターニングする前の層）を形成した場 合、遮光層の膜厚 l x mあたりの光学濃度は 1以上となることが好ましい。例えば、力 ラーフィルターの作製時など、ポストベータの際、金属微粒子が融着するのを防止す ることを考慮すると、前記遮光用着色組成物における金属微粒子の含有量は、形成 される遮光層の全固形分に対して 10〜90質量％、好ましくは 10〜80質量％程度に なるように調節することが好ましい。また、前記含有量は、金属微粒子の平均粒径に よる光学濃度の変動を考慮して行うのが好ましい。  When the light shielding layer (the layer before patterning) is formed using the light shielding coloring composition, the optical density per film thickness l x m of the light shielding layer is preferably 1 or more. For example, in consideration of preventing the metal fine particles from fusing during post-beta, such as when producing a power filter, the content of the metal fine particles in the light-shielding coloring composition is the light-shielding layer to be formed. It is preferable to adjust so that it may become 10-90 mass% with respect to the total solid content of this, Preferably it is about 10-80 mass%. In addition, the content is preferably determined in consideration of variation in optical density due to the average particle diameter of the metal fine particles.
また、後述の感光性を有する遮光用着色組成物における金属微粒子の含有量も 同様である。  The same applies to the content of metal fine particles in the light-shielding coloring composition having photosensitivity described below.
[0111] 本発明でいう「遮光画像」とは、ブラックマトリックスを包含する意味で用いられる。 「 ブラックマトリックス」とは、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、 CRT表示装置などの表示装置の周辺部に設けられた黒色の縁や、赤、青、緑の 画素間の格子状やストライプ状の黒色の部分、更に TFT遮光のためのドット状や線 状の黒色パターン等のことであり、このブラックマトリックスの定義は、例えば、菅野泰 平著、「液晶ディスプレイ製造装置用語辞典」、第 2版、 日刊工業新聞社、 1996年、 p. 64に記載されている。遮光画像の例としては、有機 ELディスプレイ（例えば、特開 2004— 103507号公幸艮）、 PDPのフロントノ ネノレ（列え ίま、、特開 2003— 51261号 公報）、 PALCではバックライトの遮光等が挙げられる。  In the present invention, the “light-shielded image” is used to include a black matrix. “Black matrix” means a black edge or a grid between red, blue, and green pixels on the periphery of display devices such as liquid crystal display devices, plasma display devices, EL display devices, and CRT display devices. This is a black part in the shape of a stripe or stripe, and also a dot-like or linear black pattern for TFT shading. The definition of this black matrix is, for example, Taihei Kanno, “Liquid Crystal Display Device Dictionary” 2nd edition, Nikkan Kogyo Shimbun, 1996, p. 64. Examples of light-shielded images include organic EL displays (for example, Japanese Patent Publication No. 2004-103507), PDP front non-nore (Nori Era, JP-A 2003-51261), and PALC for light shielding of the backlight. Etc.
ブラックマトリックスは表示コントラストを向上させるため、また薄膜トランジスター (TF Τ)を用いたアクティブマトリックス駆動方式の液晶表示装置の場合には光の電流リー クによる画質低下を防止するため、高い遮光性（光学濃度〇Dで 3以上）が必要であ る。 [0112] <感光性遮光画像作製用着色組成物 > Black matrix improves display contrast, and in the case of an active matrix liquid crystal display device using thin film transistors (TF Τ), it prevents high image quality due to light current leakage. A density of 3 or more at 0D is required. [0112] <Coloring composition for producing light-sensitive shading image>
前記遮光画像作製用着色組成物は感光性を有することがより好ましい。具体的に は、本発明の着色組成物に感光性樹脂組成物を添加することで感光性を付与する こと力 Sできる。前記感光性樹脂組成物は、バインダーとなるポリマー、光重合開始剤、 光重合性モノマー等を含有してなる態様が好ましく挙げられる。  More preferably, the colored composition for producing a light-shielding image has photosensitivity. Specifically, the photosensitivity can be imparted by adding a photosensitive resin composition to the colored composition of the present invention. A preferred embodiment of the photosensitive resin composition includes a binder polymer, a photopolymerization initiator, a photopolymerizable monomer, and the like.
[0113] 前記感光性樹脂組成物は、アルカリ水溶液で現像可能なものと、有機溶剤で現像 可能なものとがある。安全性と現像液のコストとの観点からは、アルカリ水溶液現像可 能なものが好ましレ、。前記感光性樹脂組成物にアルカリ水溶液現像性を持たせるた めにはバインダーのポリマーをアルカリ可溶性ポリマーにすることが好ましい。  [0113] The photosensitive resin composition includes those that can be developed with an alkaline aqueous solution and those that can be developed with an organic solvent. From the viewpoint of safety and the cost of the developer, those that can be developed with an aqueous alkaline solution are preferred. In order to give the photosensitive resin composition developability in an aqueous alkali solution, it is preferable that the polymer of the binder is an alkali-soluble polymer.
前記感光性樹脂組成物は、上述のような光や電子線などの放射線を受容する部分 が硬化するネガ型の組成物でもよレ、し、放射線未受容部が硬化するポジ型の組成物 であってもよい。  The photosensitive resin composition may be a negative composition in which a portion that receives radiation such as light or electron beam is cured as described above, or a positive composition in which a radiation non-receptive portion is cured. There may be.
[0114] 前記ポジ型の感光性樹脂組成物にはノボラック系の樹脂を用いたものが挙げられ る。前記ノボラック系樹脂としては、例えば、特開平 7— 43899号公報記載のアルカリ 可溶性ノボラック樹脂系を使用することができる。また、特開平 6— 148888号公報記 載のポジ型感光材料、即ち、該公報記載のアルカリ可溶性樹脂と感光剤として 1, 2 ナフトキノンジアジドスルホン酸エステルと該公報記載の熱硬化剤の混合物とを含 むポジ型感光材料を用いることができる。更に、特開平 5— 262850号公報記載の組 成物も活用可能である。  [0114] Examples of the positive photosensitive resin composition include those using a novolac resin. As the novolac resin, for example, an alkali-soluble novolac resin system described in JP-A-7-43899 can be used. Further, a positive photosensitive material described in JP-A-6-148888, that is, a mixture of an alkali-soluble resin described in the publication and 1,2 naphthoquinonediazide sulfonic acid ester as a photosensitive agent and a thermosetting agent described in the publication. The positive type photosensitive material containing it can be used. Furthermore, the composition described in JP-A-5-262850 can also be used.
[0115] ネガ型の感光性樹脂組成物としては、ネガ型ジァゾ樹脂とバインダーとからなる感 光性樹脂、光重合性組成物、アジド化合物とバインダーとからなる感光性樹脂組成 物、桂皮酸型感光性樹脂組成物等が挙げられる。その中でも、光重合開始剤、光重 合性モノマーおよびバインダーを基本構成要素として含む光重合性組成物が特に 好ましい。該光重合性組成物には、特開平 11一 133600号公報記載の「重合性化 合物 B」「重合開始剤 C」「界面活性剤」「接着助剤」や、その他の組成物が利用できる 例えば、ネガ型の感光性樹脂組成物であってアルカリ水溶液現像可能な感光性樹 脂組成物としては、主成分としてカルボン酸基含有バインダー（アルカリ可溶性バイ ンダ一）と、光重合開始剤と、光重合性モノマーと、を含んでなる感光性樹脂組成物 が挙げられる。尚、前記アルカリ可溶性バインダーとしては、前述の樹脂またはその 前駆体として例示した樹脂を好適なものとして使用できる。 [0115] The negative photosensitive resin composition includes a photosensitive resin composed of a negative diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition composed of an azide compound and a binder, and a cinnamic acid type. Examples thereof include a photosensitive resin composition. Among these, a photopolymerizable composition containing a photopolymerization initiator, a photopolymerizable monomer, and a binder as basic constituent elements is particularly preferable. As the photopolymerizable composition, “polymerizable compound B”, “polymerization initiator C”, “surfactant”, “adhesion aid” and other compositions described in JP-A-11-133600 are used. For example, a photosensitive resin composition that is a negative photosensitive resin composition and that can be developed with an aqueous alkali solution, includes a carboxylic acid group-containing binder (alkali-soluble binder) as a main component. 1), a photopolymerization initiator, and a photopolymerizable monomer. As the alkali-soluble binder, the above-described resins or resins exemplified as precursors thereof can be suitably used.
[0116] 前記アルカリ可溶性バインダーは、感光性の遮光用着色組成物の全固形分に対し て通常、 10〜95質量％含有され、更に 20〜90質量％含有されることが好ましい。 含有量が 10〜95質量％の範囲では、感光性樹脂層の粘着性が高すぎることもなく 、形成される層の強度および光感度が劣ることもない。  [0116] The alkali-soluble binder is usually contained in an amount of 10 to 95% by mass, more preferably 20 to 90% by mass, based on the total solid content of the photosensitive light-shielding coloring composition. When the content is in the range of 10 to 95% by mass, the adhesiveness of the photosensitive resin layer is not too high, and the strength and photosensitivity of the formed layer are not inferior.
[0117] 前記光重合開始剤としては、米国特許第 2367660号明細書に開示されているビ シナルポリケタルド二ルイ匕合物、米国特許第 2448828号明細書に記載されているァ シロインエーテルィヒ合物、米国特許第 2722512号明細書に記載のひ一炭化水素 で置換された芳香族ァシロイン化合物、米国特許第 3046127号および同第 29517 58号の各明細書に記載の多核キノンィ匕合物、米国特許第 3549367号明細書に記 載のトリアリールイミダゾールニ量体と p アミノケトンの組合せ、特公昭 51— 48516 号公報に記載のベンゾチアゾール化合物とトリハロメチルー s トリァジン化合物、米 国特許第 4239850号明細書に記載されているトリハロメチル— s トリアジンィ匕合物 、米国特許第 4212976号明細書に記載されているトリハロメチルォキサジァゾール 化合物等が挙げられる。特に好ましくはトリハロメチルー s—トリァジン、トリハロメチル ォキサジァゾール、トリアリールイミダゾールニ量体である。  [0117] Examples of the photopolymerization initiator include a vicinal polyketal dinitro compound disclosed in US Pat. No. 2,367,660 and a acyloin ether described in US Pat. No. 2448828. A polycyclic quinone compound described in U.S. Pat.Nos. 3046127 and 2951758, an aromatic acyloin compound substituted with a monohydrocarbon described in U.S. Pat. A combination of a triarylimidazole dimer and a p-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound and a trihalomethyl-s-triazine compound described in Japanese Patent Publication No. 51-48516, US Pat. No. 4,239,850 Examples include trihalomethyl-s triazine compounds described in the specification, trihalomethyloxadiazole compounds described in US Pat. No. 4,212,976, and the like. It is. Particularly preferred are trihalomethyl-s-triazine, trihalomethyl oxadiazole, and triarylimidazole dimer.
また、この他、特開平 11 133600号公報に記載の「重合開始剤 C」も好適なもの として挙げること力 Sできる。  In addition, “polymerization initiator C” described in JP-A-11 133600 can be cited as a suitable example.
これらの光重合開始剤または光重合開始剤系は、単独でも、二種類以上を混合し て用いてもよぐ特に二種類以上を用レ、ることが好ましい。また、感光性樹脂組成物 の全固形分に対する光重合開始剤の含有量は、 0. 5〜20質量％が一般的であり、 1〜： 15質量％が好ましい。  These photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture of two or more types. It is particularly preferable to use two or more types. The content of the photopolymerization initiator based on the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.
[0118] 黄ばみなどの着色がなぐ且つ露光感度を高くすることが可能であり優れた表示特 性を発揮することができる光重合開始剤の組み合わせの例としては、ジァゾール系 光重合開始剤と、トリアジン系光重合開始剤との組み合わせが挙げられる。中でも、 2 —トリクロロメチル 5 _ (p—スチリルスチリル）_ 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ニルメチルァミノ） - 3' -ブロモフエニル]― s -トリァジンとの組み合わせが最も好ましレ、。 [0118] Examples of combinations of photopolymerization initiators that are not yellowish and can be increased in exposure sensitivity and exhibit excellent display characteristics include a diazole photopolymerization initiator, The combination with a triazine type photoinitiator is mentioned. Among them, 2-trichloromethyl 5 _ (p-styrylstyryl) _ 1, 3, 4-oxadiazole and 2, 4- Bis (trichloromethyl) 6— [4 ′ — (N, N bisethoxycarbonylmethylamino) -3′-bromophenyl] —s-triazine is most preferred.
これらの光重合開始剤の比率は、ジァゾール系/トリァジン系の質量比率で、 95 /5〜20/80カ好ましく、より好ましく fま 90/10〜30/70であり、特に好ましく fま 8 0/20〜60/40である。これらの光重合開始剤は、特開平 1— 152449号公報、特 開平 1一 254918号公報、特開平 2— 153353号公報に記載されている。  The ratio of these photopolymerization initiators is 95/5 to 20/80, more preferably f / 90/10 to 30/70, and particularly preferably f / 80, by mass ratio of diazole / triazine. / 20-60 / 40. These photopolymerization initiators are described in JP-A-1-152449, JP-A-11-254918, and JP-A-2-153353.
更に、前記光重合開始時亜の好適な例としてはべンゾフエノン系も挙げられる。  Furthermore, a benzophenone type can also be mentioned as a suitable example of the above-mentioned photopolymerization initiation time.
[0119] また、感光性の遮光用着色組成物の固形分全体に占める顔料の割合が 15〜25 質量％付近の場合、前記光重合開始剤に、クマリン系化合物を混合することによつ ても、黄ばみなどの着色を抑制し、且つ高感度化することができる。 [0119] When the ratio of the pigment to the entire solid content of the photosensitive light-shielding coloring composition is about 15 to 25% by mass, a coumarin compound is mixed with the photopolymerization initiator. Also, coloring such as yellowing can be suppressed and high sensitivity can be achieved.
