WO2007032144A1 - Colored composition and photosensitive transfer material - Google Patents

Colored composition and photosensitive transfer material Download PDF

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Publication number
WO2007032144A1
WO2007032144A1 PCT/JP2006/314170 JP2006314170W WO2007032144A1 WO 2007032144 A1 WO2007032144 A1 WO 2007032144A1 JP 2006314170 W JP2006314170 W JP 2006314170W WO 2007032144 A1 WO2007032144 A1 WO 2007032144A1
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WO
WIPO (PCT)
Prior art keywords
light
shielding layer
display device
layer
silver
Prior art date
Application number
PCT/JP2006/314170
Other languages
French (fr)
Japanese (ja)
Inventor
Akira Hatakeyama
Hidenori Gotoh
Original Assignee
Fujifilm Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corporation filed Critical Fujifilm Corporation
Priority to CN2006800341739A priority Critical patent/CN101268151B/en
Priority to JP2007535390A priority patent/JP5252919B2/en
Publication of WO2007032144A1 publication Critical patent/WO2007032144A1/en

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/206—Filters comprising particles embedded in a solid matrix
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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

Definitions

  • the present invention relates to a colored composition and a photosensitive transfer material, a light shielding layer for a display device using the same, a method for producing the same, a color filter, a liquid crystal display element, and a substrate with a light shielding layer for a display device.
  • Color filters used for color liquid crystal displays, etc. have a colored pixel layer (R, G, B) formed on a transparent substrate, and each colored pixel of R, G, B (red, green, blue)
  • a light shielding layer for a display device is formed in the gap for the purpose of improving display contrast.
  • a light shielding layer for a display device is used to prevent deterioration in image quality due to current leakage due to light from the thin film transistor. Is required!
  • a metal film such as chromium is used as a light shielding layer.
  • a metal thin film is formed by vapor deposition or sputtering.
  • a photoresist is applied on the metal thin film, and then the photoresist layer is exposed and developed using a photomask having a pattern of a light shielding layer for a display device.
  • the exposed metal thin film is etched, and finally the resist layer on the metal thin film is removed to form a light shielding layer (see, for example, Non-Patent Document 1).
  • this method uses a metal thin film, a high light-shielding effect can be obtained even if the film thickness is thin.
  • a vacuum film forming process or an etching process such as a vapor deposition method or a sputtering method is required, resulting in high costs and an environmental load. There is a problem that cannot be ignored.
  • the metal film has a problem that the reflectivity is high and the display contrast is low under external light.
  • a countermeasure use a low-reflective chromium film (such as one that has a two-layer strength of metallic chromium and acid chromium).
  • the countermeasure method involves a problem that further increases the cost.
  • a method for forming a light shielding layer for a display device a method using a photosensitive resin composition containing a light shielding pigment such as carbon black is also known.
  • This method is an example For example, after forming R, G, B pixels on a transparent substrate, a photosensitive resin composition containing carbon black is applied on the pixels, and the entire surface from the R, G, B pixel non-formation side of the transparent substrate is applied.
  • This is a method for forming a light-shielding layer for a display device of a self-alignment type that performs exposure (see, for example, Patent Document 1).
  • this method has a lower manufacturing cost than the method by etching the metal film, there is a problem that the film thickness is increased in order to obtain a sufficient light shielding property.
  • the light-shielding layer for the display device and the R, G, B pixels overlap (steps), the flatness of the color filter deteriorates, the cell gap unevenness of the liquid crystal display element occurs, and the display of color unevenness etc. It leads to failure.
  • a light shielding layer for a display device is first prepared using a photosensitive resin composition containing carbon black on a substrate and then RGB pixels are formed, the thickness of the light shielding layer for the display device is increased. As a result, defects such as bubble generation may occur when forming RGB pixels.
  • Patent Document 2 a method for producing a light shielding layer for a display device in which light shielding metal particles are uniformly dispersed therein is known (see Patent Document 2).
  • a photosensitive resist layer containing a hydrophilic resin is formed on a transparent substrate.
  • exposure and development are performed through a photomask having a pattern of a light shielding layer for a display device 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, and the metal compound is contained in the relief and dried.
  • the obtained light shielding layer for a display device is obtained.
  • the metal particles nickel, cobalt, iron, copper, and chromium are listed, and nickel is shown as a specific example.
  • Non-Patent Document 1 Kyoritsu Shuppan Co., Ltd. “Color TFT Liquid Crystal Display” pp. 218-220 (10 April, 1997)
  • Patent Document 1 Japanese Patent Application Laid-Open No. 62-9301
  • Patent Document 2 Japanese Patent No. 3318353
  • the present invention has been made in view of the above-described problems, and is a thin film that has a high light-shielding performance, can be manufactured at low cost, and has a low environmental impact.
  • the present invention provides a coloring composition and a photosensitive transfer material capable of producing a light-shielding layer for display devices of achromatic color).
  • the present invention provides a light shielding layer for a display device using the colored composition or the photosensitive transfer material, a method for producing the same, a color filter provided with the light shielding layer for a display device, and a liquid crystal display element.
  • the present invention provides a substrate with a light shielding layer for a display device, on which the light shielding layer for a display device as described above is formed.
  • the above-mentioned problems are solved by providing the following coloring composition and photosensitive transfer material, a light shielding layer for a display device and a method for producing the same, a color filter, a liquid crystal display element, and a substrate with a light shielding layer for a display device.
  • a coloring composition comprising metal particles having a silver-tin alloy part and having an optical density after film formation of 3.5 or more per dry film thickness l; z m.
  • the volume fraction in the solid content of the metal particles having the silver-tin alloy part is 0.05 to 0.7, and transmitting C light source XYZ table of light color coordinate (X, y) and chromaticity coordinate (X, y) of the light source
  • a support and at least a photosensitive light-shielding layer is provided on the support, and the photosensitive light-shielding layer is provided.
  • the layer contains metal particles having a silver-tin alloy part, and the optical density of the photosensitive light-shielding layer is a dry film thickness.
  • the volume fraction of metal particles having a silver-tin alloy part in the photosensitive light-shielding layer is 3.5 or more per 1 ⁇ m, and 0.05 to 0.7.
  • the color system chromaticity coordinates (X, y) and the chromaticity coordinates (X, y) of the light source satisfy the relationship of (x-x) 2 + (yy) 2 ⁇ 0.01
  • a photosensitive transfer material comprising:
  • a light-shielding layer for a display device produced using the colored composition according to any one of the above (1) to (4) or the photosensitive transfer material according to (5).
  • a pair of substrates at least one of which is light transmissive, and at least a color filter, a liquid crystal layer, and a liquid crystal driving unit between the substrates, and the color filter according to (7)
  • a liquid crystal display element comprising the color filter described above.
  • a method for producing a light-shielding layer for a display device comprising a step of developing the colored composition layer after exposure through a photomask for the light-shielding layer for a display device.
  • Light-shielding for a display device comprising: a step of peeling the support from the laminate of the photosensitive transfer material and the light-transmitting substrate; and a step of developing after exposing the photosensitive light-shielding layer through a photomask for the light-shielding layer for the display device Layer manufacturing method.
  • Metal particles having a silver-tin alloy part in the optical layer are dispersed at a volume fraction of 0.05 to 0.7, and the optical density of the light shielding layer for display device is 3.5 or more per 1 m of dry film thickness.
  • the XYZ color system chromaticity coordinates (X, y) of the C light source transmitted light and the chromaticity coordinates (X, y) of the light source are (x-x ) 2 + (yy) 2 ⁇ 0.01
  • a substrate with a light shielding layer for a display device A substrate with a light shielding layer for a display device.
  • the colored composition of the present invention By using the colored composition of the present invention, a thin film with high light-shielding performance, low cost, less environmental impact, and excellent in black (achromatic and achromatic) hue. A light shielding layer is obtained. Further, the light-shielding layer for a display device obtained by the present invention has no or very little hue change due to heating.
  • the color filter using the light-shielding layer for the display device has excellent flatness, and bubbles are not mixed or very little when forming RGB pixels. Furthermore, liquid crystal display devices incorporating this power color filter do not cause cell gap unevenness between the color filter and the substrate, and display defects such as color unevenness do not occur!
  • the colored composition of the present invention comprises metal particles having a silver-tin alloy part (hereinafter simply referred to as “silver-tin alloy part-containing particles”), and the optical density of the layer formed by applying the colored composition is The dry film thickness is 3.5 or more per 1 m.
  • a colored composition has a volume fraction of silver-tin alloy part-containing particles in the solid content of 0.05 to 0.7, and is applied to the light-shielding layer formed by applying the colored composition. Therefore, the XYZ color system chromaticity coordinates (X, y) of the C light source transmitted light and the chromaticity coordinates (X, y) of the light source are (x-x) 2 + (yy) 2 ⁇ 0 01 relationship
  • the "volume fraction of the silver-tin alloy part-containing particles in the solid content” is a light-shielding layer obtained by applying and drying the colored composition (if the colored composition is photosensitive, the colored composition This means the volume fraction of the silver-tin alloy part-containing particles contained in the layer after the product is applied and exposed and cured.
  • the volume fraction also means the volume fraction of the silver-tin alloy part-containing particles contained in the light-shielding layer for a display device (the colored composition contains a binder in addition to the silver-tin alloy part-containing particles).
  • Polymers, monomers, polymerization initiators, and other optional components are included, but some of these components may be lost during coating, heat drying, etc. during the formation of the light-shielding layer. And made such a definition).
  • volume fraction is measured based on the following equation.
  • volume fraction of silver-tin alloy part-containing particles (coating amount Z of silver-tin alloy part-containing particles Z
  • the coating amount is expressed in gZm 2
  • the density is expressed in gZcm 3
  • the film thickness is expressed in m.
  • (the coating amount of the silver-tin alloy part-containing particles Z the density of the silver-tin alloy part-containing particles) represents the thickness when the silver-tin alloy part-containing particles are coated as a uniform film in units of ⁇ . Matches the value.
  • the coating amount of the silver-tin alloy part-containing particles is measured using a fluorescent X-ray apparatus.
  • the density of the silver-tin alloy part-containing particles can be calculated as follows.
  • the dried film of silver-tin alloy part-containing particles is peeled off and finely pulverized to prepare a powder sample for measurement. Furthermore, after vacuum drying for 1 hour in a desiccator, the dried sample is placed in a precisely weighed glass hydrometer (Wig) and weighed accurately to calculate the mass (W2g) of the sample. Add a liquid with a known specific gravity (Dig) into the gap until the entire sample is completely buried, and defoam using ultrasonic waves.
  • the mass of the liquid can be calculated, converted into a volume using specific gravity, and the density can be obtained using the following formula (1).
  • the capacity of the hydrometer is Vlml.
  • Density of silver-tin alloy part-containing particles W2Z ⁇ V1— (W3-W1 -W2) ZD1)
  • the XYZ color system chromaticity coordinates (X, y) of the light transmitted through the light source C of the light shielding layer are measured with a spectrophotometer or a microspectrophotometer. By calculating the values X, Y and Z, the chromaticity coordinates are obtained. Further, the XYZ color system chromaticity coordinates (X, y) of the C light source used in the present invention, X force SO. 3100, and y force 0.3164.
  • MCPD-1000 manufactured by Otsuka Electronics Co., Ltd. can be used as a commercially available spectrophotometer, and OSP-SP100 and OSP-SP200 manufactured by OLYMPUS can be used as microspectrophotometers.
  • XYZ color system chromaticity coordinates (X, y) of the light source and chromaticity coordinates (X, y) of the light source are (x—x
  • the c light source has characteristics close to those of a knock light source used in a liquid crystal display device, and the hue of the black portion is deteriorated by the influence of light transmitted through the light shielding layer for the display device when the above conditions are satisfied. It shows that there is no.
  • the above condition indicates that the chromaticity coordinate (X, y) of the transmitted light is close to the chromaticity coordinate (X, y) of the C light source.
  • satisfying the above condition indicates that the black hue is excellent without adding any other color to black.
  • the influence of ambient light (reflected light) at the place where the liquid crystal display device is used on the hue of the black part can be considered in the same manner as the transmitted light, the hue is not deteriorated by the reflected light.
  • the metal particles having a silver-tin alloy part according to the present invention each have a silver-tin alloy force, a silver-tin alloy part and another metal part force, and a silver-tin alloy. Including those composed of parts and other alloy parts.
  • the definition of metal is as described in Iwanami Physical and Chemical Dictionary, 4th edition (published by Iwanami Shoten in 1987).
  • the silver-tin alloy in the present invention is a mixture of silver and tin at the atomic level, and includes solid solutions, eutectic crystals, compounds, intermetallic compounds, and the like. Alloys are described in, for example, Iwanami Physical and Chemical Dictionary, 4th edition (published by Iwanami Shoten in 1987).
  • the silver-tin alloy part-containing particles according to the present invention are at least partially composed of a silver-tin alloy.
  • This configuration can be confirmed using, for example, HD-2300 manufactured by Hitachi, Ltd. and EDS (energy dispersive X-ray analyzer) manufactured by Noran.
  • the measurement conditions are the spectrum of the center 15nm mouth area of each particle with an acceleration voltage of 200kV. is there.
  • the silver-tin alloy part-containing particles can exhibit excellent light-shielding performance with a small amount of black density or a thin film, and have high thermal stability. Therefore, heat treatment can be performed at a high temperature (eg, 200 ° C. or more) without impairing the black density, and a high degree of light shielding can be secured stably.
  • a high temperature eg, 200 ° C. or more
  • it is suitable for a light shielding film (so-called black matrix) for a color filter which requires a high light shielding property and is generally subjected to a beta treatment.
  • the silver-tin alloy part-containing particles according to the present invention are obtained by combining (for example, alloying) Ag and tin (Sn) at a silver (Ag) ratio of 30 to 80 mol%. .
  • Ag silver
  • Sn tin
  • the proportion of Ag is preferably 40 to 75 mole 0/0, and most preferably 50 to 75 molar%.
  • particles with an Ag ratio of 75 mol% that is, AgSn alloy particles are easy to produce, and the resulting particles are also stable and preferable.
  • the colored composition of the present invention may contain one kind of silver-tin alloy part-containing particles. Two or more kinds of silver-tin alloy part-containing particles having different Ag ratios within the above range are used in combination. It may be configured.
  • the silver-tin alloy part-containing particles according to the present invention can be produced by alloying or the like by a general method such as heating, melting and mixing in a crucible or the like.
  • the melting point of Ag is around 900 ° C
  • the melting point of Sn is around 200 ° C. Therefore, it is preferable to use the particle reduction method because there is a large difference between the melting points of the two and an extra step of micronization after compounding (for example, alloying) is required.
  • an Ag compound and a Sn compound are mixed and reduced.
  • it is a method in which metal Ag and metal Sn are simultaneously deposited at close positions to simultaneously achieve compounding (for example, alloying) and micronization.
  • Ag tends to be precipitated immediately before Sn as soon as it is reduced, it is preferable to control the precipitation timing by making Ag and Z or Sn into a complex salt.
  • the Ag compound include silver nitrate (AgNO), silver acetate (Ag (CH COO)), and perchloric acid.
  • Silver (AgCIO ⁇ ⁇ ⁇ ) and the like are preferable. Of these, silver acetate is particularly preferred.
  • Sn compound examples include stannous chloride (SnCl), stannic chloride (SnCl), and stannous acetate.
  • Examples of the reduction method include a method using a reducing agent, a method of reducing by electrolysis, and the like.
  • the former method using a reducing agent is preferable in that fine particles can be obtained.
  • the reducing agent include hydroquinone, catechol, paraaminophenol, noraf-rangeamine, and hydroxyacetone. Of these, hydroxyacetone is particularly preferable because it volatilizes and does not readily affect the display device.
  • the silver-tin alloy part-containing particles according to the present invention preferably have the following physical properties, average particle size (particle size), particle shape, and the like.
  • Silver-tin alloy part-containing particles according to the present invention are obtained by differential scanning calorimetry (DSC: Differential
  • Particles having a melting point of 240 to 400 ° C as measured by scanning calorimetry are preferred. Since the melting point is within this range, it exhibits better thermal stability than metal Ag (melting point: 950 ° C) and metal Sn (melting point: 230 ° C).
  • the melting property (melting point) of AgSn alloy 20 mg was set as a sample in the measurement cell of DSC (SSC / 5200, manufactured by Seiko Instruments Inc.), and the temperature drop crystallization peak by DSC was measured. Measured by cooling from 200 ° C to room temperature with a temperature drop rate of 10 ° CZ.
  • the silver tin alloy part-containing particles according to the present invention preferably have an average particle size (number average particle size) of 500 nm or less, and more preferably have a lower limit of 2 nm or more. Furthermore, the average particle diameter is more preferably 20 to 200 nm, and particularly preferably 30 to: LOOnm.
  • the number average particle size is particularly in the above-mentioned range, unlike a metal particle, it has a black hue at any particle diameter.
  • the number average particle size exceeds 500 nm, the surface shape when the film is formed may be deteriorated.
  • the blackness may decrease and the film may become yellowish.
  • the number average particle size is measured as follows using a photograph obtained by a transmission electron microscope [EM-2010 (manufactured by JEOL Ltd.)].
  • the average particle size of the individual particles is defined as the number average particle size.
  • the photograph is taken at a magnification of 100,000x and an acceleration voltage of 200kV.
  • the particle shape of the "silver-tin alloy part-containing particles" according to the present invention may be any shape such as a cubic shape, a high aspect, a medium aspect, and a needle shape without any particular limitation.
  • the silver-tin alloy part-containing particles may further contain a salt, an organic substance, other elements (Ca, P, Na, etc.) and the like. However, even in that case, it is preferable to have and maintain the above-mentioned physical properties, particle size, and particle shape.
  • the amount of the silver-tin alloy part-containing particles in the colored composition of the present invention may be appropriately selected according to the purpose and application.
  • the amount of the silver-tin alloy part-containing particles is preferably 5 to 70% by volume and more preferably 10 to 66% by volume with respect to the total solid content (volume) of the composition from the viewpoint of obtaining a high level of light shielding properties. Preferred is 15 to 60% by volume.
  • the film thickness when formed may be thicker than 1.0 m, and when it exceeds 70% by volume, the reflectance is high and the display contrast is high. May be damaged.
  • the colored composition in the present invention preferably has photosensitivity.
  • a photosensitive resin composition is added to the colored composition.
  • the photosensitive resin composition contains a binder polymer, a monomer that undergoes addition polymerization upon irradiation with light having an ethylenically unsaturated double bond, a photopolymerization initiator, and the like.
  • photosensitive resin compositions that can be developed with an alkaline aqueous solution and those that can be developed with an organic solvent.
  • the photosensitive resin composition is preferably one that can be developed with an aqueous alkaline solution in terms of safety and the cost of the developer.
  • the photosensitive resin composition may be a negative type in which a part that receives radiation such as light or an electron beam is cured, or a positive type in which a non-radiation-receiving part is cured.
  • Examples of the positive photosensitive resin include novolac resins.
  • JP-A-7-438 An alkali-soluble novolac rosin system described in Japanese Patent No. 99 can be used.
  • a positive photosensitive resin layer that is, as a resin and a photosensitizer described in the publication, 1,2-naphthoquinonediazide sulfonate ester and thermosetting described in the publication
  • a photosensitive resin layer containing a mixture of agents can be used.
  • a composition described in JP-A-5-262850 can also be used.
  • the negative photosensitive resin includes a photosensitive resin having a negative diazo resin and a binder power, a photopolymerizable composition, a photosensitive resin composition comprising an azide compound and a binder, and a cinnamic acid type photosensitive resin. And the like.
  • photosensitive resins containing a photopolymerization initiator, a photopolymerizable monomer and a binder as basic constituents are particularly preferred.
  • the photosensitive resin layer contains “polymerizable compound B”, “polymerization initiator C”, “surfactant”, “adhesion aid” and other compositions described in JP-A-11-133600. Available.
  • a negative photosensitive photosensitive resin that can be developed in an aqueous alkali solution can be addition-polymerized by irradiation with light with a binder containing a carboxylic acid group as a main component (such as a thermoplastic resin described later). It contains an ethylenically unsaturated double bond-containing monomer and a photopolymerization initiator.
  • Noinda examples 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, JP-B-5- A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer as described in Japanese Patent No. 25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048. Examples thereof include a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer.
  • cellulose derivatives having a carboxylic acid group in the side chain can also be mentioned.
  • a polymer having a hydroxyl group added with a cyclic acid anhydride can also be preferably used.
  • the binder used for the photosensitive resin layer is selected from those having an acid value in the range of 30 to 400 mg KOHZg and a weight average molecular weight in the range of 1000 to 300,000. In addition, various performances such as developability are adversely affected to improve the strength of the cured film.
  • An alkali-insoluble polymer can be added within a range that does not resonate. Examples of these polymers include alcohol-soluble nylon and epoxy resin.
  • the binder is generally 10 to 95% by mass, more preferably 20 to 90% by mass, based on the total solid content of the photosensitive coloring composition. In the range of 10 to 95 mass%, the adhesiveness of the photosensitive resin layer is not too high, and the strength and photosensitivity of the formed layer are not inferior.
  • Photopolymerization initiators include vicinal polyketaldonyl compounds disclosed in U.S. Pat. No. 2,367,660, acyloin ether compounds described in U.S. Pat. No. 2448828, U.S. Pat. Aromatic hydrocarbon substituted with ⁇ -hydrocarbons described in US Pat. No. 2722512, polynuclear quinone compounds described in US Pat. Nos. 3046127 and 2951758, US Pat. No. 3,549,367 Combination of triarylimidazole dimer and ⁇ -aminoketone described in the specification, benzothiazole compound and torino, romethyl-s-triazine compound described in Japanese Patent Publication No.
  • the content of the photopolymerization initiator is generally 0.5 to 20% by mass, preferably 1 to 15% by mass, based on the total solid content. If it is less than 5% by mass, the photosensitivity and image strength are low. Even if it is added in excess of 20% by mass, no effect on performance improvement is observed.
  • Examples of the ethylenically unsaturated double bond-containing monomer (hereinafter simply referred to as "monomer" t) that can be addition-polymerized by light irradiation 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 funkistil (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (Meth) atarylate, trimethylol ethane triatrate, trimethylol propane triatrate, trimethylol propane diatalylate, neopentyl glycol di (meth) attaryl , Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate Rate, trimethylolpropane tri (atallyloyloxypropyl) ether,
  • urethane acrylates disclosed in JP-B-48-41708, JP-A-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49 4319 Polyfunctional talates and metatalates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid disclosed in each publication of No. 1 and 52-30490 Can be mentioned.
  • trimethylolpropane tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferred.
  • These monomers may be used alone or in combination of two or more.
  • the content of the monomer based on the entire solid content of the colored composition having photosensitivity, 5 to 50 wt% guar general, preferably 10 to 40 mass 0/0.
  • the intensity of the content of the monomer is from 5 to 50 mass 0/0 ranging in photosensitivity and image is also not reduced, it is also not name that tackiness of the photosensitive light shielding layer is excessive.
  • the photosensitive resin composition preferably further contains a thermal polymerization inhibitor in addition to the above components.
  • thermal polymerization inhibitors include, for example, hydroquinone, p-methoxyphenol, p-t-butylcatechol, 2,6-di-tert-butyl-cresol, ⁇ -naphthol, pyrogallol and other aromatic hydroxy compounds, benzoquinone, ⁇ -toluquinone Quinones such as naphthylamine, pyridine, ⁇ toluidine, phenothiazine, etc., aluminum salt or ammonium salt of ⁇ ⁇ -trosophenol hydroxylamine, chloranil, nitrobenzene, 4, 4'-thiobis (3— Methyl-6 t-butylphenol), 2, 2'-methylenebis (4-methyl-6 t-butylphenol), 2 mercaptobenzimidazole, etc. It is done.
  • the photosensitive resin composition further contains known additives as necessary, for example, plasticizers, surfactants, adhesion promoters, dispersants, plasticizers, anti-sagging agents, leveling agents, Defoamer, flame retardant
  • Brighteners, solvents and the like can be added.
  • adhesion promoters for example, alkylphenol Z formaldehyde novolac rosin, porobule ether, polyisobutyl ether, polybutyral
  • the photosensitive resin composition When the silver-tin alloy part-containing particles are used as an aqueous dispersion, the photosensitive resin composition must be aqueous.
  • a photosensitive resin composition include those described in paragraphs 0015 and 0023 of JP-A-8-271727 and commercially available products such as “SPP-manufactured by Toyo Gosei Co., Ltd.”. M20J etc. are mentioned.
  • the coloring composition having photosensitivity contains a binder, a dispersant, a solvent, and the like as required in addition to the silver-tin alloy part-containing particles as described above.
  • a binder a water-soluble resin polymer binder or a water-insoluble resin binder is appropriately used.
  • the water-soluble rosin polymer binder is preferably a protective colloid polymer.
  • the water-soluble resin polymer binder include gelatin, polybutyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkylamine, and a partial alkyl ester of polyacrylic acid.
  • those described in “Encyclopedia of Pigments (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd. 2000)” can be mentioned.
  • water-insoluble polymer binder is described in "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). It is possible to select and use at least one organic solvent soluble polymer noinder.
  • water-insoluble polymer binder examples include polyamide, polyester, polystyrene, phenolate, polyolefin such as polyethylene, polycarbonate, Silicone resin, polyurea, polyurethane, polyanhydride, polysulfone, polyimine, polysulfide, polyacrylonitrile, nylon, polyacetate butyl, polybulle ether, polyacrylic acid and polymethacrylic acid and their esters, as well as their copolymers or Is a denatured product and is soluble in an organic solvent.
  • polyamide polyamide
  • polyester polystyrene
  • phenolate polyolefin
  • polyethylene polyethylene
  • polycarbonate Silicone resin
  • polyurea polyurethane
  • polyanhydride polysulfone
  • polyimine polysulfide
  • polyacrylonitrile nylon
  • polyacetate butyl polybulle ether
  • polyacrylic acid and polymethacrylic acid and their esters as well as their copolymers or I
  • a polymer latex can also be used from the viewpoint that it can be mixed with water.
  • Polymer latex is a dispersion of water-insoluble polymer particles in water.
  • examples of the water-insoluble polymer include water-insoluble polymers as described above. Details are described, for example, in “Polymer Latex Chemistry” (Muro Muroi, published by Kobunshi Shuppankai, 1973).
  • polymer latex examples include polyester, polyurethane, polyurethane Z urethane, SBR (styrene butadiene type), MBR (MMAZ butadiene, acrylic Z butadiene), NBR (acrylonitrile / butadiene), NR (natural rubber), BR ( Examples thereof include butadiene rubber), CR (chloroprene rubber), IR (isoprene rubber), VP (SBRZ dibule pyridine), and polymer latexes of these copolymers.
  • SBR styrene butadiene type
  • MBR MMAZ butadiene, acrylic Z butadiene
  • NBR acrylonitrile / butadiene
  • NR natural rubber
  • BR examples thereof include butadiene rubber), CR (chloroprene rubber), IR (isoprene rubber), VP (SBRZ dibule pyridine), and polymer latexes of these copolymers.
  • polymer latex can be used in combination with the polymer latex.
  • polymer latexes that can be used in combination include SBR and NR, IR and NR, CR and NR, NBR with different -tolyl content, SBR with different styrene content, SBR and VP, NBR and MBR, SBR and NBR SBR and MBR, BR and CR, NBR and VP, CR and VP, etc., which is a combination of nonionic and cationic ones, is preferred! /.
  • the amount of the polymer used as the noinda is preferably 3 to 50% by mass, particularly preferably 10 to 30% by mass, in the coloring composition having no photosensitivity.
  • organic solvent can be used as a solvent.
  • Particularly preferred organic solvents include methyl alcohol, isopropyl alcohol, MEK, ethyl acetate, toluene and the like. Water is also preferred as the solvent. Mix these solvents as necessary.
  • a photosensitive transfer material is prepared using the above-described photosensitive coloring composition, and a light-shielding layer for a display device can be prepared using the photosensitive transfer material.
  • the photosensitive transfer material is a temporary support provided with a photosensitive light-shielding layer formed at least by the colored composition having photosensitivity.
  • the thickness of the photosensitive light-shielding layer is preferably in the range of 0.2 to 2 ⁇ m, particularly preferably in the range of 0.2 to 1 m.
  • the temporary support of the present invention a known support such as polyester or polystyrene can be used.
  • the temporary support biaxially stretched polyethylene terephthalate is preferable in terms of cost, heat resistance, and dimensional stability.
  • the thickness of the temporary support is preferably about 15 to 200 ⁇ m, more preferably about 30 to 150 m. If the thickness of the temporary support is less than S15 m, there is a drawback in that a tin plate-like wrinkle is generated by heat during the lamination process. Conversely, when the thickness of the temporary support exceeds 200 m, it is disadvantageous in terms of cost.
  • the temporary support may be provided with a conductive layer described in JP-A-11-149008, if necessary.
  • thermoplastic resin layer between the support and the photosensitive light-shielding layer, or between the support and the intermediate layer.
  • thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb irregularities on the underlying surface (including irregularities caused by images already formed). Therefore, it is preferable to have a property that can be deformed according to the unevenness.
  • the resin contained in the thermoplastic resin layer includes a saponified product of ethylene and an acrylate copolymer, a saponified product of styrene and a (meth) acrylic ester copolymer, Kenya products such as (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, and (meth) acrylic acid ester copolymer of (meth) acrylic acid butyl and butyl acetate, etc. It is preferable that it is at least one selected from the above.
  • thermoplastic resin layer As the resin contained in the thermoplastic resin layer, the “Plastic Performance Manual” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968) A polymer that is soluble in an alkaline aqueous solution can also be used. Of these thermoplastic resins, those having a softening point of 80 ° C or less are preferred.
  • (meth) acrylic acid is a generic term for acrylic acid and methacrylic acid, and the same applies to derivatives thereof.
  • rosins include JP-B 54-34327, JP-B 55-38961, JP-B 58-12577, JP-B 54-25957, 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-A-60-159743, OLS3504254, JP-A-60-247638, JP-A-60-208748, JP-A-60-214354, JP-A-60-230135, JP-A-60- 258539, JP 61-169829, JP 61-213213, JP 63-147159, JP 63-213837, JP 63-266448, JP 64-5 5551 JP-A-64-55550, JP-A-2-191955, JP-A-2-199403, JP-A-2-199404, JP
  • the preferred embodiment is a force capable of selecting the medium force described in the above patent specification.
  • Examples thereof include styrene Z (meth) acrylic acid copolymers described in JP-A No. 1 and JP-A-5-241340.
  • plasticizers various polymers, supercooling substances, adhesion improvers or surfactants, mold release agents, etc. may be added to these organic polymer substances in order to adjust the adhesion force to the support.
  • preferred plasticizers include polypropylene glycol, Polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphosphate, biphenyl diphosphate, polyethylene glycol mono (meth) acrylate, polyethylene glycol (meta ) Atallate, Polypropylene glycol mono (meth) acrylate, Polypropylene glycol di (meth) acrylate, Addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, Organic diisocyanate and Polyethylene glycol Addition reaction product of bis (meth) acrylate, addition reaction product of organic diisocyanate and polypropylene glycol mono (me).
  • the amount of the plasticizer in the thermoplastic resin layer is generally 200% by mass or less, preferably 20 to L00% by mass with respect to the thermoplastic resin.
  • the thickness of the thermoplastic resin layer is preferably 1. or more. If the thickness of the thermoplastic resin is 1. or more, the unevenness of the base surface can be completely absorbed.
  • the upper limit is generally about 100 m or less, preferably about 50 ⁇ m or less, from the viewpoint of developability and production suitability.