前記クマリン系化合物としては、 7- [2- [4- (3—ヒドロキシメチルビペリジノ） - 6 -ジェチルァミノ]トリアジニルァミノ] - 3-フエユルクマリンが最も好ましレ、。これらの 光重合開始剤とクマリン系化合物との比率は、光重合開始剤/クマリン系化合物の 質量比率で、 20/80〜80/20力 子ましく、より好ましくは 30/70〜70/30であり 、最も好ましくは 40/60〜60/40である。  As the coumarin-based compound, 7- [2- [4- (3-hydroxymethylbiperidino) -6-jetylamino] triazinylamino] -3-fuel coumarin is most preferred. The ratio of these photopolymerization initiators and coumarin compounds is the mass ratio of photopolymerization initiators / coumarin compounds, 20/80 to 80/20, and more preferably 30/70 to 70/30. And most preferably 40/60 to 60/40.
ただし、本発明に使用できる光重合性組成物はこれらに限定されるものではなぐ 公知のものの中力 適宜選択することできる。  However, the photopolymerizable composition that can be used in the present invention is not limited to these, and may be appropriately selected from known intermediate forces.
[0120] 前記光重合開始剤は、感光性の遮光用着色組成物の全固形分に対して、 0. 5〜 20質量％が一般的であり、：!〜 15質量％が好ましい。前記含有量が前記範囲内で あると、光感度や画像強度の低下を防止でき、十分に性能を向上させることができる [0120] The photopolymerization initiator is generally from 0.5 to 20 mass%, preferably from! To 15 mass%, based on the total solid content of the photosensitive shading coloring composition. When the content is within the above range, a decrease in photosensitivity and image intensity can be prevented, and the performance can be sufficiently improved.
[0121] 前記光重合性モノマーとしては、沸点が常圧で 100°C以上の化合物を挙げること ができる。例えば、ポリエチレングリコールモノ（メタ）アタリレート、ポリプロピレングリコ ールモノ (メタ）アタリレートおよびフヱノキシェチル (メタ）アタリレート等の単官能 (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、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ァク リレート、トリメチロールプロパンジアタリレート、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）ァク 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、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（アタ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、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若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後で (メタ）アタリレート化したもの等の多官能 (メタ[0121] Examples of the photopolymerizable monomer include compounds having a boiling point of 100 ° C or higher at normal pressure. For example, monofunctional (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoloxyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meta) ) Atalylate, trimethylolethane tritalylate, trimethylolpropane triacrylate, trimethylolpropane ditalylate, neopentylglycol di (meth) atalylate, pentaerythritol tetra (meth) atalylate, pentaerythritol tri (meta) ) Relate, Dipentaerythritol Hexa (meth) acrylate, Dipentaerythritol Penta (meth) acrylate, Hexanediol di (meth) acrylate, Trimethylol propantri (ataryloxypropyl) ether, Tri ( Addition reaction of ethylene oxide / propylene oxide to polyfunctional alcohols such as attayllooxychetyl) isocyanurate, tri (atallylooxychetyl) cyanurate, glycerin tri (meth) atallylate, trimethylolpropane or glycerin After the polyfunctionality (meta) such as (meth) acrylated
)アタリレートを挙げることができる。 ) Atarirate can be mentioned.
[0122] 更 ίこ、特公日召 48— 41708号、同 50— 6034号、特開日召 51— 37193号の各公幸艮 (こ 開示されている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号の各公報に開示されているポリエステルアタリレート類、ェポキ シ樹脂と (メタ）アクリル酸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ァク リレートやメタタリレートを挙げることができる。これらの中で、トリメチロールプロパントリ  [0122] Kosho, JP-B-48-41708, JP-A-50-6034, JP-A-51-37193, and other public goods (the disclosed urethane acrylates, JP-A-48- Polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid are disclosed in Japanese Patent Nos. 64183, 49-43191 and 52-30490. Examples include functional acrylate and metatalylate, of which trimethylolpropane tri
(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）アタリレート、ジペンタエリスリトールペンタ（メタ）アタリレートが好まし レ、。前記光重合性モノマーは、単独でも 2種類以上を混合して用いてもよい。前記光 重合性モノマーの感光性の遮光用着色組成物の全固形分に対する含有量は、 5〜 50質量％が一般的であり、 10〜40質量％が好ましい。前記含有量が前記範囲内に あると光感度や画像の強度も低下せず、感光性遮光層の粘着性が過剰になることも ない。 (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, dipentaerythritol penta (meth) acrylate are preferred. The photopolymerizable monomers may be used alone or in combination of two or more. The content of the photopolymerizable monomer with respect to the total solid content of the photosensitive coloring composition for light shielding is generally 5 to 50% by mass, and preferably 10 to 40% by mass. When the content is within the above range, the light sensitivity and the image strength are not lowered, and the adhesiveness of the photosensitive light-shielding layer is not excessive.
[0123] 感光性の遮光用着色組成物としては、前記成分の他に更に熱重合防止剤を添カロ することが好ましい。前記熱重合防止剤の例としては、例えば、ハイドロキノン、 ρ—メ トキシフエノール、 p_t—ブチルカテコール、 2, 6 _ジ一 t—ブチノレ一 p_タレゾール 、 β—ナフトール、ピロガロール等の芳香族ヒドロキシ化合物、ベンゾキノン、 ρ—トル キノン等のキノン類、ナフチルァミン、ピリジン、 ρ—トルイジン、フエノチアジン等のアミ ン類、 Ν—ニトロソフエニルヒドロキシルァミンのアルミニウム塩またはアンモニゥム塩、 クロラニール、ニトロベンゼン、 4， 4'—チォビス（3—メチル _ 6 _t_ブチルフエノー ノレ）、 2, 2 '—メチレンビス（4—メチル _ 6 _t_ブチルフエノール）、 2_メルカプトべ ンズイミダゾール等が挙げられる。 [0124] 感光性の遮光用着色組成物は、更に必要に応じて公知の添加剤、例えば、可塑 剤、界面活性剤、密着促進剤、分散剤、垂れ防止剤、レべリング剤、消泡剤、難燃化 剤、光沢剤、溶剤等を添加することができる。 [0123] It is preferable to add a thermal polymerization inhibitor to the photosensitive coloring composition for shading, in addition to the above components. Examples of the thermal polymerization inhibitor include, for example, aromatic hydroxy compounds such as hydroquinone, ρ-methoxyphenol, p_t-butylcatechol, 2, 6_di-tert-butynole p_taresol, β-naphthol, pyrogallol, etc. Quinones such as benzoquinone, ρ-toluquinone, naphthylamine, pyridine, amines such as ρ-toluidine, phenothiazine, aluminum salt or ammonium salt of ニ ト ロ -nitrosophenylhydroxylamine, chloranil, nitrobenzene, 4, 4 ' —Chobis (3-methyl-6_t_butylphenol), 2,2′-methylenebis (4-methyl_6_t_butylphenol), 2-mercaptobenzimidazole, and the like. [0124] The photosensitive light-shielding coloring composition further contains known additives as necessary, for example, plasticizers, surfactants, adhesion promoters, dispersants, anti-sagging agents, leveling agents, antifoaming agents. Agents, flame retardants, brighteners, solvents, etc. can be added.
[0125] 前記密着促進剤としては、例えばアルキルフヱノール Zホルムアルデヒドノボラック 樹脂、ポリビュルェチルエーテル、ポリビュルイソブチルエーテル、ポリビュルブチラ ール、ポリイソブチレン、スチレン一ブタジエン共重合体ゴム、ブチルゴム、塩化ビニ ルー酢酸ビニル共重合体、塩化ゴム、アクリル樹脂系粘着剤、芳香族系、脂肪族系 または脂環族系の石油樹脂、シランカップリング剤等が挙げられる。  [0125] Examples of the adhesion promoter include alkylphenol Z formaldehyde novolak resin, polybutyl ether, polybutyl isobutyl ether, polybutyl butyral, polyisobutylene, styrene monobutadiene copolymer rubber, butyl rubber, vinyl chloride. Examples include vinyl acetate copolymer, chlorinated rubber, acrylic resin-based adhesive, aromatic, aliphatic or alicyclic petroleum resin, and silane coupling agent.
[0126] 本発明の遮光用着色組成物 (感光性のものを含む）を用いてブラックマトリックスを 形成することで、薄膜で且つ光学濃度が高いブラックマトリックスを作製することがで きる。 [0126] By forming the black matrix using the light-shielding coloring composition of the present invention (including the photosensitive composition), a thin black matrix having a high optical density can be produced.
[0127] 《感光性転写材料〉〉  [0127] <Photosensitive transfer material >>
(感光性遮光層）  (Photosensitive light shielding layer)
本発明においては、本発明の金属微粒子分散物を用いて支持体上に感光性遮光 層を形成し、本発明の感光性転写材料とすることができる。本発明の感光性転写材 料を用いることで、ブラックマトリックス等の遮光画像を作製することができる。  In the present invention, a photosensitive light-shielding layer can be formed on a support using the metal fine particle dispersion of the present invention to provide the photosensitive transfer material of the present invention. By using the photosensitive transfer material of the present invention, a light-shielded image such as a black matrix can be produced.
前記感光性転写材料は、支持体上に、上述の感光性を有する遮光用着色組成物 等を用い形成された感光性遮光層を少なくとも 1層有し、必要に応じて熱可塑性榭 脂層、中間層、または保護層等を設けることができる。  The photosensitive transfer material has at least one photosensitive light-shielding layer formed on the support using the above-described light-sensitive coloring composition for light shielding, etc., and if necessary, a thermoplastic resin layer, An intermediate layer, a protective layer, or the like can be provided.
前記感光性遮光層の膜厚は 0.：!〜 4 /i mの範囲が好ましぐ特に 0.：!〜 2. O ^ m の範囲が好ましく更に 0. 2〜： 1. O /i mが好ましレ、。  The film thickness of the photosensitive light-shielding layer is preferably in the range of 0.:! To 4 / im, particularly in the range of 0.:! To 2. O ^ m, and more preferably 0.2 to: 1. O / im. I like it.
[0128] (支持体） [0128] (Support)
前記感光性転写材料における支持体としては、ポリエステル、ポリスチレン等の公 知の支持体を用いることができる。中でも 2軸延伸したポリエチレンテレフタレートはコ スト、耐熱性、寸法安定性の観点から好ましい。前記支持体の厚みは 15〜200 x m 程度、より好ましくは 30〜： 150 z m程度が好ましい。前記支持体の厚みが前記範囲 内にあると、ラミネーシヨン工程時に熱によりトタン板状のしわが発生するのを効果的 に抑制することができ、コスト上も有利である。 また前記支持体には必要に応じて特開平 11— 149008号公報に記載されている 導電性層を設けてもよい。 As the support in the photosensitive transfer material, a known support such as polyester or polystyrene can be used. Among these, biaxially stretched polyethylene terephthalate is preferable from the viewpoints of cost, heat resistance, and dimensional stability. The thickness of the support is preferably about 15 to 200 xm, more preferably about 30 to about 150 zm. When the thickness of the support is within the above range, it is possible to effectively suppress generation of a wrinkle of a tin plate due to heat during the lamination process, which is advantageous in terms of cost. The support may be provided with a conductive layer described in JP-A-11-149008 as required.
[0129] (熱可塑性樹脂層）  [0129] (Thermoplastic resin layer)
また、支持体と感光性遮光層との間、または支持体と中間層との間に、アルカリ可 溶性の熱可塑性樹脂層を設けることが好ましい。  Further, it is preferable to provide an alkali-soluble thermoplastic resin layer between the support and the photosensitive light-shielding layer or between the support and the intermediate layer.
前記熱可塑性樹脂層は、下地表面の凹凸（既に形成されている画像などによる凹 凸等も含む）を吸収することができるようにクッション材としての役割を担うものである ため、当該凹凸に応じて変形しうる性質を有していることが好ましい。  The thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb unevenness (including unevenness due to an already formed image, etc.) on the base surface. It is preferable to have a property that can be deformed.
[0130] アルカリ可溶な熱可塑性樹脂層に含まれる樹脂としては、エチレンとアクリル酸エス テル共重合体とのケン化物、スチレンと（メタ）アクリル酸エステル共重合体とのケン化 物、ビュルトルエンと（メタ）アクリル酸エステル共重合体とのケン化物、ポリ（メタ）ァク リル酸エステル、および (メタ）アクリル酸ブチルと酢酸ビュル等との（メタ）アクリル酸 エステル共重合体等のケンィ匕物、等より選ばれる少なくとも 1種であることが好ましい 。更に「プラスチック性能便覧」（日本プラスチック工業連盟、全日本プラスチック成形 工業連合会編著、工業調査会発行、 1968年 10月 25日発行）による有機高分子のう ちアルカリ水溶液に可溶なものを使用することもできる。また、これらの熱可塑性樹脂 のうち、軟化点が 80°C以下のものが好ましい。  [0130] Resins contained in the alkali-soluble thermoplastic resin layer include saponified products of ethylene and acrylic acid ester copolymers, saponified products of styrene and (meth) acrylic acid ester copolymers, and bulls. Saponification products of toluene and (meth) acrylic acid ester copolymers, poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers of butyl (meth) acrylate and butyl acetate, etc. It is preferably at least one selected from Kenya, etc. Furthermore, use organic polymers that are soluble in alkaline aqueous solutions according to the "Plastic Performance Handbook" (edited by the Japan Plastics Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968). You can also. Of these thermoplastic resins, those having a softening point of 80 ° C. or less are preferable.