  • the solvent for the thermoplastic resin layer can be used without particular limitation as long as it can dissolve the resin constituting the layer.
  • the solvent include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, i-propanol and the like.
  • an intermediate layer is provided between the temporary support and the photosensitive light-shielding layer.
  • the resin constituting the intermediate layer is preferably alkali-soluble.
  • fats include polybulal alcoholic, polypyrrole pyrrolidone, cellulose, acrylamide, polyethylene oxide, gelatin, butyl ether, polyamide, and These copolymers can be mentioned.
  • polybulal alcohol Preferable among these! / Is polybulal alcohol.
  • polybulu alcohol In particular, those having an acidity of 80% or more are preferred, and those having an acidity of 83 to 98% are more preferred.
  • this ratio is 1Z99 or less, problems such as deterioration of the surface condition of the intermediate layer and poor adhesion with the photosensitive resin layer coated thereon arise.
  • the weight ratio of both exceeds 75Z25, the oxygen barrier property of the intermediate layer decreases and the sensitivity decreases.
  • the thickness of the intermediate layer is preferably 0.1 force to 5 m, and more preferably 0.5 to 3 m. If the thickness is less than 0.1 m, the sensitivity may decrease due to a decrease in oxygen barrier properties. If the thickness exceeds 5 ⁇ m, the intermediate layer removal time during development may increase and the! / ⁇ ⁇ problem may occur. .
  • the coating solvent for the intermediate layer there is no particular limitation as long as the above resin is dissolved. A mixed solvent obtained by mixing the aforementioned water-miscible organic solvent with water is also preferable.
  • Preferable specific examples of the coating solvent for the intermediate layer include the following.
  • a solution of the coloring composition having the photosensitive property of the present invention is applied to a support, for example, spinner (spin method, slit and spin method), Ira 1 ⁇ "Higuchi 1 ⁇ ” La 1 ⁇ "Ko 1 ⁇ ” Ta ' ⁇ " ⁇ ⁇ . ⁇ ” Te, Saw' ⁇ "Ta ' ⁇ ” ⁇ Knife Ko 1 ⁇ "Ta' ⁇ ” ⁇ Wire 1 ⁇ " ⁇ 1 ⁇ " ⁇ 1 ⁇ ” ⁇ ' ⁇ "
  • thermoplastic resin layer it can be formed by applying and drying using an applicator such as Etastruder (FAS method, etc.).
  • FAS method Etastruder
  • the photosensitive transfer material of the present invention is provided with the photosensitive light-shielding layer formed from the coloring composition as described above, from now on, for a display device having a light-shielding layer that is a thin film and has a high optical density.
  • a light shielding layer can be produced.
  • the light-shielding layer for a display device is made using the colored composition or the photosensitive transfer material. Made.
  • the film thickness is about 0.1 to 2.0 m, preferably 0.1 to 0.9 m.
  • the optical density per film thickness ⁇ of the light shielding layer is 3.5 or more.
  • the light shielding layer for a display device is a layer in which silver tin alloy part-containing particles are further dispersed in a volume fraction of 0.05 to 0.7, and the color of the light transmitted through the C light source of the light shielding layer System chromaticity coordinates (X, y) and chromaticity coordinates (X
  • a method for producing a light-shielding layer for a display device using a photosensitive coloring composition is to apply a photosensitive coloring composition to a light-transmitting substrate to form a colored composition layer (application method is: This is a method for forming a light-shielding layer by exposure through a photomask for a light-shielding layer for a display device, followed by development by a conventional method, similar to the method for producing the photosensitive transfer material.
  • the colored composition does not have photosensitivity
  • the colored composition containing the silver-tin alloy part-containing particles of the present invention is applied to the light-transmitting substrate, the colored composition layer is formed.
  • a layer from a developable photosensitive resin composition is formed on the layer, and is exposed through a photomask for a light-shielding layer for a display device by a conventional method, and then developed and etched.
  • a light shielding layer can be formed.
  • 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 with the photosensitive transfer material.
  • the support is peeled off from the laminate of the photosensitive transfer material and the light-transmitting substrate, and then the layer is exposed through a photomask for a light-shielding layer for a display device and developed to develop a display device. This is a method of forming a light shielding layer.
  • the method for producing a light shielding layer for a display device of the present invention does not require a cumbersome process and is low in cost.
  • the color filter of the present invention comprises a colored layer on a light transmissive substrate and is different from each other.
  • the pixel group includes two or more pixel groups exhibiting colors, and the pixels constituting the pixel group are separated from each other by a display device light-shielding layer. It is produced using the colored composition or the photosensitive transfer material.
  • the number of pixel groups may be two, three, or four or more. For example, three hues are used: red (R), green (G), and blue (B). When three types of pixel groups of red, green, and blue are arranged, a mosaic type, a triangle type, and the like are preferable. When four or more types of pixel groups are arranged, any arrangement may be used.
  • 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.
  • a light-shielding layer for a display device is formed as described above, or first a display device is formed.
  • a light shielding layer may be formed, and then two or more pixel groups may be formed.
  • the color filter of the present invention includes the light shielding layer for a display device as described above, the display contrast is high and the flatness is excellent. Furthermore, since the thickness of the light shielding layer for the display device is small, the number of bubbles entrained when manufacturing the color filter pixel may be small.
  • One of the liquid crystal display elements of the present invention includes a pair of substrates, at least one of which is light transmissive, and a color filter, a liquid crystal layer, and a liquid crystal driving means (simple matrix driving method and active matrix driving) between the substrates.
  • a plurality of pixel groups as described above as the color filter, and each pixel constituting the pixel group is formed by the light shielding layer for a display device of the present invention.
  • the color filter is used after being separated. Since the color filter has high flatness, the liquid crystal display element including the color filter does not cause cell gap unevenness between the color filter and the substrate, and display defects such as color unevenness do not occur.
  • liquid crystal display element of the present invention a pair of substrates, at least one of which has light transmissivity, and a color filter, a liquid crystal layer, and a liquid crystal driving means are provided between the substrates.
  • the liquid crystal driving means has an active element (for example, TFT), and a light-shielding layer for a display device is formed between the active elements using the colored composition or photosensitive transfer material of the present invention. It is what has been.
  • the substrate with a light-shielding layer for a display device according to the present invention is obtained by providing the above-described light-shielding layer for a display device on a light-transmitting substrate.
  • Optical density is 3.5 or more
  • silver tin alloy part-containing particles are dispersed and contained in a volume fraction of 0.05 to 0.7
  • XYZ color system chromaticity coordinates of C light source transmitted light (X, y) and chromaticity coordinates (x, y) of the light source have a relationship of (xx) 2 + (yy) 2 ⁇ 0.01.
  • the substrate with a light-shielding layer for a display device of the present invention can be used for producing a color filter. Since a sufficient optical density can be achieved even with a thin film, the thickness of the light shielding layer for the display device can be reduced, and the number of bubbles entrained when producing the color filter pixel on the substrate with the light shielding layer for the display device is small. .
  • the liquid was further centrifuged! /, And the silver-tin alloy part-containing particles were precipitated again. Centrifugation was performed under the same conditions as described above. After centrifuging, the supernatant was discarded as described above so that the total liquid volume became 150 ml, 850 ml of pure water and 500 ml of acetone were added thereto, and the mixture was further stirred for 15 minutes to disperse the particles containing the silver-tin alloy part again. .
  • Centrifugation was again carried out in the same manner as above! /, After precipitation of the silver-tin alloy part-containing particles, the supernatant was discarded in the same manner as described above so that the liquid volume became 150 ml. Then, 1200 ml of acetone was added and the mixture was further stirred for 15 minutes to disperse the particles containing the silver-tin alloy part again. Again, centrifugation was performed. The centrifugation conditions at this time are the same as described above except that the time is extended to 90 minutes. After that, the supernatant was discarded so that the total liquid volume became 70 ml, and 30 ml of acetone was added thereto.
  • the numbers in Katsuko are the scattering angles of each ( ⁇ ) plane.
  • the number average particle size was 40 nm.
  • the number average particle size was measured by the method described above using a photograph obtained by transmission electron microscope [EM-2010 (manufactured by JEOL Ltd.)].
  • Dispersion of said silver-tin alloy part-containing particles (Dispersion A1)-50.00 parts 'Propylene glycol monomethyl ether acetate' ⁇ 28. 6 parts
  • the alkali-free glass substrate was cleaned with a UV cleaning device, brushed with a cleaning agent, and then ultrasonically cleaned with ultrapure water.
  • the substrate was heat-treated at 120 ° C for 3 minutes to stabilize the surface state.
  • the photosensitive layer coating solution of each example was applied with a glass substrate coater (manufactured by Hirata Machine Co., Ltd.) having a slit nozzle. Subsequently, part of the solvent was dried for 30 seconds with a VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) to eliminate the fluidity of the coating layer. Next, the coating solution for the protective layer was applied on this using a spin coater so that the dry film thickness was 1.5 m and dried at 100 ° C for 5 minutes to obtain a photosensitive resin layer K1.
  • the exposure mask surface with the substrate and mask (quartz exposure mask with image pattern) standing vertically
  • the distance between the photosensitive resin layer and the photosensitive resin layer was set to 200 m, and pattern exposure was performed with an exposure amount of 70 m j / cm 2 .
  • KOH containing a nonionic surfactant, trade name: CDK-1 and Fujifilm Elect Kokuku Materials Co., Ltd.
  • ultrapure water is sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, and ultrapure water is sprayed from both sides with a shower nozzle, and the attached developer and the photosensitive
  • the film thickness of the photosensitive layer was measured by the following method.
  • a photosensitive layer film was prepared by coating the glass substrate with the same coating amount as each photosensitive layer coating solution applied in the above (Preparation of photosensitive material), and using this ultra high pressure mercury lamp, the coating surface side force was also 70 miZcm 2 .
  • the photosensitive layer film was used as a measurement sample.
  • the film thickness of this measurement sample was measured using a stylus type surface roughness meter P-1 (manufactured by TENKOR).
  • Table 1 shows the film thickness of this measurement sample.
  • each measurement sample used in the film thickness measurement was used.
  • the optical density of each measurement sample was measured using a Macbeth densitometer (TD-904 manufactured by Macbeth) (OD).
  • OD Macbeth densitometer
  • the optical density of the glass substrate was measured by the same method (OD). Subtract OD from OD
  • V is the optical density of the film.
  • Table 1 shows the optical density of each measurement sample.
  • the measurement of the coating amount of the silver-tin alloy part-containing particles is carried out by using each measurement test used in the film thickness measurement.
  • the coating amount in each measurement sample was measured using a fluorescent X-ray apparatus 3370E (manufactured by Rigaku Corporation).
  • the volume fraction was calculated by the following formula. Table 1 shows the volume fraction of each measurement sample.
  • volume fraction of silver-tin alloy part-containing particles (coating amount Z of silver-tin alloy part-containing particles Z
  • grains was computed by the above-mentioned method.
  • R (R1), G (G1), and B (B1) pixel forming photosensitive transfer materials described in paragraphs 003 0 to 0036 of JP-A-2002-341127 are used on the substrate with a light shielding layer for the display device. Each color pixel was formed using the method described above.
  • the substrate with the light shielding layer for display device was heat-treated at 220 ° C. for 2 hours, and the change in hue of the light shielding layer for display device before and after the heat treatment was visually evaluated.
  • Example 1 The silver tin alloy part-containing particle dispersion (dispersion A1) used in Example 1 was changed to the silver fine particle dispersion (A2) obtained from the following, and the photosensitive layer coating liquid was changed to the following formulation: A light shielding layer for a display device was produced in the same manner as in Example 1 except for the change. The results are shown in Table 1.
  • Example 3 Instead of the silver-tin alloy part-containing particle dispersion A1 in which the volume fraction of the silver-tin alloy part-containing particles was kept constant (0.39) in Example 3 and the silver-tin alloy part-containing particles were dispersed, the average particle diameter was changed.
  • a light shielding layer for a display device was produced in the same manner as in Example 3 except that a carbon fine particle dispersion in which 30 nm carbon fine particles were dispersed was used. The results are shown in Table 1.
  • the light-shielding layer for the display device of the example has a high optical density even in a thin film of 1 ⁇ m or less, excellent in a black hue, and the hue is obtained by heating. In addition, even when a color filter was produced, it had excellent characteristics as a whole with little or no generation of bubbles, and met the practical level.
  • Example 3 except that the average particle size of the silver-tin alloy part-containing particles in the silver-tin alloy part-containing particle dispersion A1 used in Example 3 was 20 nm, 60 nm, 100 nm, 250 nm, and 500 nm, respectively.
  • a light shielding layer for a display device was formed. The results are shown in Table 2. The optical density, film thickness, black hue, heating change of hue, and bubbles were met with practical levels.
  • Examples 1 to 10 display device light-shielding layers were prepared in the same manner as in Examples 1 to 10 except that no protective layer was provided on the photosensitive layer.
  • a good light-shielding layer for a display device was obtained by exposure at a force of 500 mi / cm 2 , which was impossible to form a light-shielding layer for a display device by exposure at 70 miZcm 2 using an ultra-high pressure mercury lamp. Therefore, the exposure conditions were changed from 70 mjZcm 2 to 500 mj / cm 2 when preparing samples used for film thickness measurement, optical density measurement and volume fraction measurement. The results are shown in Table 3.
  • Comparative Examples 1 to 3 display device light-shielding layers were prepared in the same manner as Comparative Examples 1 to 3, except that no protective layer was provided on the photosensitive layer.
  • a shading layer for a display device could not be formed by an exposure of 70 miZcm 2 using an ultra-high pressure mercury lamp, and a shading layer for a display device was obtained by exposure at a force of 500 mi / cm 2 . Therefore, film thickness measurement, optical density measurement, and volume fraction measurement were also performed by changing from 70 mj / cm 2 to 500 mj / cm 2 exposure.
  • the display light-shielding layers produced from Comparative Examples 4 to 6 were not practical at the same level as Comparative Examples 1 to 3. The results are shown in Table 3.
  • a photosensitive transfer material was used to produce a light shielding layer for a display device.
  • the photosensitive transfer material is a biaxially stretched 75 m thick polyethylene terephthalate support using a slide coater to apply the following thermoplastic resin layer coating solution to a dry film thickness of ⁇ ⁇ at 100 ° C. And dried for 5 minutes. Next, an intermediate layer coating solution is applied onto this film so that the dry film thickness is 1. The coating solution is dried at 100 ° C for 5 minutes, and further a photosensitive layer coating solution is applied at 100 ° C for 5 minutes. Dried.
  • thermoplastic resin layer coating solution As the photosensitive layer coating solutions in Examples 21 to 30, photosensitive layer coating solutions having the same compositions corresponding to Examples 1 to 10, respectively, were used. In addition, as the intermediate layer coating solution formulation, a coating solution having the same composition as that of the protective layer coating solution of Example 1 was used. The composition of the thermoplastic resin layer coating solution is shown below.
  • Copolymer of styrene Z acrylic acid 70Z30 (copolymerization composition ratio (molar ratio)
  • a non-alkali glass substrate is cleaned with a rotating brush with nylon bristles while spraying a glass detergent solution adjusted to 25 ° C for 20 seconds with a shower.
  • the silane coupling solution N- ⁇ (amino Ethyl) ⁇ -aminopropyltrimethoxysilane 0.3 mass % Aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM603 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the glass substrate and the photosensitive transfer material are overlapped so that the glass substrate and the silver tin alloy part-containing particle-containing layer (ie, photosensitive layer) are in contact with each other, and a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) ) Were used to bond them together.
  • Lamination was performed on a substrate heated to 100 ° C at a rubber roller temperature of 130 ° C, a linear pressure of 100 NZcm, and a conveyance speed of 2.2 mZ. Thereafter, the polyethylene terephthalate support was peeled off.
  • the substrate and mask are used with a proximity-type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp With the quartz exposure mask standing vertically, the distance between the exposure mask surface and the thermoplastic resin layer was set to 200 m, and pattern exposure was performed at an exposure dose of 70 miZcm 2 .
  • a triethanolamine developer (containing 2.5% triethanolamine, containing a non-ionic surfactant, containing a polypropylene antifoaming agent, trade name: TPD1, Fuji Photo Film ( Shown and developed at 30 ° C for 50 seconds with a flat nozzle pressure of 0.04 MPa, and the thermoplastic resin layer and the intermediate layer were removed.
  • sodium carbonate developer (0.06 mol Z liters of sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, char-on surfactant, antifoaming agent, stabilizer, product Name: TCD1, Fuji Photo Film Co., Ltd. (diluted 5 times with pure water), shower developed at 29 ° C for 30 seconds and cone type nozzle pressure 0.15 MPa to develop the photosensitive resin layer I got a Patt für image.
  • the photosensitive layer coating solution used in Comparative Examples 1 to 3 was used instead of the photosensitive layer coating solution of Example 1 used as the photosensitive layer coating solution, respectively. Then, a light shielding layer for a display device was produced in the same manner as in Example 21. The results are shown in Table 4. The light-shielding layers for display devices obtained from Comparative Examples 7 to 9 were not at a practical level as in Comparative Examples 1 to 3.
  • the coloring composition satisfying the requirements of the present invention is excellent in black hue with high optical density even in a very thin layer close to 0.1 m, and is heated. Even when it is received, a light shielding layer for a display device having a small hue change can be obtained. In addition, since the thickness of the light shielding layer for a display device for obtaining a necessary optical density is small, the number of bubbles entrained when a color filter pixel is formed on a substrate with a light shielding layer for a display device is small.
  • the condition regarding the XYZ color system chromaticity coordinates of the C light source transmitted light can be achieved even if the average particle size and volume fraction are the same as in the present invention.
  • the hue of the light shielding layer for the display device is inferior, and the film thickness for achieving the same optical density is also increased.
  • RGB pixels were formed by the method described in Example 1 of WO2006-38731, and then a liquid crystal display device was produced.
  • the liquid crystal display device using the light-shielding layer for display device produced in the example was high in display quality without color unevenness compared with the liquid crystal display device using the light-shielding layer for display device produced in the comparative example.
  • the colored composition of the present invention is a light-shielding layer for a display device having a thin film, high light-shielding performance, low cost, and low black environmental impact (colorless and achromatic). Useful for production.
  • the light-shielding layer for a display device obtained according to the present invention has very little or no hue change due to heating, so it has excellent flatness, and bubbles may not be mixed in forming RGB pixels! / It is possible to produce a color filter with very little. Furthermore, this color filter is also used for manufacturing a liquid crystal display device.

Abstract

This invention provides a colored composition that contains metal particles having a silver tin alloy part, has an optical density, after film formation, of not less than 3.5 per μm of the dried film thickness, preferably has a volume fraction of the metal particles having a silver tin alloy part in the solid matter of 0.05 to 0.7 and can satisfy the requirement that, in a light shielding layer formed by coating the colored composition, XYZ colorimetric chromaticity coordinates (x, y) of C light source transmitted light and the chromaticity coordinates (x0, y0) of the above light source have a relationship represented by (x - x0)2 + (y - y0)2 ≤ 0.01.

Description

明 細 書  Specification
着色組成物及び感光性転写材料  Coloring composition and photosensitive transfer material
技術分野  Technical field
[0001] 本発明は、着色組成物及び感光性転写材料と、これらを用いる表示装置用遮光層 及びその製造方法、カラーフィルタ、液晶表示素子並びに表示装置用遮光層付き基 板に関する。  The present invention relates to a colored composition and a photosensitive transfer material, a light shielding layer for a display device using the same, a method for producing the same, a color filter, a liquid crystal display element, and a substrate with a light shielding layer for a display device.
背景技術  Background art
[0002] カラー液晶ディスプレイ等に用いられるカラーフィルタは、透明基板上に着色画素 層（R、 G、 B)が形成され、そして、 R、 G、 B (赤、緑、青）の各着色画素の間隙には、 表示コントラスト向上等の目的で、表示装置用遮光層が形成されている。特に薄膜ト 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素子にお!ヽ ては、薄膜トランジスターの光による電流リークに伴う画質の低下を防ぐためにも、表 示装置用遮光層には高!、遮光性が要求される。  [0002] Color filters used for color liquid crystal displays, etc. have a colored pixel layer (R, G, B) formed on a transparent substrate, and each colored pixel of R, G, B (red, green, blue) A light shielding layer for a display device is formed in the gap for the purpose of improving display contrast. In particular, in an active matrix liquid crystal display device using a thin film transistor (TFT), a light shielding layer for a display device is used to prevent deterioration in image quality due to current leakage due to light from the thin film transistor. Is required!
表示装置用遮光層の形成方法としては、例えば、クロム等の金属膜を遮光層とする 方法がある。この方法の場合には、金属薄膜を蒸着法やスパッタリング法により金属 膜を形成する。該金属薄膜の上にフォトレジストを塗布し、次いで表示装置用遮光層 の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する。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り遮 光層を形成する (例えば非特許文献 1を参照)。  As a method for forming a light shielding layer for a display device, for example, there is a method in which a metal film such as chromium is used as a light shielding layer. In this method, a metal thin film is formed by vapor deposition or sputtering. A photoresist is applied on the metal thin film, and then the photoresist layer is exposed and developed using a photomask having a pattern of a light shielding layer for a display device. Thereafter, the exposed metal thin film is etched, and finally the resist layer on the metal thin film is removed to form a light shielding layer (see, for example, Non-Patent Document 1).
この方法は、金属薄膜を用いるため、膜厚が薄くても高い遮光効果が得られる反面 、蒸着法やスパッタリング法という真空成膜工程やエッチング工程が必要となり、コス トが高くなるとともに環境に対する負荷も無視できないという問題がある。また、金属 膜であるため反射率が高ぐ強 、外光の下では表示コントラストが低 、と 、う問題もあ る。この対策としては低反射クロム膜 (金属クロムと酸ィ匕クロムの 2層力もなるもの等）を 用いる。しかし、その対策法は、更にコストアップとなる問題を伴う。  Since this method uses a metal thin film, a high light-shielding effect can be obtained even if the film thickness is thin. However, a vacuum film forming process or an etching process such as a vapor deposition method or a sputtering method is required, resulting in high costs and an environmental load. There is a problem that cannot be ignored. In addition, the metal film has a problem that the reflectivity is high and the display contrast is low under external light. As a countermeasure, use a low-reflective chromium film (such as one that has a two-layer strength of metallic chromium and acid chromium). However, the countermeasure method involves a problem that further increases the cost.
[0003] また、表示装置用遮光層の他の形成方法としては、遮光性顔料、例えばカーボン ブラックを含有する感光性榭脂組成物を用いる方法も知られている。この方法は、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 感光性榭脂組成物を塗布し、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表示装置用遮光層形成方法である（例えば特許文献 1を参照)。 [0003] As another method for forming a light shielding layer for a display device, a method using a photosensitive resin composition containing a light shielding pigment such as carbon black is also known. This method is an example For example, after forming R, G, B pixels on a transparent substrate, a photosensitive resin composition containing carbon black is applied on the pixels, and the entire surface from the R, G, B pixel non-formation side of the transparent substrate is applied. This is a method for forming a light-shielding layer for a display device of a self-alignment type that performs exposure (see, for example, Patent Document 1).
この方法は、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、表 示装置用遮光層と R、 G、 B画素との重なり（段差）が生じ、カラーフィルタの平坦性が 悪くなつて液晶表示素子のセルギャップムラが発生し、色ムラ等の表示不良につなが る。  Although this method has a lower manufacturing cost than the method by etching the metal film, there is a problem that the film thickness is increased in order to obtain a sufficient light shielding property. As a result, the light-shielding layer for the display device and the R, G, B pixels overlap (steps), the flatness of the color filter deteriorates, the cell gap unevenness of the liquid crystal display element occurs, and the display of color unevenness etc. It leads to failure.
また、最初に、基板にカーボンブラックを含有する感光性榭脂組成物を用いて表示 装置用遮光層を作製し、その後に RGB画素を形成すると、表示装置用遮光層の膜 厚が厚くなる。これに起因して、 RGB画素形成の際、気泡発生等の欠陥が生じること がある。  Further, when a light shielding layer for a display device is first prepared using a photosensitive resin composition containing carbon black on a substrate and then RGB pixels are formed, the thickness of the light shielding layer for the display device is increased. As a result, defects such as bubble generation may occur when forming RGB pixels.
また、カーボンブラックを用いた表示装置用遮光層が黒の色相において必ずしも良 好であるとはいい難い。  In addition, it is difficult to say that a light-shielding layer for a display device using carbon black is necessarily good in a black hue.
一方、遮光用の金属粒子を内部に均一分散した表示装置用遮光層を作製する方 法が知られている (特許文献 2参照)。この方法では、まず透明基板上に親水性榭脂 を含有する感光性レジスト層を形成する。次いで、表示装置用遮光層のパターンを 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する。その後 、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する。乾燥後、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 /z m の遮光用の金属粒子がその内部に均一に分散された表示装置用遮光層が得られる 。前記金属粒子としてはニッケル、コバルト、鉄、銅、クロムが列挙され、具体例として は唯一ニッケルが示されて 、る。  On the other hand, a method for producing a light shielding layer for a display device in which light shielding metal particles are uniformly dispersed therein is known (see Patent Document 2). In this method, first, a photosensitive resist layer containing a hydrophilic resin is formed on a transparent substrate. Next, exposure and development are performed through a photomask having a pattern of a light shielding layer for a display device to form a relief on the transparent substrate. Thereafter, the transparent substrate is brought into contact with an aqueous solution of a metal compound serving as a catalyst for electroless plating, and the metal compound is contained in the relief and dried. After drying, heat treatment is performed, and then the relief metal on the transparent substrate is brought into contact with the electroless plating solution to uniformly disperse the light-shielding metal particles having a particle size of 0.01 to 0.05 / zm. The obtained light shielding layer for a display device is obtained. As the metal particles, nickel, cobalt, iron, copper, and chromium are listed, and nickel is shown as a specific example.
しカゝしながら、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い。そのため、 低コストでの表示装置用遮光層作製はあまり期待できない。 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） However, in this method, there are many troublesome processing steps for handling water, such as relief formation including an exposure development step-application of electroless plating catalyst, heat treatment, electroless plating. Therefore, the production of a light shielding layer for a display device at a low cost cannot be expected so much. Non-Patent Document 1: Kyoritsu Shuppan Co., Ltd. “Color TFT Liquid Crystal Display” pp. 218-220 (10 April, 1997)
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
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
[0005] 本発明は前記のごとき問題点に鑑みてなされたものであり、薄膜で遮光性能が高く 、低コストで作製することができ、環境への影響が少なぐ黒色 (色味がつかず無彩色 )の表示装置用遮光層を作製できる着色組成物及び感光性転写材料を提供する。 また、本発明は、前記着色組成物又は感光性転写材料を用いる表示装置用遮光層 及びその製造方法、前記表示装置用遮光層が設けられたカラーフィルタ及び液晶 表示素子を提供する。さらに、本発明は、前記のごとき表示装置用遮光層が形成さ れた表示装置用遮光層付き基板を提供する。 [0005] The present invention has been made in view of the above-described problems, and is a thin film that has a high light-shielding performance, can be manufactured at low cost, and has a low environmental impact. The present invention provides a coloring composition and a photosensitive transfer material capable of producing a light-shielding layer for display devices of achromatic color). In addition, the present invention provides a light shielding layer for a display device using the colored composition or the photosensitive transfer material, a method for producing the same, a color filter provided with the light shielding layer for a display device, and a liquid crystal display element. Furthermore, the present invention provides a substrate with a light shielding layer for a display device, on which the light shielding layer for a display device as described above is formed.
課題を解決するための手段  Means for solving the problem
[0006] 前記課題は、以下の着色組成物及び感光性転写材料、表示装置用遮光層及びそ の製造方法、カラーフィルタ、液晶表示素子並びに表示装置用遮光層付き基板を提 供することにより解決される。 The above-mentioned problems are solved by providing the following coloring composition and photosensitive transfer material, a light shielding layer for a display device and a method for producing the same, a color filter, a liquid crystal display element, and a substrate with a light shielding layer for a display device. The
(1)銀錫合金部を有する金属粒子を含有し、膜形成後の光学濃度が、乾燥膜厚 l ;z m当たり 3. 5以上であることを特徴とする着色組成物。  (1) A coloring composition comprising metal particles having a silver-tin alloy part and having an optical density after film formation of 3.5 or more per dry film thickness l; z m.
(2)前記銀錫合金部を有する金属粒子の固形分中の体積分率が 0. 05〜0. 7であ り、かつ着色組成物を塗布して形成される遮光層において、 C光源透過光の XYZ表 色系色度座標 (X, y)と、前記光源の色度座標 (X , y )  (2) In a light shielding layer formed by applying a colored composition, the volume fraction in the solid content of the metal particles having the silver-tin alloy part is 0.05 to 0.7, and transmitting C light source XYZ table of light color coordinate (X, y) and chromaticity coordinate (X, y) of the light source
0 0と力 （X— X ) 2 + (y-y ) 2≤0 0 0 and force (X— X) 2 + (yy) 2 ≤0
0 0 0 0
. 01の関係を有することを特徴とする前記（1)に記載の着色組成物。 The colored composition as described in (1) above, which has a relationship of 01.
(3)前記銀錫合金部を有する金属粒子の平均粒径が 500nm以下であることを特徴 とする前記（1)または（2)に記載の着色組成物。  (3) The colored composition as described in (1) or (2) above, wherein the metal particles having the silver-tin alloy part have an average particle size of 500 nm or less.
(4)前記着色組成物が感光性を有することを特徴とする前記（ 1)な!ヽし (3)の ヽずれ 力 1に記載の着色組成物。  (4) The colored composition according to (1), wherein the colored composition has photosensitivity, (1)
[0007] (5)支持体と、その支持体上に少なくとも感光性遮光層を設けており、該感光性遮光 層が銀錫合金部を有する金属粒子を含み、感光性遮光層の光学濃度が、乾燥膜厚(5) A support, and at least a photosensitive light-shielding layer is provided on the support, and the photosensitive light-shielding layer is provided. The layer contains metal particles having a silver-tin alloy part, and the optical density of the photosensitive light-shielding layer is a dry film thickness.
1 μ m当たり 3. 5以上であり、感光性遮光層中の銀錫合金部を有する金属粒子の体 積分率が 0. 05-0. 7であり、かつ遮光層の C光源透過光の XYZ表色系色度座標（ X, y)と、前記光源の色度座標 (X , y )とが、 (x - x ) 2 + (y-y ) 2≤0. 01の関係を The volume fraction of metal particles having a silver-tin alloy part in the photosensitive light-shielding layer is 3.5 or more per 1 μm, and 0.05 to 0.7. The color system chromaticity coordinates (X, y) and the chromaticity coordinates (X, y) of the light source satisfy the relationship of (x-x) 2 + (yy) 2 ≤0.01
0 0 0 0  0 0 0 0
有することを特徴とする感光性転写材料。  A photosensitive transfer material comprising:
[0008] (6)前記（1)ないし (4)のいずれ力 1に記載の着色組成物又は前記（5)に記載の感 光性転写材料を用いて作製される表示装置用遮光層。  [0008] (6) A light-shielding layer for a display device produced using the colored composition according to any one of the above (1) to (4) or the photosensitive transfer material according to (5).
[0009] (7)光透過性基板と、その基板上に、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、該画素群を構成する各画素は互いに表示装置用遮光層により 離画され、該表示装置用遮光層が前記（6)に記載の表示装置用遮光層であることを 特徴とするカラーフィルタ。 [0009] (7) A light-transmitting substrate and two or more pixel groups that are formed of a colored layer and have different colors on the substrate, and each pixel constituting the pixel group is for a display device A color filter separated by a light shielding layer, wherein the light shielding layer for a display device is the light shielding layer for a display device according to (6).