[0131] 前記熱可塑性樹脂層に含まれる樹脂としては、上述のアルカリ可溶な熱可塑性樹 脂層に含まれる樹脂の中でも、重量平均分子量 3千〜 50万 (Tg = 0〜： 170°C)の範 囲で選択して使用することが好ましく、更には重量平均分子量 4千〜 20万 (Tg = 30 〜140°C)の範囲がより好ましレ、。これらの樹脂の具体例としては、特公昭 54— 343 号、特公昭 55— 3 1号、特公昭 δ8— 12577号、特公昭 54— 号、特開 昭 61— 134756号、特公昭 59— 44615号、特開昭 54— 92723号、特開昭 54— 9 9418号、特開昭 54— 137085号、特開昭 57— 20732号、特開昭 58— 93046号、 特開昭 59— 97135号、特開昭 60— 159743号、特開昭 60— 247638号、特開昭 6 0— 208748号、特開昭 60— 214354号、特開昭 60— 230135号、特開昭 60— 25 8539号、特開昭 61— 169829号、特開昭 61— 213213号、特開昭 63— 147159 号、特開昭 63— 213837号、特開昭 63— 266448号、特開昭 64— 55551号、特開 日召 64— 55550号、特開平 2— 191955号、特開平 2— 199403号、特開平 2— 199 404号、特開平 2— 208602号、特開平 5— 241340号の各公報に記載されている アルカリ水溶液に可溶な樹脂を挙げることができる。 [0131] As the resin contained in the thermoplastic resin layer, among the resins contained in the above-mentioned alkali-soluble thermoplastic resin layer, a weight average molecular weight of 3,000 to 500,000 (Tg = 0 to: 170 ° C) ) Is preferably selected and used, and a weight average molecular weight of 4,000 to 200,000 (Tg = 30 to 140 ° C.) is more preferable. Specific examples of these resins include JP-B 54-343, JP-B 55-31, JP-B δ8-12577, JP-B 54-, JP-A 61-134756, JP-B 59-44615. JP, 54-92723, JP 54-99418, JP 54-137085, JP 57-20732, JP 58-93046, JP 59-97135 JP, 60-159743, JP 60-247638, JP 60-208748, JP 60-214354, JP 60-230135, JP 60-25 8539 JP-A 61-169829, JP-A 61-213213, JP-A 63-147159, JP-A 63-213837, JP-A 63-266448, JP-A 64-55551, Open JP-A-64-55550, JP-A-2-191955, JP-A-2-199403, JP-A-2-199404, JP-A-2-208602, JP-A-5-241340. A resin soluble in an alkaline aqueous solution can be mentioned.
[0132] また、これらの中でも特に好ましいものとしては、特開昭 63— 147159号明細書に 記載されたメタクリル酸 /2_ェチルへキシルアタリレート Zベンジルメタタリレート Z メチルメタタリレート共重合体、特公昭 55— 38961号、特開平 5— 241340号の各公 報に記載のスチレン Z (メタ）アクリル酸共重合体が挙げられる。  [0132] Among these, as particularly preferred, methacrylic acid / 2_ethylhexyl acrylate, Z-benzyl methacrylate, and methyl methacrylate copolymer described in JP-A-63-147159 are used. And styrene Z (meth) acrylic acid copolymers described in Japanese Patent Publication Nos. 55-38961 and 5-241340.
[0133] さらに、前記熱可塑性樹脂層には、熱可塑性樹脂層と支持体との接着力を調節す るために、各種可塑剤、各種ポリマー、過冷却物質、密着改良剤、界面活性剤、また は離型剤等をカ卩えることが可能である。好ましい可塑剤の具体例としては、ポリプロピ レングリコーノレ、ポリエチレングリコーノレ、ジォクチノレフタレート、ジへプチノレフタレート [0133] Further, in order to adjust the adhesive force between the thermoplastic resin layer and the support, the thermoplastic resin layer includes various plasticizers, various polymers, supercooling substances, adhesion improvers, surfactants, It is also possible to arrange a release agent or the like. Specific examples of preferable plasticizers include polypropylene glycolol, polyethylene glycolol, dioctino phthalate, diheptino phthalate.
、ジブチルフタレート、トリクレジルフォスフェート、クレジルジフヱニルフォスフェート、 ビフエニルジフエニルフォスフェート、ポリエチレングリコールモノ（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モノ（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、エポキシ樹脂とポリエチレングリコ ールモノ (メタ）アタリレートとの付加反応生成物、有機ジイソシアナ一トとポリエチレン グリコールモノ (メタ）アタリレートとの付加反応生成物、有機ジイソシアナートとポリプ ロピレンダリコールモノ（メタ）アタリレートとの付加反応生成物、ビスフエノール Aとポリ エチレングリコールモノ (メタ）アタリレートとの縮合反応生成物等を挙げることができる 前記熱可塑性樹脂層中の可塑剤の含有量は、可塑性樹脂層の全固形分に対して 、 200質量％以下が一般的であり、好ましくは 20〜： 100質量％である。 , Dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, polyethylene glycol mono (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) Atallate, polypropylene glycol di (meth) acrylate, addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, addition reaction product of organic diisocyanate and polyethylene glycol mono (meth) acrylate Examples include addition reaction products of organic diisocyanates and polypropylene (mono) (meth) acrylate, condensation reaction products of bisphenol A and poly (ethylene glycol) mono (meth) acrylate. The plasticizer content of the thermoplastic resin layer which can, based on the total solid content of the thermoplastic resin layer, 200 mass% or less are common, preferably 20: 100% by weight.
[0134] また、前記熱可塑性樹脂層の厚みは 6 μ m以上が好ましい。熱可塑性樹脂の厚み 力 ¾ x m以上であれば、下地表面の凹凸を完全に吸収することができる。また、上限 については、現像性、製造適性から約 100 x m以下が一般的であり、好ましくは約 5 O z m以下である。 [0134] The thickness of the thermoplastic resin layer is preferably 6 μm or more. If the thickness force of the thermoplastic resin is ¾ x m or more, the unevenness of the base surface can be completely absorbed. The upper limit is generally about 100 × m or less, preferably about 5 Ozm or less, from the viewpoint of developability and production suitability.
[0135] 本発明において、熱可塑性樹脂層を形成する際に用いる塗布液の溶媒としてはこ の層を構成する樹脂を溶解するものであれば特に制限なく使用できる。前記溶媒とし ては、例えばメチルェチルケトン、シクロへキサノン、プロピレングリコールモノメチル エーテルアセテート、 n—プロパノール、 i—プロパノール等が挙げられる。 [0135] In the present invention, the solvent of the coating solution used for forming the thermoplastic resin layer can be used without particular limitation as long as it dissolves the resin constituting this layer. As the solvent Examples thereof include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, i-propanol and the like.
[0136] (中間層） [0136] (Middle layer)
本発明の感光性転写材料は、仮支持体と感光性遮光層との間に中間層を設けて あよい。  In the photosensitive transfer material of the present invention, an intermediate layer may be provided between the temporary support and the photosensitive light-shielding layer.
中間層を構成する樹脂としてはアルカリ可溶であれば特に制限はない。該樹脂の 例としては、ポリビュルアルコール系樹脂、ポリビュルピロリドン系樹脂、セルロース系 樹脂、アクリルアミド系樹脂、ポリエチレンオキサイド系樹脂、ゼラチン、ビュルエーテ ル系樹脂、ポリアミド樹脂、およびこれらの共重合体を挙げることができる。またポリェ ステルのように通常はアルカリ可溶性でない樹脂にカルボキシノレ基ゃスルホン酸基 を持つモノマーを共重合した樹脂も用いることができる。  The resin constituting the intermediate layer is not particularly limited as long as it is alkali-soluble. Examples of the resin include polybulal alcohol resins, polybulurpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, bulerite resins, polyamide resins, and copolymers thereof. be able to. Moreover, a resin obtained by copolymerizing a monomer having a carboxyl group or a sulfonic acid group with a resin that is not usually alkali-soluble, such as polyester, can also be used.
これらの中で好ましいものはポリビュルアルコールである。前記ポリビュルアルコー ルとしては鹼化度が 80%以上のものが好ましぐ 83〜98%のものがより好ましい。  Among these, polybulal alcohol is preferable. The polybulal alcohol preferably has a hatching degree of 80% or more, more preferably 83 to 98%.
[0137] 中間層を構成する樹脂は 2種類以上を混合して使用することが好ましぐ特にポリビ ニルアルコールとポリビエルピロリドンとを混合して用いることが特に好ましい。両者の 質量比はポリビエルピロリドン/ポリビニルアルコール = 1/99〜75/25の範囲が 好ましぐ更には 10/90〜50/50の範囲がより好ましい。前記質量比が前記の範 囲内にあると中間層の面状が良好であり、その上に塗設した感光性遮光層との密着 性がよぐ更に、酸素遮断性が低下して感度が低下するのを防止することができる。 尚、前記中間層には必要に応じて界面活性剤などの添加剤を添加することができ る。 [0137] It is preferable to use a mixture of two or more types of resins constituting the intermediate layer, and it is particularly preferable to use a mixture of polyvinyl alcohol and polyvinyl pyrrolidone. The mass ratio of the two is preferably polyvinyl pyrrolidone / polyvinyl alcohol = 1/99 to 75/25, and more preferably 10/90 to 50/50. When the mass ratio is within the above range, the surface shape of the intermediate layer is good, the adhesiveness with the photosensitive light-shielding layer coated thereon is good, and the oxygen barrier property is lowered to lower the sensitivity. Can be prevented. In addition, an additive such as a surfactant can be added to the intermediate layer as necessary.
[0138] 前記中間層の厚みは 0. l ~5 x m,更に 0. 5〜3 μ mの範囲が好ましレ、。中間層 の厚みが前記範囲内にあると、酸素遮断性を低下させることなぐまた、現像時の中 間層除去時間が増大するのを防止することができる。  [0138] The thickness of the intermediate layer is preferably 0.1 to 5 x m, more preferably 0.5 to 3 µm. When the thickness of the intermediate layer is within the above range, it is possible to prevent an increase in the intermediate layer removal time during development without decreasing the oxygen barrier property.
中間層の塗布溶媒としては前記の樹脂が溶解すれば、特にその他の制限はない 、中でも水が好ましぐまた水に前述の水混和性有機溶剤を混合した混合溶媒も 好ましい。好ましい塗布溶媒の具体例としては、例えば、水、水/メタノール = 90/ 10、水/メタノーノレ = 70/30、水 Zメタノーノレ = 55745、水/エタノーノレ = 70/3 0、水 /1 プロパノール = 70/30、水/アセトン = 90/10、水/メチルェチルケト ン = 95/5 (ただし比は質量比を表す）等が挙げられる。 As the coating solvent for the intermediate layer, there is no particular limitation as long as the resin is dissolved. Among them, water is preferable, and a mixed solvent obtained by mixing the water-miscible organic solvent with water is also preferable. Specific examples of preferable coating solvents include, for example, water, water / methanol = 90/10, water / methanol = 70/30, water Z methanol = 55745, water / ethanolanol = 70/3. 0, water / 1 propanol = 70/30, water / acetone = 90/10, water / methylethylketone = 95/5 (where the ratio represents a mass ratio), and the like.
[0139] (感光性転写材料の作製） [0139] (Preparation of photosensitive transfer material)
本発明の感光性転写材料は、支持体に、本発明の感光性を有する遮光用着色組 成物の溶液を、例えば、スピナ一、ホワイラー、ローラーコーター、カーテンコーター、 ナイフコーター、ワイヤーバーコ一ター、エタストルーダー等の塗布機を用いて塗布. 乾燥させることにより感光性遮光層を形成することにより作製することができる。また、 アルカリ可溶性熱可塑性樹脂の層を設ける場合にも同様にして形成することができる  The photosensitive transfer material of the present invention is prepared by applying a light-shielding coloring composition solution of the present invention to a support, such as a spinner, a wheeler, a roller coater, a curtain coater, a knife coater, or a wire bar coater. It can be prepared by forming a photosensitive light-shielding layer by applying and drying using an applicator such as Etastruder. It can also be formed in the same manner when an alkali-soluble thermoplastic resin layer is provided.
[0140] 本発明の感光性転写材料は、上述のごとき本発明の遮光用着色組成物を用いて 感光性遮光層を設けているため、薄膜で且つ光学濃度が高い遮光層を作製すること ができる。 [0140] Since the photosensitive transfer material of the present invention is provided with the photosensitive light-shielding layer using the light-shielding coloring composition of the present invention as described above, a light-shielding layer having a thin film and a high optical density can be produced. it can.
[0141] 《遮光画像の作製方法》  [0141] <Method for producing shading image>
(遮光層の形成方法）  (Method of forming light shielding layer)
本発明において、遮光画像は、本発明の金属微粒子分散物、これを含有する着色 組成物または感光性転写材料を用いて形成した遮光層をパターニングすることによ り作製される。この際、前記遮光層の膜厚は 0. 2〜2. 0 / m程度、更には 0. 9 u m 以下であることが好ましい。前記遮光層は本発明における金属微粒子を分散させた ものであるため、前記のごとき薄膜でも十分な光学濃度（〇· D3. 5以上)を発揮する こと力 Sできる。 In the present invention, the light-shielded image is produced by patterning a light-shielding layer formed using the metal fine particle dispersion of the present invention, a coloring composition containing the same, or a photosensitive transfer material. In this case, the thickness of the light shielding layer is 0. 2~2. 0 / m or so, more preferably not more than 0. 9 u m. Since the light shielding layer is made by dispersing the metal fine particles in the present invention, even a thin film as described above can exert a sufficient optical density (O · D3.5 or more).
[0142] また、本発明の金属微粒子分散物、これを含有する着色組成物または感光性転写 材料を用いて遮光画像を作製する（パターニングする）方法は特に限定はされない。 以下にブラックマトリックスのパターン形成方法の一例を挙げる。  [0142] The method for producing (patterning) the light-shielded image using the metal fine particle dispersion of the present invention, the coloring composition containing the metal fine particle dispersion or the photosensitive transfer material is not particularly limited. An example of a black matrix pattern forming method is given below.
[0143] 第 1の方法は、まず本発明における金属微粒子と本発明におけるアルカリ可溶性 ポリマーとを含有し、感光性を有する本発明の遮光用着色組成物を基板に塗布し、 金属微粒子および本発明におけるアルカリ可溶性ポリマーを含有した感光性遮光層 を形成する。第 1の方法は、その後、露光現像によりパターン以外の部分の遮光層を 除却することによりパターン形成を行レ、、遮光画像を得る方法である。また、上述の 中間層と同組成の層を前記感光性遮光層上に形成して保護層とすることもできる。こ の場合、塗布液の塗布は、上述の塗布機を用いて塗布することができ、中でもスピン コート法によって行うのが好ましい。 [0143] In the first method, first, the light-shielding coloring composition of the present invention containing the metal fine particles of the present invention and the alkali-soluble polymer of the present invention and having photosensitivity is applied to a substrate, and the metal fine particles and the present invention are applied. A photosensitive light-shielding layer containing an alkali-soluble polymer is formed. The first method is a method for obtaining a light-shielded image by performing pattern formation by removing the light-shielding layer other than the pattern by exposure and development thereafter. Also, the above A layer having the same composition as the intermediate layer may be formed on the photosensitive light-shielding layer to form a protective layer. In this case, the coating solution can be applied by using the above-described coating machine, and it is particularly preferable to perform the coating by a spin coating method.