[0010] (8)少なくとも 1つが光透過性を有する 1対の基板と、その基板の間に、カラーフィル タ、液晶層および液晶駆動手段を少なくとも備え、前記カラーフィルタが、前記（7)に 記載のカラーフィルタであることを特徴とする液晶表示素子。 [8] (8) A pair of substrates, at least one of which is light transmissive, and at least a color filter, a liquid crystal layer, and a liquid crystal driving unit between the substrates, and the color filter according to (7) A liquid crystal display element comprising the color filter described above.
(9)少なくとも 1つが光透過性を有する 1対の基板と、その基板の間に、カラーフィル タ、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 子を有し、各アクティブ素子の間に前記（6)に記載の表示装置用遮光層が形成され て 、ることを特徴とする液晶表示素子。  (9) A pair of substrates, at least one of which is light transmissive, and at least a color filter, a liquid crystal layer, and a liquid crystal driving unit between the substrates, wherein the liquid crystal driving unit has an active element, A liquid crystal display element, wherein the light shielding layer for a display device according to (6) is formed between active elements.
[0011] (10)光透過性基板と、その基板の上に、前記（1)ないし (4)のいずれ力 1に記載の 着色組成物の層を形成する工程、及び [10] (10) a step of forming a light-transmitting substrate and a layer of the colored composition according to any one of (1) to (4) above on the substrate; and
前記着色組成物の層を表示装置用遮光層用フォトマスクを介して露光した後現像す る工程を有する表示装置用遮光層の製造方法。  A method for producing a light-shielding layer for a display device, comprising a step of developing the colored composition layer after exposure through a photomask for the light-shielding layer for a display device.
(11)光透過性基板の上に、支持体に少なくとも感光性遮光層を設けた前記 (5)に 記載の感光性転写材料を、前記感光性遮光層が接するように積層する工程、前記 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する工程、及び表示 装置用遮光層用フォトマスクを介して前記感光性遮光層を露光した後現像する工程 を有する表示装置用遮光層の製造方法。  (11) A step of laminating the photosensitive transfer material according to (5) above, wherein at least a photosensitive light-shielding layer is provided on a support on a light-transmitting substrate, so that the photosensitive light-shielding layer is in contact with the photosensitive material. Light-shielding for a display device, comprising: a step of peeling the support from the laminate of the photosensitive transfer material and the light-transmitting substrate; and a step of developing after exposing the photosensitive light-shielding layer through a photomask for the light-shielding layer for the display device Layer manufacturing method.
[0012] (12)光透過性基板及び該基板の上に表示装置用遮光層を有し、該表示装置用遮 光層中に銀錫合金部を有する金属粒子が体積分率 0. 05〜0. 7で分散されており、 表示装置用遮光層の光学濃度が、乾燥膜厚 1 m当たり 3. 5以上であり、かつ、表 示装置用遮光層において、 C光源透過光の XYZ表色系色度座標 (X, y)と、前記光 源の色度座標 (X , y )とが、 (x - x ) 2+ (y-y ) 2≤0. 01の関係を有することを特徴 [0012] (12) A light-transmitting substrate and a display device light-shielding layer on the substrate, wherein the display device light-shielding layer is provided. Metal particles having a silver-tin alloy part in the optical layer are dispersed at a volume fraction of 0.05 to 0.7, and the optical density of the light shielding layer for display device is 3.5 or more per 1 m of dry film thickness. In addition, in the light shielding layer for the display device, the XYZ color system chromaticity coordinates (X, y) of the C light source transmitted light and the chromaticity coordinates (X, y) of the light source are (x-x ) 2 + (yy) 2 ≤0.01
0 0 0 0  0 0 0 0
とする表示装置用遮光層付き基板。  A substrate with a light shielding layer for a display device.
発明の効果  The invention's effect
[0013] 本発明の着色組成物を用いることにより、薄膜で遮光性能が高ぐ低コストで、環境 への影響が少なく、黒色 (色味がつかず無彩色)の色相に優れた表示装置用遮光層 が得られる。また、本発明により得られる表示装置用遮光層は、加熱による色相変化 もないか非常に少ない。  [0013] By using the colored composition of the present invention, a thin film with high light-shielding performance, low cost, less environmental impact, and excellent in black (achromatic and achromatic) hue. A light shielding layer is obtained. Further, the light-shielding layer for a display device obtained by the present invention has no or very little hue change due to heating.
また、この表示装置用遮光層を用いたカラーフィルタは平坦性に優れ、 RGB画素 を形成する際に気泡が混入することがないかあるいは非常に少ない。さらに、この力 ラーフィルタを組み込んだ液晶表示装置は、カラーフィルタと基板の間にセルギヤッ プムラが発生せず色ムラ等の表示不良が発生しな!、。  In addition, the color filter using the light-shielding layer for the display device has excellent flatness, and bubbles are not mixed or very little when forming RGB pixels. Furthermore, liquid crystal display devices incorporating this power color filter do not cause cell gap unevenness between the color filter and the substrate, and display defects such as color unevenness do not occur!
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0014] [着色組成物] [0014] [Coloring composition]
本発明の着色組成物は、銀錫合金部を有する金属粒子 (以下、単に「銀錫合金部 含有粒子」とよぶ)を含み、該着色組成物を塗布して形成される層の光学濃度が、乾 燥膜厚 1 m当たり 3. 5以上であることを特徴とする。このような着色組成物は、固形 分中の銀錫合金部含有粒子の体積分率が 0. 05〜0. 7であり、かつ、前記着色組 成物を塗布して形成される遮光層にお ヽて、 C光源透過光の XYZ表色系色度座標 ( X, y)と、前記光源の色度座標 (X , y )とが、 (x - x ) 2+ (y-y ) 2≤0. 01の関係を The colored composition of the present invention comprises metal particles having a silver-tin alloy part (hereinafter simply referred to as “silver-tin alloy part-containing particles”), and the optical density of the layer formed by applying the colored composition is The dry film thickness is 3.5 or more per 1 m. Such a colored composition has a volume fraction of silver-tin alloy part-containing particles in the solid content of 0.05 to 0.7, and is applied to the light-shielding layer formed by applying the colored composition. Therefore, the XYZ color system chromaticity coordinates (X, y) of the C light source transmitted light and the chromaticity coordinates (X, y) of the light source are (x-x) 2 + (yy) 2 ≤0 01 relationship
0 0 0 0  0 0 0 0
有するものが好ましい。  What has is preferable.
[0015] 前記「固形分中の銀錫合金部含有粒子の体積分率」は、前記着色組成物を塗布 乾燥して得られる遮光層（前記着色組成物が感光性を有する場合は、着色組成物を 塗布し露光硬化した後の層）に含まれる銀錫合金部含有粒子の体積分率を意味す る。また、前記体積分率は、表示装置用遮光層中に含まれる銀錫合金部含有粒子 の体積分率をも意味する (着色組成物には、銀錫合金部含有粒子以外にバインダー であるポリマーやモノマー、重合開始剤、その他の任意成分が含まれているが、遮光 層の形成中に、これらの成分の一部は、塗布、加熱乾燥等の工程で消失する場合が あるので、このような定義を行った)。 [0015] The "volume fraction of the silver-tin alloy part-containing particles in the solid content" is a light-shielding layer obtained by applying and drying the colored composition (if the colored composition is photosensitive, the colored composition This means the volume fraction of the silver-tin alloy part-containing particles contained in the layer after the product is applied and exposed and cured. The volume fraction also means the volume fraction of the silver-tin alloy part-containing particles contained in the light-shielding layer for a display device (the colored composition contains a binder in addition to the silver-tin alloy part-containing particles). Polymers, monomers, polymerization initiators, and other optional components are included, but some of these components may be lost during coating, heat drying, etc. during the formation of the light-shielding layer. And made such a definition).
ここで、体積分率の測定は、以下の式に基づいて行われる。  Here, the volume fraction is measured based on the following equation.
銀錫合金部含有粒子の体積分率 = (銀錫合金部含有粒子の塗設量 Z  Volume fraction of silver-tin alloy part-containing particles = (coating amount Z of silver-tin alloy part-containing particles Z
銀錫合金部含有粒子の密度) Z膜厚  (Density of silver-tin alloy part-containing particles) Z film thickness
但し、塗設量は gZm2で表し、密度は gZcm3で表し、膜厚 (遮光層又は表示装置 用遮光層の膜厚）は mで表す。前記式において、（銀錫合金部含有粒子の塗設量 Z銀錫合金部含有粒子の密度）は、銀錫合金部含有粒子を均一な膜として塗設した 場合の厚みを πι単位で表した値と一致する。また、銀錫合金部含有粒子の塗設量 は蛍光 X線装置を用いて測定される。 However, the coating amount is expressed in gZm 2 , the density is expressed in gZcm 3 , and the film thickness (film thickness of the light shielding layer or the light shielding layer for display device) is expressed in m. In the above formula, (the coating amount of the silver-tin alloy part-containing particles Z the density of the silver-tin alloy part-containing particles) represents the thickness when the silver-tin alloy part-containing particles are coated as a uniform film in units of πι. Matches the value. The coating amount of the silver-tin alloy part-containing particles is measured using a fluorescent X-ray apparatus.
[0016] 尚、銀錫合金部含有粒子の密度は、以下によって算出することができる。 [0016] The density of the silver-tin alloy part-containing particles can be calculated as follows.
まず、銀錫合金部含有粒子溶液を蒸発皿等に移して自然乾燥した後、乾燥された 銀錫合金部含有粒子の皮膜を剥がし取り、細カゝく粉砕し測定用粉末試料を調製する 。更に、デシケーター中で 1時間真空乾燥を行なった後、精秤したガラス製の比重計 (Wig)に乾燥した試料を入れ、精秤することにより試料の質量 (W2g)を算出し、比 重計の空隙部分に比重が既知 (Dig)の液体を試料全体が完全に埋没するまで添 加し、超音波を用いて脱泡を行なう。粉末試料が完全に沈降した後、さらに上記液体 を追加して比重計に液体を十分充填し、温度を 25°Cに調整し、比重計の蓋をして全 体の質量 (W3g)を精秤する。これにより上記液体の質量を算出し、これを比重を用 いて体積に変換し、下記（1)式を用いて密度を求めることができる。尚、この時の比 重計の容量を Vlmlとする。  First, after the silver-tin alloy part-containing particle solution is transferred to an evaporating dish or the like and dried naturally, the dried film of silver-tin alloy part-containing particles is peeled off and finely pulverized to prepare a powder sample for measurement. Furthermore, after vacuum drying for 1 hour in a desiccator, the dried sample is placed in a precisely weighed glass hydrometer (Wig) and weighed accurately to calculate the mass (W2g) of the sample. Add a liquid with a known specific gravity (Dig) into the gap until the entire sample is completely buried, and defoam using ultrasonic waves. After the powder sample has completely settled, add the above liquid and fill the hydrometer with sufficient liquid, adjust the temperature to 25 ° C, cover the hydrometer, and adjust the total mass (W3g). Weigh. Thus, the mass of the liquid can be calculated, converted into a volume using specific gravity, and the density can be obtained using the following formula (1). The capacity of the hydrometer is Vlml.
銀錫合金部含有粒子の密度 =W2Z{V1— (W3-W1 -W2) ZD1) Density of silver-tin alloy part-containing particles = W2Z {V1— (W3-W1 -W2) ZD1)
•••(1)式 •••(1 set
[0017] 遮光層の C光源透過光の XYZ表色系色度座標 (X, y)は、分光光度計又は顕微分 光光度計でスペクトル測定を行い、このスペクトルカゝら C光源における原刺激値 X、 Y 、 Zを計算することにより色度座標が求められる。また、本発明において用いた C光源 の XYZ表色系色度座標（X , y ) ίま、 X力 SO. 3100、 y力0. 3164である。 市販の分光光度計としては、大塚電子 (株)製の MCPD— 1000を、顕微分光光度計 としては、 OLYMPUS製の OSP—SP100及び OSP—SP200等を用いることができる。 [0017] The XYZ color system chromaticity coordinates (X, y) of the light transmitted through the light source C of the light shielding layer are measured with a spectrophotometer or a microspectrophotometer. By calculating the values X, Y and Z, the chromaticity coordinates are obtained. Further, the XYZ color system chromaticity coordinates (X, y) of the C light source used in the present invention, X force SO. 3100, and y force 0.3164. MCPD-1000 manufactured by Otsuka Electronics Co., Ltd. can be used as a commercially available spectrophotometer, and OSP-SP100 and OSP-SP200 manufactured by OLYMPUS can be used as microspectrophotometers.
[0018] 本発明の着色組成物において、前記銀錫合金部含有粒子の平均粒径及び体積 分率が本発明の条件を満たすと、該組成物から形成される遮光層において、 C光源 透過光の XYZ表色系色度座標 (X, y)と、前記光源の色度座標 (X , y )とが、（x— x [0018] In the colored composition of the present invention, when the average particle size and volume fraction of the silver-tin alloy part-containing particles satisfy the conditions of the present invention, in the light shielding layer formed from the composition, XYZ color system chromaticity coordinates (X, y) of the light source and chromaticity coordinates (X, y) of the light source are (x—x
0 0 0 0 0 0
) 2 + (y-y ) 2≤0. 01の関係を満たす。 ) 2 + (yy) 2 ≤0.01 is satisfied.
0  0
前記 c光源は液晶表示装置に用いるノ ックライト光源と近い特性を有するもので、 前記条件を満たすことにより表示装置用遮光層を透過する光の影響を受けて黒色部 の色相が悪ィ匕することがないことを示している。前記の条件は、透過光の色度座標 (X , y)が C光源の色度座標 (X , y )に近いことを示す。しかし、ある光の色度座標 (X, y  The c light source has characteristics close to those of a knock light source used in a liquid crystal display device, and the hue of the black portion is deteriorated by the influence of light transmitted through the light shielding layer for the display device when the above conditions are satisfied. It shows that there is no. The above condition indicates that the chromaticity coordinate (X, y) of the transmitted light is close to the chromaticity coordinate (X, y) of the C light source. However, the chromaticity coordinates of some light (X, y
0 0  0 0
)がじ光源の色度座標 (X , y )に近いということは、その光が無彩色に近いことを意味  ) Close to the chromaticity coordinates (X, y) of the light source means that the light is close to an achromatic color
0 0  0 0
する。そのため、前記条件を満たすことは黒に他の色味が加わらず黒の色相が優れ ていることを示す。また、液晶表示装置を用いる場所の環境光 (反射光）が黒色部の 色相に及ぼす影響は透過光と同様に考え得るので、反射光により色相が悪化するこ ともない。  To do. Therefore, satisfying the above condition indicates that the black hue is excellent without adding any other color to black. In addition, since the influence of ambient light (reflected light) at the place where the liquid crystal display device is used on the hue of the black part can be considered in the same manner as the transmitted light, the hue is not deteriorated by the reflected light.
[0019] 銀錫合金部を有する金属粒子  [0019] Metal particles having a silver-tin alloy part
本発明に係る銀錫合金部を有する金属粒子 (銀錫合金部含有粒子)は、各粒子が 、銀錫合金力もなるもの、銀錫合金部分とその他の金属部分力もなるもの、及び銀錫 合金部分と他の合金部分からなるものを含む。  The metal particles having a silver-tin alloy part according to the present invention (silver-tin alloy part-containing particles) each have a silver-tin alloy force, a silver-tin alloy part and another metal part force, and a silver-tin alloy. Including those composed of parts and other alloy parts.
[0020] 本発明において、金属の定義については、岩波理化学辞典 第 4版（1987年、岩 波書店発行）に記載されている通りである。本発明における銀錫合金は、銀と錫を原 子レベルで混合したもので、固溶体、共晶、化合物、金属間化合物などが含まれる。 なお、合金については、例えば、岩波理化学辞典 第 4版（1987年、岩波書店発行 )に記載されている。  [0020] In the present invention, the definition of metal is as described in Iwanami Physical and Chemical Dictionary, 4th edition (published by Iwanami Shoten in 1987). The silver-tin alloy in the present invention is a mixture of silver and tin at the atomic level, and includes solid solutions, eutectic crystals, compounds, intermetallic compounds, and the like. Alloys are described in, for example, Iwanami Physical and Chemical Dictionary, 4th edition (published by Iwanami Shoten in 1987).
[0021] 本発明に係る銀錫合金部含有粒子は、少なくとも一部が銀錫合金で構成されてい る。この構成は、例えば、（株）日立製作所製の HD— 2300とノーラン (Noran)社製 の EDS (エネルギー分散型 X線分析装置）とを用いて確認することができる。その測 定条件は、加速電圧 200kVによる各々の粒子の中心 15nm口エリアのスペクトルで ある。 [0021] The silver-tin alloy part-containing particles according to the present invention are at least partially composed of a silver-tin alloy. This configuration can be confirmed using, for example, HD-2300 manufactured by Hitachi, Ltd. and EDS (energy dispersive X-ray analyzer) manufactured by Noran. The measurement conditions are the spectrum of the center 15nm mouth area of each particle with an acceleration voltage of 200kV. is there.
[0022] 銀錫合金部含有粒子は、黒濃度が高ぐ少量であるいは薄膜で優れた遮光性能を 発現し得ると共に、高い熱安定性を有する。従って、黒濃度を損なうことなく高温 (例 えば 200°C以上)での熱処理が可能であり、安定的に高度の遮光性を確保すること ができる。例えば、高度の遮光性が要求され、一般にベータ処理が施されるカラーフ ィルタ用の遮光膜 (いわゆるブラックマトリクス)などに好適である。  [0022] The silver-tin alloy part-containing particles can exhibit excellent light-shielding performance with a small amount of black density or a thin film, and have high thermal stability. Therefore, heat treatment can be performed at a high temperature (eg, 200 ° C. or more) without impairing the black density, and a high degree of light shielding can be secured stably. For example, it is suitable for a light shielding film (so-called black matrix) for a color filter which requires a high light shielding property and is generally subjected to a beta treatment.
[0023] 本発明に係る銀錫合金部含有粒子は、銀 (Ag)の割合を 30〜80モル％として Ag と錫（Sn)とを複合化 (例えば合金化）して得られるものである。 Agの割合を特に前記 範囲とすることで、高温域での熱安定性が高ぐ光の反射率を抑えた高い黒濃度を 得ることができる。  [0023] The silver-tin alloy part-containing particles according to the present invention are obtained by combining (for example, alloying) Ag and tin (Sn) at a silver (Ag) ratio of 30 to 80 mol%. . By setting the Ag ratio in the above-described range, a high black density can be obtained while suppressing the reflectance of light, which has high thermal stability at high temperatures.
[0024] 換言すれば、 Agの割合が 30モル％未満であると、融点が低くなり熱変化しやすく 熱安定性が低下する。また、 Agの割合が 80モル％を超えると、光の反射率が高くな る。中でも、 Agの割合は、好ましくは 40〜75モル0 /0であり、最も好ましくは 50〜75モ ル％である。 In other words, if the Ag ratio is less than 30 mol%, the melting point becomes low and heat changes easily, and the thermal stability decreases. On the other hand, when the Ag ratio exceeds 80 mol%, the light reflectance increases. Among them, the proportion of Ag is preferably 40 to 75 mole 0/0, and most preferably 50 to 75 molar%.
特に、 Agの割合が 75モル％である粒子、すなわち AgSn合金粒子は作製が容易 であり、得られた粒子も安定で好ましい。  In particular, particles with an Ag ratio of 75 mol%, that is, AgSn alloy particles are easy to produce, and the resulting particles are also stable and preferable.
[0025] 本発明の着色組成物は、銀錫合金部含有粒子を一種単独で含有してもよぐ Agの 割合が前記範囲内で異なる二種以上の銀錫合金部含有粒子を併用して構成するよ うにしてもよい。 [0025] The colored composition of the present invention may contain one kind of silver-tin alloy part-containing particles. Two or more kinds of silver-tin alloy part-containing particles having different Ag ratios within the above range are used in combination. It may be configured.
[0026] 本発明に係る銀錫合金部含有粒子の製造は、坩堝などの中で加熱、溶融混合し て形成する等の一般的方法で合金化等により形成することが可能である。 Agの融点 は 900°C付近で、 Snの融点は 200°C付近である。従って、両者の融点に大きな差が あるうえ、複合化 (例えば合金化)後の微粒子化工程が余分に必要になることから、 粒子還元法によるのが好ましい。例えば、 Ag化合物と Snィ匕合物とを混合し、これを 還元する。即ち、金属 Agと金属 Snを同時に接近した位置で析出させ、複合化 (例え ば合金化）と微粒子化とを同時に達成する方法である。 Agは還元されやすぐ Snより も先に析出する傾向にあるため、 Ag及び Z又は Snを錯塩にすることにより析出タイミ ングをコントロールすることが好適である。 [0027] 前記 Ag化合物としては、硝酸銀 (AgNO )、酢酸銀 (Ag (CH COO) )、過塩素酸 [0026] The silver-tin alloy part-containing particles according to the present invention can be produced by alloying or the like by a general method such as heating, melting and mixing in a crucible or the like. The melting point of Ag is around 900 ° C, and the melting point of Sn is around 200 ° C. Therefore, it is preferable to use the particle reduction method because there is a large difference between the melting points of the two and an extra step of micronization after compounding (for example, alloying) is required. For example, an Ag compound and a Sn compound are mixed and reduced. In other words, it is a method in which metal Ag and metal Sn are simultaneously deposited at close positions to simultaneously achieve compounding (for example, alloying) and micronization. Since Ag tends to be precipitated immediately before Sn as soon as it is reduced, it is preferable to control the precipitation timing by making Ag and Z or Sn into a complex salt. [0027] Examples of the Ag compound include silver nitrate (AgNO), silver acetate (Ag (CH COO)), and perchloric acid.
3 3  3 3
銀 (AgCIO ·Η Ο)等が好適に挙げられる。中でも特に、酢酸銀が好ましい。  Silver (AgCIO · Η Ο) and the like are preferable. Of these, silver acetate is particularly preferred.
4 2  4 2
[0028] 前記 Sn化合物としては、塩化第一錫 (SnCl )、塩化第二錫 (SnCl )、酢酸第一錫  [0028] Examples of the Sn compound include stannous chloride (SnCl), stannic chloride (SnCl), and stannous acetate.
2 4  twenty four
(Sn(CH COO) )等が好適に挙げられる。中でも特に、酢酸第一錫が好ましい。  (Sn (CH 3 COO) 2) and the like are preferred. Of these, stannous acetate is particularly preferable.
3 2  3 2
[0029] 還元方法は、還元剤を用いる方法、電解により還元する方法等を挙げることができ る。中でも、還元剤を用いた前者による方法が、微細な粒子が得られる点で好ましい 。前記還元剤としては、ハイドロキノン、カテコール、パラアミノフエノール、ノ ラフエ- レンジァミン、ヒドロキシアセトンなどが挙げられる。中でも、揮発しやすぐ表示装置 に悪影響を与えにくい点で、ヒドロキシアセトンが特に好ましい。  [0029] Examples of the reduction method include a method using a reducing agent, a method of reducing by electrolysis, and the like. Among these, the former method using a reducing agent is preferable in that fine particles can be obtained. Examples of the reducing agent include hydroquinone, catechol, paraaminophenol, noraf-rangeamine, and hydroxyacetone. Of these, hydroxyacetone is particularly preferable because it volatilizes and does not readily affect the display device.
[0030] 本発明に係る銀錫合金部含有粒子は、以下に示す物理的性質や、平均粒径 (粒 子サイズ)、粒子形状等を有するのが好ましい。  [0030] The silver-tin alloy part-containing particles according to the present invention preferably have the following physical properties, average particle size (particle size), particle shape, and the like.
[0031] 本発明に係る銀錫合金部含有粒子は、示差走査熱量測定法 (DSC： Differential  [0031] Silver-tin alloy part-containing particles according to the present invention are obtained by differential scanning calorimetry (DSC: Differential
Scanning Calorimetry)による測定で、 240〜400°Cの融点を有する粒子である ことが好適である。融点が該範囲であるため、金属 Ag (融点： 950°C)や金属 Sn (融 点：230°C)に比し、良好な熱安定性を示す。  Particles having a melting point of 240 to 400 ° C as measured by scanning calorimetry) are preferred. Since the melting point is within this range, it exhibits better thermal stability than metal Ag (melting point: 950 ° C) and metal Sn (melting point: 230 ° C).
具体的には、 AgSn合金の融解性 (融点）は、試料として AgSn合金 20mgを DSC ( SSC/5200,セイコーインスツル (株）製）の測定セルにセットし、 DSCによる降温結 晶化ピークを、 10°CZ分の降温速度で 200°Cから室温まで冷却して測定される。  Specifically, regarding the melting property (melting point) of AgSn alloy, 20 mg of AgSn alloy was set as a sample in the measurement cell of DSC (SSC / 5200, manufactured by Seiko Instruments Inc.), and the temperature drop crystallization peak by DSC was measured. Measured by cooling from 200 ° C to room temperature with a temperature drop rate of 10 ° CZ.
[0032] 本発明に係る銀錫合金部含有粒子は、平均粒径 (数平均粒子サイズ)が 500nm 以下であることが好ましぐまた下限値は 2nm以上であることがより好ましい。更に、そ の平均粒径は、より好ましくは 20〜200nmであり、特に好ましくは 30〜： LOOnmであ る。数平均粒子サイズが特に前記範囲であると、金属の粒子とは異なり、いずれの粒 子径でも黒い色相を有する。なお、数平均粒子サイズが、 500nmを超えると成膜し たときの面状が悪くなることがあり、 2nm未満であると黒さが減って黄色味を帯びてく ることがある。  [0032] The silver tin alloy part-containing particles according to the present invention preferably have an average particle size (number average particle size) of 500 nm or less, and more preferably have a lower limit of 2 nm or more. Furthermore, the average particle diameter is more preferably 20 to 200 nm, and particularly preferably 30 to: LOOnm. When the number average particle size is particularly in the above-mentioned range, unlike a metal particle, it has a black hue at any particle diameter. When the number average particle size exceeds 500 nm, the surface shape when the film is formed may be deteriorated. When the number average particle size is less than 2 nm, the blackness may decrease and the film may become yellowish.
[0033] 前記数平均粒子サイズは、透過型電子顕微^ [EM— 2010 (日本電子 (株)製）に より得た写真を用いて次のようにして測定される。  [0033] The number average particle size is measured as follows using a photograph obtained by a transmission electron microscope [EM-2010 (manufactured by JEOL Ltd.)].
粒子 100個を選び、それぞれの粒子像と同じ面積の円の直径を粒子径とし、 100 個の粒子の粒子径の平均を数平均粒子サイズとする。なお、写真は、倍率 10万倍、 加速電圧 200kVで撮影したものを用いる。 Select 100 particles, and let the diameter of a circle with the same area as each particle image be the particle diameter. The average particle size of the individual particles is defined as the number average particle size. The photograph is taken at a magnification of 100,000x and an acceleration voltage of 200kV.
[0034] 本発明に係る「銀錫合金部含有粒子」の粒子形状としては、特に制限はなぐキュ 一ビック状、高アスペクト、中アスペクト、針状等のいずれの形状であってもよい。  [0034] The particle shape of the "silver-tin alloy part-containing particles" according to the present invention may be any shape such as a cubic shape, a high aspect, a medium aspect, and a needle shape without any particular limitation.
[0035] 銀錫合金部含有粒子には、 Ag及び Sn以外に、更に塩や有機物、その他の元素（ Ca、 P、 Na等）などを含んでいてもよい。ただし、その場合であっても上記の物理的 性質、粒子サイズ、粒子形状を有し、かつ維持されることが好ましい。  [0035] In addition to Ag and Sn, the silver-tin alloy part-containing particles may further contain a salt, an organic substance, other elements (Ca, P, Na, etc.) and the like. However, even in that case, it is preferable to have and maintain the above-mentioned physical properties, particle size, and particle shape.
[0036] 銀錫合金部含有粒子の、本発明の着色組成物中における量としては、目的や用途 に応じて適宜選択すればよい。その銀錫合金部含有粒子の量は、高度の遮光性を 得る観点からは、組成物の全固形分 (体積）に対して、 5〜70体積％が好ましぐ 10 〜66体積％がより好ましぐ 15〜60体積％が最も好ましい。銀錫合金部含有粒子の 量が特に前記範囲であると、光の反射率が抑えられ、黒濃度が高ぐ薄膜で高い遮 光性を得ることができる。特に、カラーフィルタのブラックマトリクスなど、画像表示領 域の遮光材料として用いた場合には、高コントラストで鮮やかな表示画像を得ること が可能である。なお、銀錫合金部含有粒子の量が、 5体積％未満であるときには成 膜した際の膜厚が 1. 0 mより厚くなることがあり、 70体積％を超えるときには反射率 が高く表示コントラストを損なうことがある。  [0036] The amount of the silver-tin alloy part-containing particles in the colored composition of the present invention may be appropriately selected according to the purpose and application. The amount of the silver-tin alloy part-containing particles is preferably 5 to 70% by volume and more preferably 10 to 66% by volume with respect to the total solid content (volume) of the composition from the viewpoint of obtaining a high level of light shielding properties. Preferred is 15 to 60% by volume. When the amount of the silver-tin alloy part-containing particles is particularly in the above range, the light reflectance is suppressed, and a high light shielding property can be obtained with a thin film having a high black density. In particular, when used as a light shielding material in an image display area such as a black matrix of a color filter, it is possible to obtain a vivid display image with high contrast. When the amount of the silver-tin alloy part-containing particles is less than 5% by volume, the film thickness when formed may be thicker than 1.0 m, and when it exceeds 70% by volume, the reflectance is high and the display contrast is high. May be damaged.
[0037] (感光性を有する着色組成物）  [0037] (Coloring composition having photosensitivity)
本発明における着色組成物は感光性を有することが好ま 、。感光性を付与する ためには、前記着色組成物に感光性榭脂組成物が添加される。感光性榭脂組成物 は、バインダーポリマー、エチレン性不飽和二重結合を有する光の照射によって付 加重合するモノマー、光重合開始剤等を含有する。  The colored composition in the present invention preferably has photosensitivity. In order to impart photosensitivity, a photosensitive resin composition is added to the colored composition. The photosensitive resin composition contains a binder polymer, a monomer that undergoes addition polymerization upon irradiation with light having an ethylenically unsaturated double bond, a photopolymerization initiator, and the like.
[0038] 感光性榭脂組成物は、アルカリ水溶液現像可能なものと、有機溶剤で現像可能な ものがある。感光性榭脂組成物として、安全性と現像液のコストの点で、アルカリ水溶 液現像可能なものが好まし 、。  [0038] There are photosensitive resin compositions that can be developed with an alkaline aqueous solution and those that can be developed with an organic solvent. The photosensitive resin composition is preferably one that can be developed with an aqueous alkaline solution in terms of safety and the cost of the developer.
感光性榭脂組成物は、光、電子線などの放射線を受容する部分が硬化するネガ型 でも放射線未受容部が硬化するポジ型でもよ ヽ。  The photosensitive resin composition may be a negative type in which a part that receives radiation such as light or an electron beam is cured, or a positive type in which a non-radiation-receiving part is cured.