[0144] 第 2の方法は、まず、まず本発明における金属微粒子と本発明におけるアルカリ可 溶性ポリマーとを含有し、非感光性の本発明の着色組成物を基板に塗布して、金属 微粒子および本発明におけるアルカリ可溶性ポリマーを含有した遮光層を形成する 。その後、該遮光層上に感光性レジスト液を塗布してレジスト層を形成する。第 2の方 法は、次いで露光によりレジスト層を露光現像してレジスト層にパターンを形成した後 、このパターンに応じて遮光層の非パターン部を溶解し、遮光層にパターンを形成す る。最後にレジスト層を除却して、遮光画像を作製する方法である。  [0144] In the second method, first, the fine metal particles according to the present invention and the alkali-soluble polymer according to the present invention are coated on the substrate with the non-photosensitive coloring composition of the present invention. A light shielding layer containing an alkali-soluble polymer in the present invention is formed. Thereafter, a photosensitive resist solution is applied on the light shielding layer to form a resist layer. In the second method, the resist layer is then exposed and developed by exposure to form a pattern in the resist layer, and then the non-patterned portion of the light shielding layer is dissolved according to this pattern to form a pattern in the light shielding layer. Finally, the resist layer is removed to produce a light-shielded image.
[0145] 第 3の方法は、予め基板上のパターン以外の部分に塗布層を形成しておき、この 上に金属微粒子および本発明におけるアルカリ可溶性ポリマーを含有した、非感光 性の本発明の遮光用着色組成物を塗布して微粒子含有層を含む遮光層を形成する  [0145] In the third method, a coating layer is previously formed on a portion other than the pattern on the substrate, and the non-photosensitive light-shielding material of the present invention containing the metal fine particles and the alkali-soluble polymer of the present invention thereon. A light-shielding layer including a fine particle-containing layer by applying a coloring composition
。次いで、初めに形成した塗布層を上の遮光層とともに除却し、遮光画像が作製され る。 . Next, the coating layer formed first is removed together with the upper light shielding layer to produce a light shielding image.
[0146] 前記感光性転写材料を用いる遮光画像の作製方法としては、光透過性基板の上 に、前記感光性転写材料を、感光性転写材料の感光性遮光層が接触するように配 置して積層する。次に、感光性転写材料と光透過性基板との積層体から支持体を剥 離し、その後、前記層を露光した後現像して遮光画像を形成する方法である。  [0146] As a method for producing a light-shielded image using the photosensitive transfer material, the photosensitive transfer material is placed on a light-transmitting substrate so that the photosensitive light-shielding layer of the photosensitive transfer material is in contact therewith. And stack. Next, the support is peeled off from the laminate of the photosensitive transfer material and the light transmissive substrate, and then the layer is exposed and developed to form a light-shielded image.
この遮光画像の製造方法は、煩瑣な工程を行うことを必要とせず、低コストである。  This method for producing a light-shielded image does not require a cumbersome process and is low in cost.
[0147] (露光および現像） [0147] (Exposure and development)
次に、前記露光および現像工程について述べる。  Next, the exposure and development process will be described.
前記基板上に形成された遮光層の上方に所定のマスクを配置し、その後該マスク 上方から露光し、次いで現像液による現像を行レ、、パターニング画像を得、引き続き 必要に応じて、水洗処理を行う、という工程により、本発明の遮光画像を得ることがで きる。露光は上述のようなマスクを配置する方法以外に、マスクを介さずに直接に画 像データに基づいて露光光を相対走查することでパターン画像を得てもよい。  A predetermined mask is placed above the light-shielding layer formed on the substrate, then exposed from above the mask, then developed with a developing solution, and a patterned image is obtained, and subsequently washed with water as necessary. The light-shielded image of the present invention can be obtained by performing the process. In addition to the method of arranging the mask as described above, the pattern image may be obtained by directly striking the exposure light based on the image data without using the mask.
ここで、前記露光の光源としては、感光性樹脂層を硬化しうる波長域の光（例えば、 365nm、 405nmなど）を照射できるものであれば適宜選定して用いることができる。 具体的には、超高圧水銀灯、高圧水銀灯、メタルハライドランプ、 LD、超高圧水銀 灯、 YAG— SHG固体レーザー、 KrFレーザー、固体レーザー等が挙げられる。露 光量としては、通常 5〜200mj/cm2程度であり、好ましくは 10〜100mj/cm2程度 である。 Here, as the light source for the exposure, light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.) can be appropriately selected and used. Specific examples include ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, LDs, ultra-high pressure mercury lamps, YAG-SHG solid-state lasers, KrF lasers, and solid-state lasers. The amount of exposure is usually about 5 to 200 mj / cm 2 , and preferably about 10 to 100 mj / cm 2 .
この際に使用する露光機は、特に限定されるわけではないが、前記マスクを介して 露光するプロキシミティ露光機の他、散乱光線露光機、平行光線露光機、ステッパー 、およびレーザー露光などを用いることができる。  Although the exposure machine used in this case is not particularly limited, a scattered light exposure machine, a parallel light exposure machine, a stepper, and a laser exposure are used in addition to the proximity exposure machine that exposes through the mask. be able to.
[0148] また、前記現像液としては、特に制約はなぐ特開平 5— 72724号公報に記載のも のなど、公知の現像液を使用することができ、本発明ではアルカリ性物質の希薄水 溶液が好ましく用いられる。詳しくは、現像液は感光性樹脂層が溶解型の現像挙動 をするものが好ましい。尚、更に水と混和性を有する有機溶剤を少量添加してもよい また、前記現像の前には、純水をシャワーノズノレ等にて噴霧して、該感光性遮光層 の表面を均一に湿らせることが好ましい。 [0148] As the developer, known developers such as those described in JP-A-5-72724, which are not particularly limited, can be used. In the present invention, a dilute aqueous solution of an alkaline substance is used. Preferably used. Specifically, the developer is preferably one in which the photosensitive resin layer exhibits a dissolution type development behavior. In addition, a small amount of an organic solvent miscible with water may be added. Also, before the development, pure water is sprayed with a shower nozzle or the like to make the surface of the photosensitive light-shielding layer uniform. It is preferable to moisten.
[0149] 前記遮光画像の塗布による形成方法および感光性転写材料を用いる形成方法に おける、前記アルカリ性物質としては、アルカリ金属水酸化物類（例えば、水酸化ナト リウム、水酸化カリウム）、アルカリ金属炭酸塩類 (例えば、炭酸ナトリウム、炭酸力リウ ム）、アルカリ金属重炭酸塩類 (例えば、炭酸水素ナトリウム、炭酸水素カリウム）、ァ ルカリ金属ケィ酸塩類（例えば、ケィ酸ナトリウム、ケィ酸カリウム）、アルカリ金属メタ ケィ酸塩類（例えば、メタケイ酸ナトリウム、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ニゥム ヒドロキシド類 (例えば、テトラメチルアンモニゥムヒドロキシド）、燐酸三ナトリウム、等 が挙げられる。アルカリ性物質の濃度は、 0. 01〜30質量％が好ましぐ pHは 8〜1 4が好ましい。 [0149] In the formation method by application of the light-shielding image and the formation method using a photosensitive transfer material, the alkaline substance includes alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal Carbonates (eg, sodium carbonate, lithium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate, potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali Metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg, tetramethylammonium hydroxy) D), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably 0.01 to 30% by mass. The pH is preferably 8 to 14.
[0150] 前記「水と混和性の有機溶斉 としては、例えば、メタノーノレ、エタノール、 2_プロ パノーノレ、 1 _プロパノーノレ、ブタノーノレ、ジアセトンァノレコーノレ、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ェチノレエーテノ エチレングリコーノレモ ノ 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 —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 —力プロラタタム 、 Ν_メチルピロリドン等が好適に挙げられる。水と混和性の有機溶剤の濃度は 0. 1 〜30質量％が好ましい。更に、公知の界面活性剤を添加することもでき、該界面活 性剤の濃度としては 0. 01〜： 10質量％が好ましい。 [0150] Examples of the organic miscibility miscible with water include, for example, methanolol, ethanol, 2_propanol, 1_propanol, butanol, diacetone ethanol, ethylene glycol monomethinoreateol, ethylene Glyconoremonoetinoreetheno Ethyleneglyco-reno N-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-force prolatatone, γ-butyroratatone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, lactate ethyl, methyl lactate, ε-force Prolatatam, Ν_methylpyrrolidone and the like are preferable. The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass. Furthermore, a known surfactant may be added, and the concentration of the surfactant is preferably 0.01 to 10% by mass.
[0151] 前記現像液は、浴液としても、或いは噴霧液としても用いることができる。遮光層の 未硬化部分を除去する場合、現像液中で回転ブラシや湿潤スポンジで擦るなどの方 法を組み合わせることができる。現像液の液温度は、通常室温付近から 40°Cが好ま しい。現像時間は、遮光層の組成、現像液のアルカリ性や温度、有機溶剤を添加す る場合にはその種類と濃度、等に依るが、通常 10秒〜 2分程度である。短すぎると非 露光部の現像が不充分となると同時に紫外線の吸光度も不充分となることがあり、長 すぎると露光部もエッチングされることがある。いずれの場合にも、遮光画像形状を好 適なものとすることが困難となる。この現像工程にて、遮光画像が形成される。  [0151] The developer may be used as a bath solution or a spray solution. When removing the uncured portion of the light shielding layer, methods such as rubbing with a rotating brush or wet sponge in the developer can be combined. The developer temperature is usually from about room temperature to 40 ° C. The development time depends on the composition of the light-shielding layer, the alkalinity and temperature of the developer, and the type and concentration of the organic solvent when added, but is usually about 10 seconds to 2 minutes. If it is too short, the development of the unexposed area may be insufficient, and the absorbance of ultraviolet rays may be insufficient, and if it is too long, the exposed area may be etched. In either case, it is difficult to make the light-shielded image shape suitable. In this development step, a light-shielded image is formed.
[0152] 《遮光画像付き基板》  [0152] 《Substrate with shading image》
本発明の遮光画像付き基板は、光透過性基板の上に本発明の金属微粒子分散物 またはこれを含む本発明の着色組成物、或いは、本発明の感光性転写材料を用い て形成された遮光層を前記のようにしてパターニングすることにより作製される。 この遮光画像付き基板 (好ましくは、ブラックマトリックス基板）における遮光画像の 膜厚は 0. 2〜2. 0 /i mが好ましぐ特に 0. 2〜0· 9 μ ΐηが好ましレ、。前記ブラックマ トリックス基板における遮光層は本発明における金属微粒子を分散させたものである ため、前記のごとき薄膜でも十分な光学濃度を有する。  The substrate with a light-shielding image of the present invention is a light-shielding formed by using the metal fine particle dispersion of the present invention or the coloring composition of the present invention containing the same, or the photosensitive transfer material of the present invention on a light-transmitting substrate. It is produced by patterning the layer as described above. The film thickness of the light-shielded image on this substrate with a light-shielded image (preferably a black matrix substrate) is preferably 0.2 to 2.0 / im, particularly 0.2 to 9 · 9 μΐη. Since the light shielding layer in the black matrix substrate is obtained by dispersing the metal fine particles in the present invention, the thin film as described above has a sufficient optical density.
[0153] 本発明の遮光画像付き基板は、テレビ、パーソナルコンピュータ、液晶プロジェクタ 一、ゲーム機、携帯電話などの携帯端末、デジタルカメラ、カーナビなどの用途に特 に制限なく適用できる。また、下記カラーフィルターの作製においても好適に用いるこ とができる。  [0153] The substrate with a light-shielding image of the present invention can be applied to a TV, personal computer, liquid crystal projector, portable terminal such as a game machine or a mobile phone, a digital camera, a car navigation, and the like without any limitation. Further, it can be suitably used in the production of the following color filter.
[0154] 《カラーフイノレター》  [0154] Color Fino Letter
本発明のカラーフィルタ一は、光透過性基板の上に、着色層からなり、互いに異な る色を呈する 2以上の画素群を有し、前記画素群を構成する各画素は互いに遮光画 像（ブラックマトリックス）により離画されている構成を有する。前記ブラックマトリックス は、本発明の金属微粒子分散物、またはこれを用いた本発明の着色組成物若しくは 感光性転写材料を用いて作製される。前記画素群は 2つでも、 3つでも 4つ以上でも よい。例えば 3つの場合は赤 (R)、緑 (G)および青（B)の 3つの色相が好適に用いら れる。赤、緑、青の 3種の画素群を配置する場合は、モザイク型、トライアングル型等 の配置が好ましぐ 4種以上の画素群を配置する場合ではどのような配置であっても よい。 The color filter of the present invention comprises a colored layer on a light-transmitting substrate and is different from each other. And each pixel constituting the pixel group is separated from each other by a light-shielding image (black matrix). The black matrix is produced using the metal fine particle dispersion of the present invention, or the colored composition or photosensitive transfer material of the present invention using the same. The number of pixel groups may be two, three, or four or more. For example, in the case of three, three hues of red (R), green (G) and blue (B) are preferably used. When three types of pixel groups of red, green, and blue are arranged, any arrangement may be used when four or more types of pixel groups are preferred, such as mosaic type and triangle type.
[0155] 前記光透過性基板としては、表面に酸化珪素皮膜を有するソーダガラス板、低膨 張ガラス板、ノンアルカリガラス板、石英ガラス板等の公知のガラス板或いはプラスチ ックフィルム等が用いられる。  [0155] As the light-transmitting substrate, a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, or a plastic film is used.
本発明のカラーフィルターを作製するには、光透過性の基板に常法により 2以上の 画素群を形成した後、前記のようにしてブラックマトリックスを形成してもよいし、或い は、最初にブラックマトリックスを形成し、その後 2以上の画素群を形成してもよい。 本発明のカラーフィルタ一は上述のごとき薄膜で高濃度であるブラックマトリックスを 備えているため、表示コントラストが高くまた平坦性に優れている。  In order to produce the color filter of the present invention, two or more pixel groups may be formed on a light-transmitting substrate by a conventional method, and then a black matrix may be formed as described above. Alternatively, a black matrix may be formed, and then two or more pixel groups may be formed. Since the color filter of the present invention is provided with a black matrix having a high density and a thin film as described above, it has a high display contrast and excellent flatness.