[0039] ポジ型感光性榭脂にはノボラック系の樹脂が挙げられる。例えば、特開平 7—438 99号公報記載のアルカリ可溶性ノボラック榭脂系を使用する事ができる。また、特開 平 6— 148888号公報記載の、ポジ型感光性榭脂層、即ち、該公報記載の榭脂と感 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 の混合物を含む感光性榭脂層を用いる事ができる。また特開平 5— 262850号公報 記載の組成物も使用可能である。 [0039] Examples of the positive photosensitive resin include novolac resins. For example, JP-A-7-438 An alkali-soluble novolac rosin system described in Japanese Patent No. 99 can be used. Further, as described in JP-A-6-148888, a positive photosensitive resin layer, that is, as a resin and a photosensitizer described in the publication, 1,2-naphthoquinonediazide sulfonate ester and thermosetting described in the publication A photosensitive resin layer containing a mixture of agents can be used. A composition described in JP-A-5-262850 can also be used.
[0040] ネガ型感光性榭脂としては、ネガ型ジァゾ榭脂とバインダー力もなる感光性榭脂、 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榭脂組成物、桂皮酸 型感光性榭脂組成物等が挙げられる。その中でも特に好ま ヽのは光重合開始剤、 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感光性榭脂である。 該感光性榭脂層には、特開平 11— 133600号公報記載の「重合性ィ匕合物 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。 [0040] The negative photosensitive resin includes a photosensitive resin having a negative diazo resin and a binder power, a photopolymerizable composition, a photosensitive resin composition comprising an azide compound and a binder, and a cinnamic acid type photosensitive resin. And the like. Among these, photosensitive resins containing a photopolymerization initiator, a photopolymerizable monomer and a binder as basic constituents are particularly preferred. The photosensitive resin layer contains “polymerizable compound B”, “polymerization initiator C”, “surfactant”, “adhesion aid” and other compositions described in JP-A-11-133600. Available.
例えば、ネガ型感光性榭脂で、アルカリ水溶液現像可能な感光性榭脂は、主成分 としてカルボン酸基含有のバインダー（後述の熱可塑性榭脂等）と光の照射によって 付加重合することのできるエチレン性不飽和二重結合含有モノマーと光重合開始剤 を含んでいる。  For example, a negative photosensitive photosensitive resin that can be developed in an aqueous alkali solution can be addition-polymerized by irradiation with light with a binder containing a carboxylic acid group as a main component (such as a thermoplastic resin described later). It contains an ethylenically unsaturated double bond-containing monomer and a photopolymerization initiator.
[0041] ノインダ一としては、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 5 4— 25957号公報、特開昭 59— 53836号公報、及び特開昭 59— 71048号公報に 記載されているようなメタクリル酸共重合体、アクリル酸共重合体、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 などを挙げることができる。また側鎖にカルボン酸基を有するセルロース誘導体も挙 げることができる。この他にも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も挙げることができる。  [0041] Examples of Noinda 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, JP-B-5- A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer as described in Japanese Patent No. 25957, Japanese Patent Laid-Open No. 59-53836, and Japanese Patent Laid-Open No. 59-71048. Examples thereof include a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. In addition, cellulose derivatives having a carboxylic acid group in the side chain can also be mentioned. In addition to this, a polymer having a hydroxyl group added with a cyclic acid anhydride can also be preferably used. In particular, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid as described in U.S. Pat. No. 4,139,391, or a multi-component copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers. Polymers can also be mentioned.
[0042] 感光性榭脂層に用いられるバインダーは、 30〜400mgKOHZg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力 選択して使用される。 その他に、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、アルカリ不溶性のポリマーを添加することができる。これらのポ リマーとしては、アルコール可溶性ナイロンあるいはエポキシ榭脂を挙げることができ る。 [0042] The binder used for the photosensitive resin layer is selected from those having an acid value in the range of 30 to 400 mg KOHZg and a weight average molecular weight in the range of 1000 to 300,000. In addition, various performances such as developability are adversely affected to improve the strength of the cured film. An alkali-insoluble polymer can be added within a range that does not resonate. Examples of these polymers include alcohol-soluble nylon and epoxy resin.
ノ インダ一は、感光性を有する着色組成物の全固形分に対して通常、 10〜95質 量％、さらに 20〜90質量％が好ましい。 10〜95質量％の範囲では、感光性榭脂層 の粘着性が高すぎることもなぐ形成される層の強度及び光感度が劣ることもない。  The binder is generally 10 to 95% by mass, more preferably 20 to 90% by mass, based on the total solid content of the photosensitive coloring composition. In the range of 10 to 95 mass%, the adhesiveness of the photosensitive resin layer is not too high, and the strength and photosensitivity of the formed layer are not inferior.
[0043] 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 ルポリケタルドニル化合物、米国特許第 2448828号明細書に記載されて ヽるァシロ インエーテル化合物、米国特許第 2722512号明細書に記載の α—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号及び同第 2951758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 ρ—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イ匕合物とトリノ、ロメチル— s—トリアジンィ匕合物、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イ匕合 物等が挙げられる。特に好ましくはトリハロメチル— s—トリァジン、トリハロメチルォキ サジァゾーノレ、トリアリーノレイミダゾーノレ二量体である。 [0043] Photopolymerization initiators include vicinal polyketaldonyl compounds disclosed in U.S. Pat. No. 2,367,660, acyloin ether compounds described in U.S. Pat. No. 2448828, U.S. Pat. Aromatic hydrocarbon substituted with α-hydrocarbons described in US Pat. No. 2722512, polynuclear quinone compounds described in US Pat. Nos. 3046127 and 2951758, US Pat. No. 3,549,367 Combination of triarylimidazole dimer and ρ-aminoketone described in the specification, benzothiazole compound and torino, romethyl-s-triazine compound described in Japanese Patent Publication No. 51-48516, US The trihalomethyl-s-triazine compound described in Japanese Patent No. 4239850 and the trihalomethyl oxadiazole compound described in US Pat. No. 4212976 are listed. It is. Particularly preferred are trihalomethyl-s-triazine, trihalomethyloxazazonole, and triarinoreidamidole dimer.
感光性を有する着色組成物において、光重合開始剤の含有量は、全固形分に対 して 0. 5〜20質量％が一般的で、 1〜15質量％が好ましい。 0. 5質量％未満では 光感度や画像の強度が低ぐ 20質量％を超えて添加しても性能向上への効果が認 められない。  In the coloring composition having photosensitivity, the content of the photopolymerization initiator is generally 0.5 to 20% by mass, preferably 1 to 15% by mass, based on the total solid content. If it is less than 5% by mass, the photosensitivity and image strength are low. Even if it is added in excess of 20% by mass, no effect on performance improvement is observed.
[0044] 光照射によって付加重合できるエチレン性不飽和二重結合含有モノマー（以下、 単に「モノマー」 t 、う）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）アタリレート及びフ ノキシェチル (メタ)アタリレート等の単官能 (メタ)ァク 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アタリレ 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）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、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 チロールプロパンもしくはグリセリン等の多官能アルコールにエチレンォキシドゃプロ ピレンォキシドを付加反応させた後で (メタ)アタリレートイ匕したもの等の多官能 (メタ） アタリレートを挙げることができる。 [0044] Examples of the ethylenically unsaturated double bond-containing monomer (hereinafter simply referred to as "monomer" t) that can be addition-polymerized by light irradiation 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 funkistil (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (Meth) atarylate, trimethylol ethane triatrate, trimethylol propane triatrate, trimethylol propane diatalylate, neopentyl glycol di (meth) attaryl , Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate Rate, trimethylolpropane tri (atallyloyloxypropyl) ether, tri (atallylooxychetyl) isocyanurate, tri (atalylooxychetyl) cyanurate, glycerin tri (meth) atarylate, trimethylolpropane or Mention may be made, for example, of polyfunctional (meth) acrylates such as those obtained by addition reaction of ethylene oxide or propylene oxide with polyfunctional alcohols such as glycerin.
[0045] さらに、特公昭 48— 41708号、同 50— 6034号、特開昭 51— 37193号の各公報 に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 4319 1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 キシ榭脂と (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 タ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（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 しい。これらモノマーは、単独でも 2種類以上を混合して用いてもよい。そのモノマー の含有量は、感光性を有する着色組成物の全固形分に対して、 5〜50質量％がー 般的で、 10〜40質量0 /0が好ましい。そのモノマーの含有量が 5〜50質量0 /0の範囲 では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。 [0045] Further, urethane acrylates disclosed in JP-B-48-41708, JP-A-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49 4319 Polyfunctional talates and metatalates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid disclosed in each publication of No. 1 and 52-30490 Can be mentioned. Of these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferred. . These monomers may be used alone or in combination of two or more. The content of the monomer, based on the entire solid content of the colored composition having photosensitivity, 5 to 50 wt% guar general, preferably 10 to 40 mass 0/0. The intensity of the content of the monomer is from 5 to 50 mass 0/0 ranging in photosensitivity and image is also not reduced, it is also not name that tackiness of the photosensitive light shielding layer is excessive.
[0046] 感光性榭脂組成物は、上記成分の他に更に熱重合防止剤を含むことが好ま 、。  [0046] The photosensitive resin composition preferably further contains a thermal polymerization inhibitor in addition to the above components.
熱重合防止剤の例としては、例えば、ハイドロキノン、 p—メトキシフエノール、 p—t— ブチルカテコール、 2, 6 ジ tーブチルー p クレゾール、 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 -トロソフエ- ルヒドロキシルァミンのアルミニウム塩またはアンモ-ゥム塩、クロラニール、ニトロベン ゼン、 4, 4'ーチォビス（3—メチルー 6 t—ブチルフエノール）、 2, 2'—メチレンビス (4ーメチルー 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。 Examples of thermal polymerization inhibitors include, for example, hydroquinone, p-methoxyphenol, p-t-butylcatechol, 2,6-di-tert-butyl-cresol, β-naphthol, pyrogallol and other aromatic hydroxy compounds, benzoquinone, ρ-toluquinone Quinones such as naphthylamine, pyridine, ρ toluidine, phenothiazine, etc., aluminum salt or ammonium salt of ト ロ -trosophenol hydroxylamine, chloranil, nitrobenzene, 4, 4'-thiobis (3— Methyl-6 t-butylphenol), 2, 2'-methylenebis (4-methyl-6 t-butylphenol), 2 mercaptobenzimidazole, etc. It is done.
[0047] 感光性榭脂組成物は、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、可塑剤、垂れ防止剤、レべリング剤、消泡剤、難燃化剤 [0047] The photosensitive resin composition further contains known additives as necessary, for example, plasticizers, surfactants, adhesion promoters, dispersants, plasticizers, anti-sagging agents, leveling agents, Defoamer, flame retardant
、光沢剤、溶剤等を添加することができる。 , Brighteners, solvents and the like can be added.
密着促進剤としては、例えばアルキルフエノール Zホルムアルデヒドノボラック榭脂 、ポロ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 As adhesion promoters, for example, alkylphenol Z formaldehyde novolac rosin, porobule ether, polyisobutyl ether, polybutyral
、ポリイソブチレン、スチレン ブタジエン共重合体ゴム、ブチルゴム、塩化ビ-ルー 酢酸ビニル共重合体、塩化ゴム、アクリル榭脂系粘着剤、芳香族系、脂肪族系また は脂環族系の石油榭脂、シランカップリング剤等が挙げられる。 , Polyisobutylene, styrene butadiene copolymer rubber, butyl rubber, vinyl chloride vinyl acetate copolymer, chlorinated rubber, acrylic resin adhesive, aromatic, aliphatic or alicyclic petroleum resin And silane coupling agents.
[0048] また、銀錫合金部含有粒子を水分散物として用いる場合には、前記感光性榭脂組 成物としては水系のものが必要である。このような感光性榭脂組成物としては特開平 8— 271727号公報の段落 0015な!ヽし 0023に記載のものの他、市販のものとして は例えば、東洋合成工業 (株)製の「SPP -M20J等が挙げられる。  [0048] When the silver-tin alloy part-containing particles are used as an aqueous dispersion, the photosensitive resin composition must be aqueous. Examples of such a photosensitive resin composition include those described in paragraphs 0015 and 0023 of JP-A-8-271727 and commercially available products such as “SPP-manufactured by Toyo Gosei Co., Ltd.”. M20J etc. are mentioned.
[0049] (感光性をもたない着色組成物）  [0049] (Coloring composition having no photosensitivity)
本発明にお 、て感光性をもたな 、着色組成物は、前記のごとき銀錫合金部含有粒 子の他、必要に応じバインダー、分散剤、溶媒等を含有する。バインダーとしては水 溶性榭脂ポリマーバインダーや非水溶性榭脂バインダーが適宜用いられる。  In the present invention, the coloring composition having photosensitivity contains a binder, a dispersant, a solvent, and the like as required in addition to the silver-tin alloy part-containing particles as described above. As the binder, a water-soluble resin polymer binder or a water-insoluble resin binder is appropriately used.
水溶性榭脂ポリマーバインダーは保護コロイド性のあるポリマーが好まし 、。水溶性 榭脂ポリマーバインダーは、例えば、ゼラチン、ポリビュルアルコール、メチルセル口 ース、ヒドロキシプロピルセルロース、ポリアルキルァミン、ポリアクリル酸の部分アルキ ルエステル等が挙げられる。その他、「顔料の事典 (伊藤征司郎編、（株)朝倉書院発 行 2000年）」に記載されて ヽるものが挙げられる。  The water-soluble rosin polymer binder is preferably a protective colloid polymer. Examples of the water-soluble resin polymer binder include gelatin, polybutyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkylamine, and a partial alkyl ester of polyacrylic acid. In addition, those described in “Encyclopedia of Pigments (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd. 2000)” can be mentioned.
[0050] また、非水溶性ポリマーバインダーとしては、「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）に記載されている有機溶媒可溶ポリマーノインダ一力も少なくと も 1つを選択して使用することができる。  [0050] In addition, the water-insoluble polymer binder is described in "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). It is possible to select and use at least one organic solvent soluble polymer noinder.
非水溶性ポリマーバインダーの好ましい具体例としては、ポリアミド、ポリエステル、 ポリスチレン、フエノーノレ榭旨、ポリエチレンなどのポリオレフイン、ポリカーボネート、 シリコーン榭脂、ポリウレア、ポリウレタン、ポリ酸無水物、ポリスルホン、ポリイミン、ポリ スルフイド、ポリアクリロニトリル、ナイロン、ポリ酢酸ビュル、ポリビュルエーテル、ポリ アクリル酸及びポリメタクリル酸並びにこれらのエステル、さらにこれらのコポリマー又 は変性体であって、有機溶媒に可溶なものが挙げられる。 Preferable specific examples of the water-insoluble polymer binder include polyamide, polyester, polystyrene, phenolate, polyolefin such as polyethylene, polycarbonate, Silicone resin, polyurea, polyurethane, polyanhydride, polysulfone, polyimine, polysulfide, polyacrylonitrile, nylon, polyacetate butyl, polybulle ether, polyacrylic acid and polymethacrylic acid and their esters, as well as their copolymers or Is a denatured product and is soluble in an organic solvent.
[0051] また、非水溶性ポリマーバインダーとしては、水に混合できるという観点から、ポリマ 一ラテックスも使用できる。ポリマーラテックスとは水不溶のポリマーの微粒子が水に 分散したものである。水不溶のポリマーには前記のごとき非水溶性ポリマーが挙げら れる。詳細には、例えば、「高分子ラテックスの化学」（室井宗ー著、高分子刊行会発 行、昭和 48年）に記載されている。  [0051] As the water-insoluble polymer binder, a polymer latex can also be used from the viewpoint that it can be mixed with water. Polymer latex is a dispersion of water-insoluble polymer particles in water. Examples of the water-insoluble polymer include water-insoluble polymers as described above. Details are described, for example, in “Polymer Latex Chemistry” (Muro Muroi, published by Kobunshi Shuppankai, 1973).