[0156] 《表示素子》 [0156] << Display element >>
本発明の金属微粒子分散物は、表示素子に好適に用いることができる。前記表示 素子としてはプラズマディスプレイ表示装置、 EL表示装置、 CRT表示装置、液晶表 示装置等が挙げられ、中でも液晶表示装置に用いた場合に本発明の本発明の金属 微粒子分散物の効果が顕著に発揮される。表示素子の定義や各表示装置の説明は 、例えば「電子ディスプレイデバイス (佐々木 昭夫著、隅工業調查会 1990毎発行 )」、 「ディスプレイデバイス (伊吹 順幸著、産業図書側 平成元年発行)」などに記 載されている。  The metal fine particle dispersion of the present invention can be suitably used for a display element. Examples of the display element include a plasma display device, an EL display device, a CRT display device, a liquid crystal display device, and the like, and particularly when used in a liquid crystal display device, the effect of the metal fine particle dispersion of the present invention is remarkable. To be demonstrated. For the definition of display elements and explanation of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Sumi Industrial Research Association 1990)”, “Display Device (written by Junyuki Ibuki, published in 1989 by Sangyo Tosho)” It is described in.
[0157] 本発明の液晶表示装置は、前記カラーフィルター以外に電極基板、偏光フィルム、 位相差フィルム、バックライト、スぺーサ.視野角補償フィルム、反射防止フィルム、光 拡散フィルム、防眩フィルムなどさまざまな部材から一般的に構成される。本発明に おける遮光画像はこれらの公知の部材で構成される液晶表示装置に適用することが できる。これらの部材については例えば「'94液晶ディスプレイ周辺材料 ·ケミカルズ の巿場（島 健太郎 （株)シーエムシー 1994年発行）」、「2003液晶関連市場の 現状と将来展望（下巻）（表良吉 (株）富士キメラ総研 2003等発行)」に記載されて おり、 LCDの種類としては、 STN、 TN、 VA、 IPS、 OCS、および R_〇CB等が挙げ られる。 [0157] In addition to the color filter, the liquid crystal display device of the present invention includes an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle compensation film, an antireflection film, a light diffusion film, an antiglare film, and the like. Generally composed of various members. The light-shielded image in the present invention can be applied to a liquid crystal display device composed of these known members. it can. For example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Kayaba (issued by Kentaro Shima CMC 1994)” and “2003 Current Status and Future Prospects of Liquid Crystal Related Markets (Volume 2)” ) Fuji Chimera Research Institute 2003, etc.) ”, and LCD types include STN, TN, VA, IPS, OCS, and R_CB.
[0158] 液晶表示装置の一つとしては、少なくとも一方が光透過性の 1対の基板の間に、力 ラーフィルター、液晶層および液晶駆動手段（単純マトリックス駆動方式およびァクテ イブマトリックス駆動方式を含む）を少なくとも備えたものが挙げられる。  [0158] One of the liquid crystal display devices includes a power color filter, a liquid crystal layer, and liquid crystal driving means (including a simple matrix driving method and an active matrix driving method) between a pair of substrates that are at least one of light-transmitting substrates. ) At least.
前記カラーフィルタ一としては、前記のごとき複数の画素群を有し、前記画素群を 構成する各画素が、互いに本発明による遮光画像により離画されてレ、るカラーフィノレ ターが好適に用いることができる。前記カラーフィルタ一は平坦性が高いため、この力 ラーフィルターを備える液晶表示装置は、カラーフィルターと基板との間にセルギヤッ プムラが発生せず、色ムラ等の表示不良の発生が改善される。  The color filter preferably has a plurality of pixel groups as described above, and each pixel constituting the pixel group is preferably separated from each other by a light-shielded image according to the present invention. it can. Since the color filter has high flatness, the liquid crystal display device provided with the power filter does not generate cell gap unevenness between the color filter and the substrate, and the occurrence of display defects such as color unevenness is improved.
[0159] また、前記液晶表示装置の別の態様としては、少なくとも一方が光透過性の 1対の 基板の間に、カラーフィルター、液晶層および液晶駆動手段を少なくとも備え、前記 液晶駆動手段がアクティブ素子 (例えば TFT)を有し、且つ各アクティブ素子の間に 本発明の金属微粒子分散物、または、これを用いた着色組成物若しくは感光性転写 材料を用いて作製されるブラックマトリックスが形成されているものである。  [0159] As another aspect of the liquid crystal display device, at least one of them is provided with a color filter, a liquid crystal layer, and a liquid crystal driving means between a pair of light-transmitting substrates, and the liquid crystal driving means is active. A black matrix produced using the metal fine particle dispersion of the present invention, a coloring composition using the same, or a photosensitive transfer material is formed between the active elements. It is what.
液晶表示装置にっレ、ては、例えば「次世代液晶ディスプレイ技術（内田 龍男編集 、側工業調査会 1994年発行)」に記載されている。本発明の表示装置 (液晶表示 装置）には特に制限はなぐ例えば前記の「次世代液晶ディスプレイ技術」に記載さ れている色々な方式の液晶表示装置に適用できる。本発明はこれらの中でも、特に カラー TFT方式の液晶表示装置に対して有効である。  The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Side Industry Research Committee, 1994)”. The display device (liquid crystal display device) of the present invention is not particularly limited. For example, it can be applied to various types of liquid crystal display devices described in the above-mentioned “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device.
[0160] また、カラー TFT方式の液晶表示装置については、例えば「カラー TFT液晶デイス プレイ（共立出版 (株） 1996年発行）」に記載されている。更に本発明はもちろん IPS などの横電界駆動方式、 MVAなどの画素分割方式などの視野角が拡大された液晶 表示装置にも適用できる。これらの方式については例えば「EL、 PDP、 LCDデイス プレイ—技術と市場の最新動向—（東レリサーチセンター調査研究部門 2001年発 行） jの 43ページに記載されてレ、る。 [0160] Further, a color TFT liquid crystal display device is described in, for example, "Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)". Furthermore, the present invention can be applied to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field drive method such as IPS and a pixel division method such as MVA. For example, “EL, PDP, LCD display-latest trends in technology and market-(Toray Research Center Research Division 2001) Line) j, page 43.
[0161] 前記液晶表示装置に用いることのできる液晶としては、ネマチック液晶、コレステリッ ク液晶、スメクチック液晶、強誘電液晶等が挙げられる。  [0161] Examples of liquid crystals that can be used in the liquid crystal display device include nematic liquid crystals, cholesteric liquid crystals, smectic liquid crystals, and ferroelectric liquid crystals.
[0162] 実施例  [0162] Examples
以下、実施例によって本発明を具体的に説明するが、本発明はこれに限定される ものではない。また、特に限定のない限り、「部」は「質量部」を意味する。  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Further, unless otherwise specified, “part” means “part by mass”.
[0163] [実施例 1]  [0163] [Example 1]
( 1 )アル力リ可溶性ポリマー試験  (1) Al force resoluble polymer test
pH12. 0に調整した NaOH水溶液 20mlに上述の高分子化合物 PO— 33を 0. 2g 添加して、激しく攪拌し、 25°Cの恒温層中に 6時間放置し溶解性を確認した。同時に 蒸留水 20mlに評価対象の化合物（この場合、前記高分子化合物 P〇一 33) 0. 2gを 添加して、激しく攪拌し、 25°Cの恒温層中に 6時間放置後に溶解性を確認した。この 際、白濁、沈降物が確認されれば不溶（X )、白濁、沈降物が確認されなければ可溶 (〇）と判定した。  To 20 ml of NaOH aqueous solution adjusted to pH 12.0, 0.2 g of the above polymer compound PO-33 was added, stirred vigorously, and left in a constant temperature layer at 25 ° C. for 6 hours to confirm solubility. At the same time, add 0.2 g of the compound to be evaluated (in this case, the polymer compound P0-33) in 20 ml of distilled water, stir vigorously, and leave it in a constant temperature layer at 25 ° C for 6 hours to confirm the solubility. did. At this time, if white turbidity and sediment were confirmed, it was judged as insoluble (X), and if white turbidity and sediment were not confirmed, it was judged as soluble (◯).
結果、上述の高分子化合物 PO— 33は pHの NaOH水溶液に可溶（〇）であり、蒸 留水に不溶（X )であった。  As a result, the above-mentioned polymer compound PO-33 was soluble (◯) in pH NaOH aqueous solution and insoluble (X) in distilled water.
また、前記高分子化合物 PO— 33を下記記載の高分子化合物 PO— 25, 7， 11， 2 0, 23, 19, 32, S— 1 (ビックケミ一社製の Disperbyk— 161) , S— 2 (ビックケミー 社製の Disperbyk— 190)、 T—：!〜 4に置き換えて同様の評価を行った。結果を表 1に示す。  In addition, the polymer compound PO-33 is replaced with the polymer compounds PO-25, 7, 11, 20, 23, 19, 32, S-1 (Disperbyk-161, manufactured by Bicchemi), S-2 (Disperbyk-190 manufactured by Big Chemie Co., Ltd.), T— :! The results are shown in Table 1.
[0164] [化 6] [0164] [Chemical 6]
™ [9910] ™ [9910]
Figure imgf000045_0001
Figure imgf000045_0001
9t-90Ze/900^df/X3d 9t-90Ze / 900 ^ df / X3d
Τ Γ91"0/Ζ,00Ζ OAV
Figure imgf000046_0001
[表 1]Τ Γ91 "0 / Ζ, 00Ζ OAV
Figure imgf000046_0001
[table 1]
Figure imgf000046_0002
Figure imgf000046_0002
( (0 X ))HH20に可溶、アル W溶液にも可溶((0 X)) soluble in HH 2 0, soluble in Al W solution
20に不港、アルか J性に可溶  20 non-portable, Al or J soluble
(本発明におけるアルカリ溶解性ポリマー)  (Alkali-soluble polymer in the present invention)
(2)銀ナノ粒子分散液の調製：金属含有分散液 A— 1 (2) Preparation of silver nanoparticle dispersion: Metal-containing dispersion A— 1
1Nの水酸化ナトリウム水溶液を用レ、、 pHを 12. 0に調整した水溶液 2. 5Lに、前 記高分子化合物 PO— 33を 3g加え、完全に溶解するまで 45。Cで 30分攪拌した。 この溶液を 45°Cに温度制御し、ァスコルビン酸 12gを含む水溶液と、硝酸銀 30gを 含む水溶液を同時に温添加して、黒色の銀ナノ粒子含有液を調製した。 Use 1N sodium hydroxide aqueous solution, and adjust the pH to 12.0 2.5 mL. Add 3 g of the polymer compound PO-33 to 45 L until complete dissolution. Stir at C for 30 min. The temperature of this solution was controlled at 45 ° C., and an aqueous solution containing 12 g of ascorbic acid and an aqueous solution containing 30 g of silver nitrate were added at the same time to prepare a black silver nanoparticle-containing solution.
得られた銀微粒子は、算術平均粒径：52nm、算術標準偏差 33nmの不定形のジ ャガイモ状の粒子であった。  The obtained silver fine particles were amorphous potato-like particles having an arithmetic average particle diameter of 52 nm and an arithmetic standard deviation of 33 nm.
調製した銀ナノ粒子含有液に遠心分離処理（12000rpm' 30min)を行い、上澄み 液を捨てて、蒸留水を加え水洗を 3度繰り返した。更に、前記銀ナノ粒子含有液にァ セトンを加え、スターラーで攪拌後、遠心分離処理（12000rpm' 30min)を行った。 その後、上澄み液を除去して、 1—メトキシ _ 2 _プロピルアセテートをカ卩え、ブランソ ン社製「ソニファー (Sonifier) II型」超音波ホモジナイザーを用いて 20kHzの超音波 を 5分間照射した。その後、ブランソン社製「モデル（Model) 200bdc_h 40 : 0. 8 型超音波ホモジナイザー」で 40kHzの超音波を 10分間照射した。これにより得られ た銀ナノ粒子分散液は、粒子形成後と同様の形状、色味を有していた。また得られ た銀ナノ粒子分散液を原子吸光法により Ag含有量を測定した結果、 Ag濃度 8. 0質 量％であった。また TG— DTA (セイコー (株)製）を用いて、乾燥減量から得られた 高分子化合物 PO— 33の溶剤分散物中の濃度は 1. 1質量％であった。この銀ナノ 粒子分散液を金属含有分散液 A— 1とする。  The prepared silver nanoparticle-containing liquid was centrifuged (12000 rpm '30 min), the supernatant liquid was discarded, distilled water was added, and washing was repeated three times. Further, acetone was added to the silver nanoparticle-containing solution, and the mixture was stirred with a stirrer and centrifuged (12000 rpm'30 min). Thereafter, the supernatant was removed, 1-methoxy-2-propyl acetate was prepared, and 20 kHz ultrasonic waves were irradiated for 5 minutes using a “Sonifier type II” ultrasonic homogenizer manufactured by Branson. Then, 40 kHz ultrasonic waves were irradiated for 10 minutes with a “Model 200bdc_h 40: 0.8 type ultrasonic homogenizer” manufactured by Branson. The silver nanoparticle dispersion thus obtained had the same shape and color as that after the formation of the particles. Moreover, as a result of measuring the Ag content of the obtained silver nanoparticle dispersion by atomic absorption, the Ag concentration was 8.0 mass%. The concentration of the polymer compound PO-33 obtained from loss on drying using TG-DTA (manufactured by Seiko Co., Ltd.) in the solvent dispersion was 1.1% by mass. This silver nanoparticle dispersion is designated as metal-containing dispersion A-1.
[0168] 得られた金属含有分散液 A—1を Ag濃度 =4. 0 X 10— 4モル/ Lとなるようにアセトン 溶剤で適時に希釈して、 日立 (株)製「U— 3410形自記分光光度形」を用レ、、分光 吸収を測定した。波長 450nmと 550nmでの吸収の比、すなわち黒色度 k=Abs (4 50nm) /Abs (550nm)は 1. 4であった。 [0168] The resulting metal-containing dispersion A-1 Ag concentration = 4. 0 X 10- 4 diluted in time with acetone solvent such that the mole / L, Hitachi Ltd. "U- 3410 form Spectral absorption was measured using a self-recording spectrophotometric form. The ratio of absorption at wavelengths of 450 nm and 550 nm, that is, the blackness k = Abs (450 nm) / Abs (550 nm) was 1.4.
[0169] (3)銀微粒子分散液の調製:金属含有分散液 A—2〜A— 14 [0169] (3) Preparation of silver fine particle dispersion: Metal-containing dispersion A-2 to A-14
前記（2)において、高分子化合物 P〇一 33を下記表 2に記載の高分子化合物に置 き換えた以外は、前記（2)と同様にして金属粒子含有液の調製を行った。得られた 銀微粒子の算術平均粒径、算術標準偏差、粒子形状を下記表 2に示す。  A metal particle-containing solution was prepared in the same manner as in the above (2) except that in the above (2), the polymer compound P01-33 was replaced with the polymer compounds described in Table 2 below. The arithmetic average particle diameter, arithmetic standard deviation, and particle shape of the obtained silver fine particles are shown in Table 2 below.
次いで前記（2)と同様に得られた金属粒子含有液を処理し、 Ag濃度 8. 0質量％ の金属粒子分散液を調製した。この際、金属粒子含有液に加えた溶剤は、高分子化 合物の溶解性を考慮し、 1—メトキシ— 2 _プロピルアセテート或いはプロピルアルコ ールを選択した。同様に黒色度 =kを測定し、結果を下記表 2に記載した。 [0170] (4)銀金合金微粒子 (ナノ粒子)分散液の調製：金属含有分散液 A— 15Next, the metal particle-containing liquid obtained in the same manner as in the above (2) was processed to prepare a metal particle dispersion having an Ag concentration of 8.0% by mass. At this time, 1-methoxy-2-propyl acetate or propyl alcohol was selected as the solvent added to the metal particle-containing liquid in consideration of the solubility of the polymer compound. Similarly, the blackness = k was measured, and the results are shown in Table 2 below. [0170] (4) Preparation of silver-gold alloy fine particle (nanoparticle) dispersion: Metal-containing dispersion A— 15
1Nの水酸化ナトリウム水溶液を用い、 pHを 12. 2に調整した水溶液 2. 5Lに、前 記高分子化合物 PO— 20を 3g加え、完全に溶解するまで 45°Cで 30分攪拌した。 この溶液を 50°Cに温度制御し、水素化ホウ素ナトリウム 3gを含む水溶液と、硝酸銀 24gを含む水溶液と塩化金酸 24. 2g含む水溶液とを同時に添加して、黒褐色の銀 金合金ナノ粒子含有液を調製した。得られた銀金合金ナノ粒子の算術平均粒径、算 術標準偏差、粒子形状、を下記表 2に示す。 3 g of the polymer compound PO-20 was added to 2.5 L of an aqueous solution adjusted to pH 12.2 using 1N aqueous sodium hydroxide solution, and stirred at 45 ° C. for 30 minutes until it was completely dissolved. The temperature of this solution is controlled at 50 ° C, and an aqueous solution containing 3 g of sodium borohydride, an aqueous solution containing 24 g of silver nitrate, and an aqueous solution containing 24.2 g of chloroauric acid are added at the same time to contain black-brown silver-gold alloy nanoparticles. A liquid was prepared. Table 2 below shows the arithmetic mean particle diameter, arithmetic standard deviation, and particle shape of the obtained silver-gold alloy nanoparticles.
次いで前記（2)と同様に得られた銀金合金ナノ粒子含有液を処理し、 1ーメトキシ _ 2—プロピルアセテートを加え金属濃度 0. 74mol/L (銀と金の合計）の銀金合金 ナノ粒子分散液を調製し、これを金属含有分散液 A— 15とした。同様に黒色度 =k を測定し、結果を下記表 2に記載した。  Next, the silver-gold alloy nanoparticle-containing liquid obtained in the same manner as in (2) above was processed, and 1-methoxy_2-propyl acetate was added to add a silver concentration of 0.74 mol / L (total of silver and gold). A particle dispersion was prepared, and this was designated as metal-containing dispersion A-15. Similarly, the blackness = k was measured, and the results are shown in Table 2 below.
[0171] (5)銀錫合金ナノ粒子分散液の調製:金属含有分散液 A— 16 [0171] (5) Preparation of silver tin alloy nanoparticle dispersion: Metal-containing dispersion A— 16
1Nの水酸化ナトリウム水溶液を用い、 pHを 12. 0に調整した水溶液 2. 5Lに、高 分子化合物 PO— 20を 3g加え、完全に溶解するまで 45°Cで 30分攪拌した。  To 2.5 L of an aqueous solution adjusted to pH 12.0 using 1N aqueous sodium hydroxide solution, 3 g of the high molecular compound PO-20 was added and stirred at 45 ° C for 30 minutes until completely dissolved.
この溶液 50°Cに温度制御し、水素化ホウ素ナトリウム 3gを含む水溶液酢酸銀 (I) 2 3. 6g、塩ィヒスズ (II)水和物 13. 3gを含む水溶液を添加して、黒褐色の銀錫合金ナ ノ粒子含有液を調製した。得られた銀微粒子の算術平均粒径、算術標準偏差、粒子 形状、を表 2に示す。  This solution was temperature-controlled at 50 ° C and an aqueous solution containing 2 g of sodium acetate (I) 23.6 g containing sodium borohydride 3 g and an aqueous solution 13.3 g hydrated salt (II) hydrate was added. A liquid containing tin alloy nanoparticles was prepared. Table 2 shows the arithmetic average particle diameter, arithmetic standard deviation, and particle shape of the obtained silver fine particles.
次いで前記（2)と同様に得られた金属微粒子を処理し、 1ーメトキシー 2—プロピル アセテートを加え金属濃度 0. 74mol/L (銀と錫の合計）の銀錫合金ナノ粒子分散 液を調製し、これを金属含有分散液 A— 16とした。同様に黒色度 =kを測定し、結果 を下記表 2に記載した。  Next, the obtained metal fine particles were treated in the same manner as in (2) above, and 1-methoxy-2-propyl acetate was added to prepare a silver-tin alloy nanoparticle dispersion with a metal concentration of 0.74 mol / L (total of silver and tin). This was designated as metal-containing dispersion A-16. Similarly, the blackness = k was measured, and the results are shown in Table 2 below.
[0172] [表 2]
Figure imgf000049_0001
[0172] [Table 2]
Figure imgf000049_0001
[0173] (6)感光性遮光層用塗布液 Β— 1 (遮光画像形成用塗布液）の調製 [6173] (6) Preparation of photosensitive light-shielding layer coating solution Β—1 (light-shielding image-forming coating solution)
下記処方の成分を混合して黒色材料用微粒子含有組成物 (感光性遮光層用塗布 夜 Β— 1)を作製した。  Components of the following formulation were mixed to prepare a black material fine particle-containing composition (photosensitive light-shielding layer coating night 1).
[0174] 〔組成〕 [Composition] [Composition]
•金属含有分散液 Α— 1 100. 00部  • Metal-containing dispersion Α— 1 100.00 parts
'プロピレングリコールモノメチルエーテルアセテート 25. 0部  'Propylene glycol monomethyl ether acetate 25.0 parts
14. 0部  14.0 copies
'フッ素系界面活性剤 0. 1部  'Fluorosurfactant 0.1 part
(商品名： F780F、大日本インキ化学工業 (株)製）  (Product name: F780F, manufactured by Dainippon Ink & Chemicals, Inc.)
•ヒドロキノンモノメチルエーテル 0. 001¾  Hydroquinone monomethyl ether 0. 001¾
'ベンジルメタクリレート/メタクリル酸共重合体 2. 1部  'Benzyl methacrylate / methacrylic acid copolymer 2. 1 part
(モノレ];匕 = 73/27、分子量 30000)  (Monole); 匕 = 73/27, molecular weight 30000)
'ビス [4— [N— [4— (4, 6—ビストリクロロメチルー s - _ 2 _ィル）フエニル ]力ルバモイル]フエニル]セバケ一ト  'Bis [4— [N— [4— (4,6-Bistrichloromethyl-s-_ 2 _yl) phenyl] force rubermoyl] phenyl] sebacate
0. 1部  0. 1 copy
'ジペンタエリスリトールへキサアタリレート  'Dipentaerythritol Hexaatalylate
(商品名： KAYARAD DPHA、 日本化薬社製）） ※尚、前記ジペンタエリスリトールへキサアタリレートの添カ卩量は、塗布液におけるべ ンジルメタタリレート/メタクリル酸共重合体の量と高分子化合物 PO— 33の量との総 質量を 1としたときの質量比率で 0. 9となる量とした。〕 (Product name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) * The amount of dipentaerythritol hexatalylate added is the total mass of the amount of benzyl methacrylate / methacrylic acid copolymer and the amount of polymer compound PO-33 in the coating solution. The mass ratio was 0.9. ]
[0175] (7)保護層用塗布液の調製 [0175] (7) Preparation of coating solution for protective layer
下記組成を混合して、保護層用塗布液を調製した。  The following compositions were mixed to prepare a protective layer coating solution.
〔組成〕  [Composition]
'ポリビュルアルコール 3. 0部  'Polybulol alcohol 3.0 parts
(商品名： PVA205、（株）クラレ製）  (Product name: PVA205, manufactured by Kuraray Co., Ltd.)
•ポリビ二ノレピロリドン 1. 3部  • Polyvinylol pyrrolidone 1. 3 parts
(商品名： PVP— K30、アイエスピ一'ジャパン社製）  (Product name: PVP—K30, manufactured by ISPI Japan)
•蒸留水 50. 7部  • 50. 7 parts distilled water
'メチノレアノレ ーノレ 45. 0¾  'Methinorenorenorere 45. 0¾
[0176] (8)感光材料の作製  [0176] (8) Production of photosensitive material
ガラス基板上に、スピンコーターを用いて乾燥膜厚が 1. Ο μ ΐηになるように調製後 3 時間経過の感光性遮光層用塗布液 B—1を塗布して 100°Cで 5分間乾燥し感光性 遮光層を形成した。次いで、感光性遮光層の上にスピンコーターを用いて前記保護 層用塗布液を乾燥膜厚が 1. 5 μ ΐηになるように塗布して、 100°Cで 5分間乾燥し保 護層を形成し、本発明の感光材料 P— 1を作製した。  On the glass substrate, apply the coating solution B-1 for photosensitive light-shielding layer 3 hours after preparation so that the dry film thickness becomes 1. Ο μ ΐη using a spin coater and dry at 100 ° C for 5 minutes. A photosensitive light-shielding layer was formed. Next, the protective layer coating solution is applied onto the photosensitive light-shielding layer using a spin coater so that the dry film thickness is 1.5 μΐη, and dried at 100 ° C. for 5 minutes to form a protective layer. Then, photosensitive material P-1 of the present invention was produced.
また、調製後 3日間経過した感光性遮光層用塗布液 B— 1を用い、前記と同様にガ ラス基板上に塗布して処理を行い、保護層を有する感光材料 Z— 1を得た。  In addition, the photosensitive light-shielding layer coating solution B-1 that had passed 3 days after the preparation was coated on a glass substrate and processed in the same manner as described above to obtain a photosensitive material Z-1 having a protective layer.
[0177] (9)ブラックマトリックスの作製 [0177] (9) Preparation of black matrix
超高圧水銀灯を有すプロキシミティ型露光機（日立電子エンジニアリング (株)製）を 用レ、、前記感光材料 P - 1とマスク（画像パターンを有す石英露光マスク）とを垂直に 立てた状態で、露光マスク面と保護層塗布面との間の距離を 200 x mに設定し、露 光量 70mj/cm2でパターン露光した。次いで、現像処理液 TCD (富士写真フィルム (株)製、アルカリ現像液）を用いて現像処理（33°C · 20秒）を行った。 Using a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, the photosensitive material P-1 and the mask (quartz exposure mask with image pattern) are set upright Then, the distance between the exposure mask surface and the protective layer coating surface was set to 200 xm, and pattern exposure was performed with an exposure light amount of 70 mj / cm 2 . Subsequently, development processing (33 ° C. · 20 seconds) was performed using a development processing solution TCD (manufactured by Fuji Photo Film Co., Ltd., alkaline developer).
これにより、画面サイズ 10インチ、および、画素数力 S480 X 640であり、また、ブラッ クマトリックス幅が 24 μ mであり、画素部の開口が 86 μ τη Χ 304 μ mであるブラックマ トリックス P— 1を得た。 As a result, the black size has a screen size of 10 inches, a pixel power of S480 X 640, a black matrix width of 24 μm, and an aperture in the pixel area of 86 μτη Χ 304 μm. Obtained Trix P—1.
また、前記感光材料 Z—1を用い、同様にしてブラックマトリックス Z—1を得た。  Further, using the photosensitive material Z-1, a black matrix Z-1 was obtained in the same manner.
[0178] (10)評価 [0178] (10) Evaluation
得られたブラックマトリックスについて下記の評価を行った。結果を下記表 3に示す  The obtained black matrix was evaluated as follows. The results are shown in Table 3 below.
[0179] (塗布液経時安定性評価） [0179] (Evaluation of stability over time of coating solution)
前記ブラックマトリックス P— 1および Z— 1の光学濃度を測定した。ブラックマトリック ス Z_ 1の光学濃度の絶対値からブラックマトリックス P_ 1の光学濃度の絶対値を差 し引いて、濃度変動値を算出した。また、濃度変動値の絶対値から、 3日経時前後に おける塗布液の経時安定性を下記の基準に従って評価した。各結果を下記表 3に示 す  The optical densities of the black matrices P-1 and Z-1 were measured. The density fluctuation value was calculated by subtracting the absolute value of the optical density of the black matrix P_1 from the absolute value of the optical density of the black matrix Z_1. In addition, the stability with time of the coating solution before and after the lapse of 3 days was evaluated from the absolute value of the concentration fluctuation value according to the following criteria. Each result is shown in Table 3 below.
〔基準〕  [Standard]
〇 ：OD変化の絶対値が 0. 4未満  ○: Absolute value of OD change is less than 0.4
X : OD変化の絶対値が 0. 4以上 1. 0未満  X: Absolute value of OD change is 0.4 or more and less than 1.0
X X : OD変化の絶対値が 1. 0以上  X X: Absolute value of OD change is 1.0 or more
[0180] 一光学濃度の測定 [0180] Measurement of optical density
前記ブラックマトリックスの光学濃度は以下の方法で測定した。  The optical density of the black matrix was measured by the following method.
まず、ブラックマトリックス作製前のガラス基板上に塗設された感光性遮光層に前述 の超高圧水銀灯を用いて塗布面側から 500mj/cm2の露光を行った。更に 240°C で 120分間ベータを行レ、、その後の光学濃度（OD )を、マクベス濃度計（商品名： T First, the photosensitive light-shielding layer coated on the glass substrate before the black matrix was exposed to 500 mj / cm 2 from the coated surface side using the above-described ultrahigh pressure mercury lamp. Further, beta was performed at 240 ° C for 120 minutes, and then the optical density (OD) was measured using a Macbeth densitometer (trade name: T
1  1
D— 904、マクベス社製）を用いて測定した。  D-904, manufactured by Macbeth Co.).
また、別途ガラス基板の光学濃度（〇D )を同様の方法で測定し、前記〇D力 OD  Separately, the optical density (OD) of the glass substrate is measured in the same way, and the OD force OD is measured.
0 1 を差し弓 Iレ、て、各ブラックマトリックスの光学濃度とした。  0 1 is the bow I and the optical density of each black matrix.
0  0
[0181] 《ブラックマトリックスの品位》  [0181] 《Black Matrix Quality》
ブラックマトリックス Z— 1におけるブラックマトリックスの品位（色味）を目視にて観察 し、下記の基準に従って評価した。結果を下記表 3に示す  The quality (color) of the black matrix in Black Matrix Z-1 was visually observed and evaluated according to the following criteria. The results are shown in Table 3 below.
〔基準〕  [Standard]
◎: 良好な色相の黒色像を有し、ブラックマトリックスとしての品位が優れる。 〇： ブラックマトリックスの黒色度として十分の品位を満たす力 若干黄色みを帯び ている。 A: A black image having a good hue is obtained, and the quality as a black matrix is excellent. ○: Power to satisfy the black matrix's blackness is slightly yellowish.
： 黄茶褐色を有していて、ブラックマトリックスとしての品位が十分でない。  : It has yellowish brown color, and the quality as a black matrix is not enough.
[0182] (11)ブラックマトリックス P2〜P16、 Z— 2〜Z— 16の作製  [0182] (11) Preparation of black matrix P2 to P16, Z-2 to Z-16
前記（6)感光性遮光層用塗布液 B— 1の調製において、組成中の金属含有分散 液 A—1の代わりに金属含有分散液 A— 2〜： 16を用いた以外は同様にして、各分散 液に対応する、ブラックマトリックス P— 2〜； 16および Z— 2〜： 16を作製し、同様に塗 布液経時安定性およびブラックマトリックスの品位（色味）を評価した。結果を下記表 3に示す。  In the preparation of the coating liquid B-1 for photosensitive light-shielding layer (6), except that the metal-containing dispersion A-2 to 16 was used instead of the metal-containing dispersion A-1 in the composition, Black matrix P-2 to 16 and Z-2 to 16 corresponding to each dispersion were prepared, and the coating solution stability over time and the quality (color) of the black matrix were similarly evaluated. The results are shown in Table 3 below.
[0183] [表 3]  [0183] [Table 3]
Figure imgf000052_0001
表 3から、本発明におけるアルカリ可溶性ポリマーを用いて調製した遮光用着色組 成物（塗布液）は、いずれも経時劣化による〇D低下は小さく、また、得られたブラック マトリックスの〇Dが 3. 5以上と高ぐ色味も黒色を維持しており、ブラックマトリクスとし ての品位が高かった。
Figure imgf000052_0001
From Table 3, all of the light-shielding coloring compositions (coating liquids) prepared using the alkali-soluble polymer of the present invention have a small decrease in ○ D due to deterioration over time, and the obtained black matrix has a ○ D of 3 The black color was maintained at a color level of 5 or higher, and the quality of the black matrix was high.
これに対し、比較例の B_ 9、 B— 10の遮光用着色組成物は、経時劣化による〇D 低下は小さいが、黄色みを有しており、得られたブラックマトリックスの O. Dが低 ブ ラックマトリックスとして満足のいく性能を発揮できなかった。 In contrast, the light-shielding coloring compositions of B_9 and B-10 in Comparative Examples have a small yellow color reduction due to deterioration over time, but have a yellowish color, and the resulting black matrix has a low O.D. The We were unable to demonstrate satisfactory performance as a rack matrix.
また比較例の B— 11〜B— 14は経時前の遮光用着色組成物では、 O. Dが 3. 5以 上の高い性能を有するブラックマトリックスを形成できたが、経時後に性能が大きく劣 化し、得られたブラックマトリックスは、満足のいく性能を発揮できなかった。  In addition, Comparative Examples B-11 to B-14 were the light-shielding coloring compositions before aging, and they were able to form a black matrix having a high performance of OD of 3.5 or more. The resulting black matrix was unable to exhibit satisfactory performance.
[0185] [実施例 2]  [0185] [Example 2]
ぐ液晶表示装置の作製 >  LCD device>
実施例 1で得られたブラックマトリックス Z - 1を形成した基板を用いて、特開平 11 _ 242243号公報の第一実施例 [0079]〜 [0082]に記載の方法を用いて、液晶表示 装置 R—1を作製したところ、誤作動なく表示することを確認した。  Using the substrate on which the black matrix Z-1 obtained in Example 1 was formed, a liquid crystal display device using the method described in the first example [0079] to [0082] of JP-A-11-242243 When R-1 was produced, it was confirmed that it displayed without malfunction.
[0186] また、前記ブラックマトリックス Z—1を、実施例 1のブラックマトリックス Z— 2〜16に 置き換えた以外は同様にして、液晶表示装置 R—2〜： 16を作製したところ、誤作動な く表示することを確認した。  [0186] Further, when the black matrix Z-1 was replaced with the black matrix Z-2 to 16 of Example 1 in the same manner, a liquid crystal display device R-2 to 16 was produced. It was confirmed that
[0187] 《ムラ評価》  [0187] 《Evaluation of unevenness》
得られた各液晶表示装置について、下記の評価を行った。結果を下記表 4に示す ムラの測定  The following evaluation was performed about each obtained liquid crystal display device. The results are shown in Table 4 below.
液晶表示装置にグレイのテスト信号を入力させた時に、表示部を目視およびルー ぺにて観察し、ムラの発生の有無を判断した。ムラがまったく観察されなかったものを 「◎」、ムラがわずかに確認されたものを「〇」、ムラが顕著に確認されたものを「X」と した。  When a gray test signal was input to the liquid crystal display device, the display was observed visually and with a magnifying glass to determine the presence or absence of unevenness. “◎” indicates that no unevenness was observed, “◯” indicates that unevenness was slightly observed, and “X” indicates that unevenness was significantly observed.
[0188] [表 4] [0188] [Table 4]
遮光層用 For light shielding layer
液晶 高分子 微粒子 表示  Liquid crystal polymer fine particle display
着色 儎考 表示装置 化合物 組成 ムラ  Coloring Consideration Display device Compound Composition Unevenness
組成物  Composition
R-1 B-1 PO-33 Ag O 本発明  R-1 B-1 PO-33 Ag O The present invention
R-2 B-2 PO-25 Ag O 本発明  R-2 B-2 PO-25 Ag O The present invention
R-3 B-3 PO-7 Ag 〇 本発明  R-3 B-3 PO-7 Ag ○ The present invention
R-4 B-4 PO-11 Ag 本発明 R-4 B-4 PO-11 Ag The present invention
-5 B-5 PO-20 Ag ◎ 本発明  -5 B-5 PO-20 Ag ◎ present invention
R-6 B-6 PO-23 Ag ◎ 本発明  R-6 B-6 PO-23 Ag ◎ present invention
R - 7 B-7 PO-19 Ag 0 本発明  R-7 B-7 PO-19 Ag 0 The present invention
R-8 B-8 PO-32 Ag ◎ 本発明  R-8 B-8 PO-32 Ag ◎ present invention
R-9 B-9 S-1 Ag X 比較例  R-9 B-9 S-1 Ag X Comparative example
R-10 B-10 S-2 Ag X 比較例  R-10 B-10 S-2 Ag X Comparative example
R-11 B-1 1 T-1 Ag 比較例  R-11 B-1 1 T-1 Ag Comparative Example
R-12 B-12 T-2 Ag X 比較例  R-12 B-12 T-2 Ag X Comparative example
R-13 B-13 T-3 Ag X 比較例  R-13 B-13 T-3 Ag X Comparative example
R-14 B - 14 T-4 Ag X 比較例  R-14 B-14 T-4 Ag X Comparative example
R-15 B-15 PO-20 AgAu ◎ 本発明  R-15 B-15 PO-20 AgAu ◎ The present invention
R-16 B-16 PO-20 AgSn 本発明  R-16 B-16 PO-20 AgSn The present invention
[0189] 表 4から、本発明の金属微粒子分散物を用いた液晶表示装置は、表示ムラがなく 表示品質が良ぐより表示品位の高い液晶表示装置が提供できることがわかる。 [0189] From Table 4, it can be seen that the liquid crystal display device using the metal fine particle dispersion of the present invention can provide a liquid crystal display device with high display quality without display unevenness and good display quality.
[0190] [実施例 3]  [0190] [Example 3]
《感光性転写材料の作製》  << Production of photosensitive transfer material >>
2軸延伸した 75 μ m厚みのポリエチレンテレフタレートフィルム支持体表面に、スリ ット状ノズノレを有するガラス基板用コーター（エフ'エー 'エス'ジャパン社製、商品名： MH— 1600)を用いて、下記のように調製した熱可塑性樹脂層用塗布液を厚みが 1 5 / mになるように塗布して 100°Cで 5分間乾燥し、熱可塑性樹脂層を形成した。次 いで、この上に実施例 1の（6)における保護層用塗布液と同組成の中間層用塗布液 を乾燥膜厚が 1· 5 μ ιηになるように塗布して、 100°Cで 5分間乾燥し、中間層を形成 した。更にこの上に、調液から 3日経時した実施例 1の（6)の感光性遮光層用塗布液 B— 1を、乾燥膜厚 1. 0 / mになるよう塗布して 100°Cで 5分間乾燥し、感光性遮光 層を形成し、感光性転写材料を作製した。 Using a biaxially stretched 75 μm-thick polyethylene terephthalate film support surface, a glass substrate coater (made by F'S Japan Co., Ltd., trade name: MH-1600) having a slit-shaped nosole, The thermoplastic resin layer coating solution prepared as described below was applied to a thickness of 15 / m and dried at 100 ° C. for 5 minutes to form a thermoplastic resin layer. Next, an intermediate layer coating solution having the same composition as that of the protective layer coating solution in Example 1 (6) was applied on this so that the dry film thickness was 1.5 μιη. Dry for 5 minutes to form an intermediate layer did. Further, on this, the photosensitive light-shielding layer coating solution B-1 of Example 1 (6), which was aged for 3 days from the preparation, was applied to a dry film thickness of 1.0 / m at 100 ° C. It was dried for 5 minutes to form a photosensitive light-shielding layer, and a photosensitive transfer material was produced.
<熱可塑性樹脂層用塗布液の調製 > <Preparation of coating solution for thermoplastic resin layer>
下記組成を混合して熱可塑性樹脂層用塗布液を調製した。  The following composition was mixed to prepare a coating solution for a thermoplastic resin layer.
'メチルメタタリレート Z2—ェチルへキシルアタリレート zベンジルメタタリレート Zメタ クリノレ酸（55Z11. 7/4. 5/28. 8)の共重合体（分子量 80000)  'Methylmetatalylate Z2—Ethylhexyl talylate z Benzylmetatalylate Z Copolymer (55Z11. 7/4. 5/28. 8) (Molecular weight 80000)
58部  58 copies
•スチレン/アクリル酸 = 63/37の共重合体（分子量 7000)  • Copolymer of styrene / acrylic acid = 63/37 (molecular weight 7000)
136¾  136¾
•2, 2_ビス [4— (メタクリロキシポリエトキシ）フエニル]プロパン  • 2, 2_bis [4 -— (methacryloxypolyethoxy) phenyl] propane
(新中村化学工業 (株)製、多官能アタリレート） 90  (Shin-Nakamura Chemical Co., Ltd., polyfunctional acrylate) 90
'フッ素系界面活性剤 1部 'Fluorosurfactant 1 part
(商品名： F780F、大日本インキ化学工業 (株)製）  (Product name: F780F, manufactured by Dainippon Ink & Chemicals, Inc.)
•メチルェチルケトン 541部  • Methyl ethyl ketone 541 parts
•1ーメトキシー 2—プロパノール 63部 • 1-methoxy-2-propanol 63 parts
•メチノレ了ノレ ーノレ 111咅  • Mechinore no Norenore 111 咅
《感光材料の作製》 << Production of photosensitive material >>
ガラス基板と前記より得られた感光性転写材料とを、感光性遮光層がガラス基板に 接触するように重ね合わせ、ラミネーター（ (株）日立インダストリィズ社製 (LamicII型 ) )を用いて両者を貼り合わせた。ラミネーシヨン条件は、ゴムローラー温度 130°C、線 圧 100N/cm、搬送速度 2. 2mZ分であった。その後、感光性転写材料から支持 体（ポリエチレンテレフタレートフィルム）を剥離し、感光材料 G—1を作製した。  The glass substrate and the photosensitive transfer material obtained above are overlapped so that the photosensitive light-shielding layer is in contact with the glass substrate, and both are laminated using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)). Pasted together. The lamination conditions were rubber roller temperature 130 ° C, linear pressure 100N / cm, and conveyance speed 2.2mZ. Thereafter, the support (polyethylene terephthalate film) was peeled from the photosensitive transfer material to prepare Photosensitive Material G-1.
《ブラックマトリックスの作製》 <Production of black matrix>
実施例 1の（9)と同様の露光機、同様の露光条件にて露光を行った。次いで以下 の 3工程の現像処理を行レ、、ブラックマトリックス H—1を得た。  The exposure was performed under the same exposure machine and the same exposure conditions as those in Example 1 (9). Subsequently, the following three steps of development processing were performed to obtain a black matrix H-1.
〔現像処理〕 [Development processing]
第 1工程:現像処理液（商品名： T_PD1、富士写真フィルム (株)製、アルカリ現像 液）を用い、温度 30°C ·40秒の条件で現像処理を行った。 First step: Development processing solution (trade name: T_PD1, manufactured by Fuji Photo Film Co., Ltd., alkali development Development was performed at a temperature of 30 ° C for 40 seconds.
第 2工程:現像処理液（商品名： Τ CD1、富士写真フィルム (株)製、アルカリ現像 液）を用い、温度 33°C · 20秒の条件で現像処理を行った。  Second step: Development processing was performed using a developing solution (trade name: Τ CD1, manufactured by Fuji Photo Film Co., Ltd., alkaline developer) at a temperature of 33 ° C for 20 seconds.
第 3工程:現像処理液（商品名： T_ SD1、富士写真フィルム (株)製、アルカリ現像 液）を用レ、、温度 33°C · 20秒の条件で現像処理を行った。  Third step: Development processing (trade name: T_SD1, manufactured by Fuji Photo Film Co., Ltd., alkaline developer) was carried out under conditions of a temperature of 33 ° C. for 20 seconds.
[0194] また、前記《感光性転写材料の作製》におレ、て、感光性遮光層用塗布液 B_ 1を感 光性遮光層用塗布液 B— 2〜： 16に置き換えた以外は同様にして、ブラックマトリック ス H— 2〜： 16を得た。 [0194] In addition, in the above-mentioned "Preparation of photosensitive transfer material", the same applies except that photosensitive liquid-shielding layer coating solution B_1 was replaced with photosensitive light-shielding layer coating liquid B-2-. As a result, Black Matrix H-2 to 16 was obtained.
[0195] 《評価》 [0195] << Evaluation >>
実施例 1と同様にして、ブラックマトリックスの光学濃度と品位との評価を行った。結 果を下記表 5に示す。  In the same manner as in Example 1, the optical density and quality of the black matrix were evaluated. The results are shown in Table 5 below.
[0196] [表 5] [0196] [Table 5]
金厲 Gold candy
ブラック 高分子 光学濃度  Black polymer optical density
微敉子 品位 慊考 マ卜リックス 化合物 (経時後）  Fine egg grade Consideration Matrix compound (after time)
組成  Composition
H - 1 PO-33 Ag 3.8 o 本発明 H-1 PO-33 Ag 3.8 o The present invention
H- 2 PO-25 Ag 3.7 o 本発明H-2 PO-25 Ag 3.7 o The present invention
H-3 PO-7 Ag 4.1 ◎ 本発明H-3 PO-7 Ag 4.1 ◎ The present invention
H-4 PO-1 1 Ag 4.1 ◎ 本発明H-4 PO-1 1 Ag 4.1 ◎ The present invention
H-5 PO-20 Ag 4.2 ◎ 本発明H-5 PO-20 Ag 4.2 ◎ The present invention
H-6 PO-23 Ag 3.8 ◎ 本発明H-6 PO-23 Ag 3.8 ◎ The present invention
H - 7 PO-19 Ag 3.9 o 本発明H-7 PO-19 Ag 3.9 o The present invention
H-8 PO-32 Ag 3.8 o 本発明H-8 PO-32 Ag 3.8 o The present invention
H-9 S-1 Ag 1.6 X 比較例H-9 S-1 Ag 1.6 X Comparative example
H-10 S-2 Ag 1.9 X 比較例H-10 S-2 Ag 1.9 X Comparative example
H-1 1 T-1 Ag 2.2 X 比較例H-1 1 T-1 Ag 2.2 X Comparative example
H-12 T-2 Ag 2.7 X 比較例H-12 T-2 Ag 2.7 X Comparative example
H-13 T-3 Ag 1.9 X 比較例H-13 T-3 Ag 1.9 X Comparative example
H-14 ト 4 Ag 2.2 X 比較例H-14 G 4 Ag 2.2 X Comparative Example
H-15 PO-20 AgAu 4.2 ◎ 本発明H-15 PO-20 AgAu 4.2 ◎ The present invention
H-16 PO-20 AgSn 4.2 本発明 H-16 PO-20 AgSn 4.2 The present invention
[0197] 表 5から、本発明のブラックマトリックスは、いずれも 3. 5以上の ODを有し、色味も 黒色を維持しており、ブラックマトリクスとしての品位が高かった。 [0197] From Table 5, all of the black matrices of the present invention had an OD of 3.5 or more, and the color was maintained black, and the quality as a black matrix was high.
[0198] <カラーフィルターの作製および評価 >  [0198] <Production and evaluation of color filter>
本発明および比較例で得られた格子状遮光画像 (ブラックマトリクス）に対し、特開 2 004 - 347831号公報の [0075]〜 [0086]に記載の転写型の感光性樹脂フィルム を用いて赤色、緑色、青色の所定サイズ、形状の着色パターンを形成しカラーフィル ターを作製した。  Using the transfer type photosensitive resin film described in [0075] to [0086] of Japanese Patent Application Laid-Open No. 2004-347831, the grid-shaped light-shielded image (black matrix) obtained in the present invention and the comparative example is red. A color filter having a predetermined size and shape of green and blue was formed to produce a color filter.
本発明において、比較例で作製したカラーフィルターと比較して、特に欠陥がない カラーフィルターが作製できた。  In the present invention, compared with the color filter produced in the comparative example, a color filter having no particular defect could be produced.
[0199] <液晶表示装置の作製および評価〉 前記で得られた本発明のカラーフィルター、および比較例のカラーフィルターを用 レ、て液晶表示装置を形成した。 [0199] <Production and evaluation of liquid crystal display device> A liquid crystal display device was formed using the color filter of the present invention obtained above and the color filter of the comparative example.
比較例のカラーフィルターを用いた液晶表示装置と比較して、本発明のカラーフィ ルターを用いた液晶表示装置が良好な表示特性を示すことを確認した。  Compared with the liquid crystal display device using the color filter of the comparative example, it was confirmed that the liquid crystal display device using the color filter of the present invention showed good display characteristics.
[0200] ぐ液晶表示装置の作製および評価 >  [0200] Production and Evaluation of Gug Liquid Crystal Display>
前記で得られた本発明のカラーフィルター、および比較例のカラーフィルターを用 レ、、 RGBのパターンに対応してガラス基板上に薄膜トランジスタ、画素電極を形成し 、配向膜を設けたアクティブマトリックス基板を作製した。次いで、カラーフィルター上 に ITOと配向膜を形成し対向基板を作製した。このアクティブマトリクス基板と対向電 極間に TN液晶を封入し、シール剤を介して貼り合わせ、各基板の両側に偏光板を クロスニコルにて配置し、アクティブマトリックス基板側にバックライトを配置して液晶 表示装置とした。  Using the color filter of the present invention obtained above and the color filter of the comparative example, an active matrix substrate in which a thin film transistor and a pixel electrode are formed on a glass substrate corresponding to an RGB pattern, and an alignment film is provided. Produced. Next, ITO and an alignment film were formed on the color filter to produce a counter substrate. TN liquid crystal is sealed between this active matrix substrate and the counter electrode, and bonded via a sealant. Polarizers are placed on both sides of each substrate in crossed Nicols, and a backlight is placed on the active matrix substrate side. A liquid crystal display device was obtained.
比較例のカラーフィルターを用いた液晶表示装置と比較して、本発明のカラーフィ ルターを用いた液晶表示装置が良好な表示特性を示すことを確認できた。  Compared with the liquid crystal display device using the color filter of the comparative example, it was confirmed that the liquid crystal display device using the color filter of the present invention showed good display characteristics.
[0201] 本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、 特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記さ れた場合と同程度に、本明細書中に参照により取り込まれる。 [0201] All documents, patent applications, and technical standards mentioned in this specification are the same as if each document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. To the extent it is incorporated herein by reference.
産業上の利用可能性  Industrial applicability
[0202] 本発明の金属微粒子分散液は例えば、塗料、印刷インク、インクジェットインク、力 ラーフィルター、遮光画像作製用着色組成物、画像作製用着色組成物、黒色画像 付き基板、液晶表示装置等を用途として挙げることができる。とりわけ高性能が要求 され、実用上特に重要なものとしては、遮光画像作製用着色組成物、堅牢な塗料ま たはインクジェットインク用着色組成物およびカラーフィルター用着色組成物が挙げ られる。 [0202] The metal fine particle dispersion of the present invention includes, for example, paints, printing inks, inkjet inks, power color filters, shading image preparation coloring compositions, image preparation coloring compositions, substrates with black images, liquid crystal display devices, and the like. It can be mentioned as a use. Particularly, high performance is required, and particularly important in practical use include a coloring composition for producing a light-shielding image, a robust paint or coloring composition for ink-jet ink, and a coloring composition for a color filter.

Claims

請求の範囲 The scope of the claims
[1] 硫黄原子および Zまたは窒素原子を 1個以上有するアルカリ溶解性ポリマーの存 在下で金属イオンを還元し、金属微粒子を形成する金属微粒子分散物の製造方法  [1] A method for producing a metal fine particle dispersion in which metal ions are reduced to form metal fine particles in the presence of an alkali-soluble polymer having at least one sulfur atom and Z or nitrogen atom
[2] 前記アルカリ溶解性ポリマーが、酸性基を有する請求項 1に記載の金属微粒子分 散物の製造方法。 [2] The method for producing a metal fine particle dispersion according to [1], wherein the alkali-soluble polymer has an acidic group.
[3] 前記アルカリ溶解性ポリマーの酸性基が、カルボキシル基である請求項 2に記載の 金属微粒子分散物の製造方法。  [3] The method for producing a metal fine particle dispersion according to [2], wherein the acidic group of the alkali-soluble polymer is a carboxyl group.
[4] 前記アルカリ溶解性ポリマーの有機概念図における有機性/無機性比 (I/O値） 力 0. 44以上 1. 65以下である請求項 1に記載の金属微粒子分散物の製造方法。 4. The method for producing a metal fine particle dispersion according to claim 1, wherein the organic / inorganic ratio (I / O value) in the organic conceptual diagram of the alkali-soluble polymer is 0.44 or more and 1.65 or less.
[5] 前記金属微粒子が、周期律表の第 2族〜第 14族から選ばれる 1種または 2種以上 の金属を含有する請求項 1に記載の金属微粒子分散物の製造方法。 5. The method for producing a metal fine particle dispersion according to claim 1, wherein the metal fine particles contain one or more metals selected from Groups 2 to 14 of the periodic table.
[6] 硫黄原子および/または窒素原子を 1個以上有するアルカリ溶解性ポリマーと、金 属微粒子と、を含有する金属微粒子分散物。 [6] A metal fine particle dispersion containing an alkali-soluble polymer having at least one sulfur atom and / or nitrogen atom and metal fine particles.
[7] 黒色である請求項 6に記載の金属微粒子分散物。 7. The metal fine particle dispersion according to claim 6, which is black.
[8] 前記アルカリ溶解性ポリマーが、酸性基を有することを特徴する請求項 6に記載の 金属微粒子分散物。  [8] The fine metal particle dispersion according to [6], wherein the alkali-soluble polymer has an acidic group.
[9] 前記アルカリ溶解性ポリマーの酸性基が、カルボキシル基である請求項 8に記載の 金属微粒子分散物。  [9] The metal fine particle dispersion according to [8], wherein the acidic group of the alkali-soluble polymer is a carboxyl group.
[10] 前記アルカリ溶解性ポリマーの有機概念図における有機性/無機性比（I/O値） が、 0. 44以上 1. 65以下である請求項 6に記載の金属微粒子分散物。  10. The metal fine particle dispersion according to claim 6, wherein the organic / inorganic ratio (I / O value) in the organic conceptual diagram of the alkali-soluble polymer is 0.44 or more and 1.65 or less.
[11] 前記金属微粒子が、周期律表の第 2族〜第 14族から選ばれる 1種または 2種以上 の金属を含有する請求項 6に記載の金属微粒子分散物。  [11] The metal fine particle dispersion according to [6], wherein the metal fine particles contain one or more metals selected from Group 2 to Group 14 of the Periodic Table.
[12] 請求項 6に記載の金属微粒子分散物を含有する着色組成物。  [12] A coloring composition comprising the metal fine particle dispersion according to claim 6.
[13] 黒色である請求項 12に記載の着色組成物。  13. The colored composition according to claim 12, which is black.
[14] 支持体上に少なくとも一層の感光性遮光層を設けた感光性転写材料であって、前 記感光性遮光層が請求項 6に記載の金属微粒子分散物を用いて形成される感光性 転写材料。 [14] A photosensitive transfer material in which at least one photosensitive light-shielding layer is provided on a support, wherein the photosensitive light-shielding layer is formed using the metal fine particle dispersion according to claim 6. Transfer material.
[15] 請求項 6に記載の金属微粒子分散物を用いて形成される遮光画像を有する遮光 画像付き基板。 [15] A substrate with a light-shielding image having a light-shielding image formed using the metal fine particle dispersion according to [6].
[16] 請求項 14に記載の感光性転写材料を用いて作製される遮光画像を有する遮光画 像付き基板。  [16] A substrate with a light-shielding image having a light-shielding image produced using the photosensitive transfer material according to [14].
[17] 請求項 6に記載の金属微粒子分散物を用いて形成されるカラーフィルター。  [17] A color filter formed using the fine metal particle dispersion according to [6].
[18] 請求項 6に記載の金属微粒子分散物を用いて形成される液晶表示装置。 18. A liquid crystal display device formed using the metal fine particle dispersion according to claim 6.
PCT/JP2006/320646 2005-10-19 2006-10-17 Method for producing metal particle dispersion, metal particle dispersion, and colored composition, photosensitive transfer material, substrate with light-blocking image, color filter and liquid crystal display each using such metal particle dispersion WO2007046371A1 (en)

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