前記ポリマーラテックスとしては、例えば、ポリエステル、ポリウレタン、ポリウレァ Zゥ レタン、 SBR (スチレン ブタジエン系）、 MBR(MMAZブタジエン、アクリル Zブタ ジェン）、 NBR (アクリロニトリル/ブタジエン）、 NR (天然ゴム）、 BR (ブタジエンゴム） 、 CR (クロロプレンゴム）、 IR (イソプレンゴム）、 VP (SBRZジビュルピリジン）及びこ れらの共重合体力 なるポリマーラテックスが挙げられる。  Examples of the polymer latex include polyester, polyurethane, polyurethane Z urethane, SBR (styrene butadiene type), MBR (MMAZ butadiene, acrylic Z butadiene), NBR (acrylonitrile / butadiene), NR (natural rubber), BR ( Examples thereof include butadiene rubber), CR (chloroprene rubber), IR (isoprene rubber), VP (SBRZ dibule pyridine), and polymer latexes of these copolymers.
[0052] また、前記ポリマーラテックスには、種類の異なるポリマーラテックスを併用すること もできる。併用できるポリマーラテックスとしては、例えば、 SBRと NR、 IRと NR、 CRと NR、 NBRで-トリル量が異なるもの、 SBRでスチレン量が異なるもの、 SBRと VP、 N BRと MBR、 SBRと NBR、 SBRと MBR、 BRと CR、 NBRと VP、 CRと VPなど、了二 オン性のものとカチオン性のものの組合わせでな 、ものが好まし！/、。  [0052] In addition, different types of polymer latex can be used in combination with the polymer latex. Examples of polymer latexes that can be used in combination include SBR and NR, IR and NR, CR and NR, NBR with different -tolyl content, SBR with different styrene content, SBR and VP, NBR and MBR, SBR and NBR SBR and MBR, BR and CR, NBR and VP, CR and VP, etc., which is a combination of nonionic and cationic ones, is preferred! /.
ァ-オン性のものとしては、カルボキシル基を導入したもの、カチオン性のものとし ては、アミノ基ゃアンモニゥム基を導入したものがある。  There are those having a carboxyl group introduced as a cation property, and those having an amino group or an ammonium group introduced as a cationic one.
[0053] 前記ノインダ一としてのポリマーの使用量は、感光性をもたない着色組成物中、 3 〜 50質量％が好ましぐ特に 10〜30質量％が好ましい。  [0053] The amount of the polymer used as the noinda is preferably 3 to 50% by mass, particularly preferably 10 to 30% by mass, in the coloring composition having no photosensitivity.
また、溶媒としては、公知の有機溶媒を用いることができる。特に好ましい有機溶媒 としては、メチルアルコール、イソプロピルアルコール、 MEK、酢酸ェチル、トルエン 等が挙げられる。また、水も溶媒として好ましい。これらの溶媒は必要に応じて混合使 用してちょい。  Moreover, a well-known organic solvent can be used as a solvent. Particularly preferred organic solvents include methyl alcohol, isopropyl alcohol, MEK, ethyl acetate, toluene and the like. Water is also preferred as the solvent. Mix these solvents as necessary.
[0054] [感光性転写材料] 本発明においては、前記の感光性を有する着色組成物を用いて、感光性転写材 料を作製し、これを用いて表示装置用遮光層を作製することができる。 [0054] [Photosensitive transfer material] In the present invention, a photosensitive transfer material is prepared using the above-described photosensitive coloring composition, and a light-shielding layer for a display device can be prepared using the photosensitive transfer material.
前記感光性転写材料は、仮支持体に少なくとも前記の感光性を有する着色組成物 カゝら形成される感光性遮光層を設けたものである。感光性遮光層の膜厚は 0. 2〜2 μ mの範囲が好ましぐ特に 0. 2〜1 mの範囲が好ましい。  The photosensitive transfer material is a temporary support provided with a photosensitive light-shielding layer formed at least by the colored composition having photosensitivity. The thickness of the photosensitive light-shielding layer is preferably in the range of 0.2 to 2 μm, particularly preferably in the range of 0.2 to 1 m.
本発明の仮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 事ができる。その中でも、仮支持体としては、 2軸延伸したポリエチレンテレフタレート がコスト、耐熱性、寸法安定性の観点力も好ましい。仮支持体の厚みは 15から 200 μ m程度、より好ましくは 30から 150 m程度が好ましい。仮支持体において、厚み 力 S15 m未満の場合は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 という欠点がある。逆に仮支持体の厚みが 200 mを超える場合はコスト上不利であ る。  As the temporary support of the present invention, a known support such as polyester or polystyrene can be used. Among them, as the temporary support, biaxially stretched polyethylene terephthalate is preferable in terms of cost, heat resistance, and dimensional stability. The thickness of the temporary support is preferably about 15 to 200 μm, more preferably about 30 to 150 m. If the thickness of the temporary support is less than S15 m, there is a drawback in that a tin plate-like wrinkle is generated by heat during the lamination process. Conversely, when the thickness of the temporary support exceeds 200 m, it is disadvantageous in terms of cost.
また仮支持体には必要に応じて特開平 11— 149008に記載されている導電性層 を設けてもよい。  The temporary support may be provided with a conductive layer described in JP-A-11-149008, if necessary.
[0055] (熱可塑性榭脂層） [0055] (Thermoplastic resin layer)
また、支持体と感光性遮光層、又は支持体と中間層の間に、熱可塑性榭脂層を設 けることが好ましい。  Moreover, it is preferable to provide a thermoplastic resin layer between the support and the photosensitive light-shielding layer, or between the support and the intermediate layer.
熱可塑性榭脂層は、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。その 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 irregularities on the underlying surface (including irregularities caused by images already formed). Therefore, it is preferable to have a property that can be deformed according to the unevenness.
[0056] 熱可塑性榭脂層に含まれる榭脂としては、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 ェンと (メタ)アクリル酸エステル共重合体とのケンィ匕物、ポリ (メタ)アクリル酸エステル 、及び (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。さらに、熱可塑性 榭脂層に含まれる榭脂としては、「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、これらの熱可塑性榭脂の内、軟ィ匕点が 80°C以下のものが好ましい。尚、本願 明細書において、「(メタ)アクリル酸」とは、アクリル酸及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。 [0056] The resin contained in the thermoplastic resin layer includes a saponified product of ethylene and an acrylate copolymer, a saponified product of styrene and a (meth) acrylic ester copolymer, Kenya products such as (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, and (meth) acrylic acid ester copolymer of (meth) acrylic acid butyl and butyl acetate, etc. It is preferable that it is at least one selected from the above. In addition, as the resin contained in the thermoplastic resin layer, the “Plastic Performance Manual” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968) A polymer that is soluble in an alkaline aqueous solution can also be used. Of these thermoplastic resins, those having a softening point of 80 ° C or less are preferred. In the present specification, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, and the same applies to derivatives thereof.
[0057] これらの榭脂の中で、重量平均分子量 5万〜 50万（Tg = 0〜140°C)の範囲で、更 に好ましくは重量平均分子量6万〜20万 8 = 30〜110° の範囲の榭脂から選 択して使用することができる。これらの榭脂の具体例としては、特公昭 54— 34327号 、特公昭 55— 38961号、特公昭 58— 12577号、特公昭 54— 25957号、特開昭 61 — 134756号、特公昭 59— 44615号、特開昭 54— 92723号、特開昭 54— 99418 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、 OLS3504254号、特開昭 60— 2476 38号、特開昭 60— 208748号、特開昭 60— 214354号、特開昭 60— 230135号、 特開昭 60— 258539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— 5 5551号、特開昭 64— 55550号、特開平 2— 191955号、特開平 2— 199403号、 特開平 2— 199404号、特開平 2— 208602号、特願平 4— 39653号、特開平 5— 2 41340号の各公報明細書に記載されているアルカリ水溶液に可溶な榭脂を挙げる ことができる。特に好ましいのは、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/ベンジルメタタリレート/メチルメタクリレー ト共重合体である。 [0057] Among these榭脂, the range of weight average molecular weight from 50,000 to 500,000 (Tg = 0~140 ° C), more preferably at a weight-average molecular weight of 60,000 to 20 million in 8 = 30 to 110 ° It can be used by selecting from a range of resins. Specific examples of these rosins include JP-B 54-34327, JP-B 55-38961, JP-B 58-12577, JP-B 54-25957, 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-A-60-159743, OLS3504254, JP-A-60-247638, JP-A-60-208748, JP-A-60-214354, JP-A-60-230135, JP-A-60- 258539, JP 61-169829, JP 61-213213, JP 63-147159, JP 63-213837, JP 63-266448, JP 64-5 5551 JP-A-64-55550, JP-A-2-191955, JP-A-2-199403, JP-A-2-199404, JP-A-2-208602, JP-A-4-39653, JP-A-5- 2 Soot soluble in alkaline aqueous solution described in each specification of No. 41340 It can be mentioned. Particularly preferred is a methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate described in JP-A-63-147159.
[0058] また、上記した種々の榭脂の中から、好ましくは重量平均分子量 3千〜 3万 (Tg = 3 [0058] Further, among the above various rosins, the weight average molecular weight is preferably 3,000 to 30,000 (Tg = 3
0〜 170°C)の範囲で、更に好ましくは重量平均分子量 4千〜 2万（Tg = 60〜 140°C0 to 170 ° C), more preferably weight average molecular weight 4,000 to 20,000 (Tg = 60 to 140 ° C)
)の範囲で選択して使用することができる。好ましい具体例は、上記の特許明細書に 記載されているものの中力も選ぶことができる力 特に好ましくは、特公昭 55— 3896) Can be selected and used. The preferred embodiment is a force capable of selecting the medium force described in the above patent specification.
1号、特開平 5— 241340号明細書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。 Examples thereof include styrene Z (meth) acrylic acid copolymers described in JP-A No. 1 and JP-A-5-241340.
また、これらの有機高分子物質中に支持体との接着力を調節するために、各種可 塑剤、各種ポリマーや過冷却物質、密着改良剤あるいは界面活性剤、離型剤等を加 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ル、 ポリエチレングリコール、ジォクチルフタレート、ジヘプチルフタレート、ジブチルフタ レート、トリクレジルフォスフェート、クレジルジフエ-ルフォスフェート、ビフエ-ルジフ ェ-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、エポキシ榭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、有機ジイソシアナー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グリコ 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。熱可塑性 榭脂層中の可塑剤の量は、該熱可塑性榭脂に対して、 200質量％以下が一般的で 、好ましくは 20〜： L00質量％である。熱可塑性榭脂層の厚みは 1. 以上が好ま しい。熱可塑性榭脂の厚みが 1. 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 m以下 が一般的であり、好ましくは約 50 μ m以下である。 In addition, various plasticizers, various polymers, supercooling substances, adhesion improvers or surfactants, mold release agents, etc. may be added to these organic polymer substances in order to adjust the adhesion force to the support. Is possible. Specific examples of preferred plasticizers include polypropylene glycol, Polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphosphate, biphenyl diphosphate, polyethylene glycol mono (meth) acrylate, polyethylene glycol (meta ) Atallate, Polypropylene glycol mono (meth) acrylate, Polypropylene glycol di (meth) acrylate, Addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, Organic diisocyanate and Polyethylene glycol Addition reaction product of bis (meth) acrylate, addition reaction product of organic diisocyanate and polypropylene glycol mono (meth) acrylate, bisphenol A and polyethylene glycol And a condensation reaction product with an alcohol mono (meth) acrylate. The amount of the plasticizer in the thermoplastic resin layer is generally 200% by mass or less, preferably 20 to L00% by mass with respect to the thermoplastic resin. The thickness of the thermoplastic resin layer is preferably 1. or more. If the thickness of the thermoplastic resin is 1. or more, the unevenness of the base surface can be completely absorbed. The upper limit is generally about 100 m or less, preferably about 50 μm or less, from the viewpoint of developability and production suitability.
[0059] 本発明にお ヽて、熱可塑性榭脂層の溶媒としてはこの層を構成する榭脂を溶解す るものであれば特に制限なく使用できる。その溶媒の例としては、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。 In the present invention, the solvent for the thermoplastic resin layer can be used without particular limitation as long as it can dissolve the resin constituting the layer. Examples of the solvent include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, i-propanol and the like.
[0060] (中間層）  [0060] (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 ちょい。  In the photosensitive transfer material of the present invention, an intermediate layer is provided between the temporary support and the photosensitive light-shielding layer.
中間層を構成する榭脂としては特に制限はないが、アルカリ可溶性であることが好 ましい。榭脂の例としてポリビュルアルコール系榭脂、ポリビュルピロリドン系榭脂、セ ルロース系榭脂、アクリルアミド系榭脂、ポリエチレンオキサイド系榭脂、ゼラチン、ビ -ルエーテル系榭脂、ポリアミド榭脂、及びこれらの共重合体を挙げる事ができる。ま たポリエステルのように通常はアルカリ可溶性でな ヽ榭脂にカルボキシル基やスルホ ン酸基を持つモノマーを共重合した榭脂も用いる事ができる。  There is no particular limitation on the resin constituting the intermediate layer, but it is preferably alkali-soluble. Examples of fats include polybulal alcoholic, polypyrrole pyrrolidone, cellulose, acrylamide, polyethylene oxide, gelatin, butyl ether, polyamide, and These copolymers can be mentioned. Further, it is also possible to use a resin obtained by copolymerizing a monomer having a carboxyl group or a sulfonic acid group with a resin that is usually alkali-soluble, such as polyester.
これらの中で好まし!/、ものはポリビュルアルコールである。ポリビュルアルコールとし ては酸ィ匕度が 80%以上のものが好ましぐ 83から 98%のものがより好ましい。 Preferable among these! / Is polybulal alcohol. As polybulu alcohol In particular, those having an acidity of 80% or more are preferred, and those having an acidity of 83 to 98% are more preferred.
中間層を構成する榭脂は 2種類以上を混合して使用する事が好ましぐ特にポリビ -ルアルコールとポリビュルピロリドンを混合して用いる事が特に好まし 、。両者の重 量比はポリビュルピロリドン Zポリビュルアルコール = 1Z99力ら 75Z25、より好まし くは 10Z90から 50Z50の範囲が好ましい。この比が 1Z99以下になると中間層の 面状の悪化、その上に塗設した感光性榭脂層との密着不良といった問題が生じる。 逆に両者の重量比が 75Z25を超えると中間層の酸素遮断性が低下して感度が低 下する。  It is preferable to use a mixture of two or more types of the resin constituting the intermediate layer. Particularly, it is particularly preferable to use a mixture of polyvinyl alcohol and polybutylpyrrolidone. The weight ratio of the two is preferably polybulurpyrrolidone Z polybulal alcohol = 1Z99 force and 75Z25, more preferably in the range of 10Z90 to 50Z50. When this ratio is 1Z99 or less, problems such as deterioration of the surface condition of the intermediate layer and poor adhesion with the photosensitive resin layer coated thereon arise. Conversely, if the weight ratio of both exceeds 75Z25, the oxygen barrier property of the intermediate layer decreases and the sensitivity decreases.
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してもよい。  You may add additives, such as surfactant, to an intermediate | middle layer as needed.
中間層の厚みは 0. 1力ら 5 m、より好ましくは 0. 5から 3 mの範囲が好ましい。 厚みが 0. 1 m未満の場合酸素遮断性の低下により感度が低下することがあり、 5 μ mを超える場合は現像時の中間層除去時間の増大と!/ヽぅ問題が起こることがある。 中間層の塗布溶媒としては上記の榭脂が溶解すれば、特にその他の制限はない 力 水が好ましい。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。 中間層の塗布溶媒の好ましい具体例としては次のようなものがある。水、水 Zメタノー ル = 90ZlO、水 Ζメタノール =70Ζ30、水 Ζメタノール =55Ζ45、水 Ζエタノー ル =70Ζ30、水 Zl—プロパノール =70Ζ30、水 Ζアセトン = 90ZlO、水,メチ ルェチルケトン = 95/5 (質量比）。  The thickness of the intermediate layer is preferably 0.1 force to 5 m, and more preferably 0.5 to 3 m. If the thickness is less than 0.1 m, the sensitivity may decrease due to a decrease in oxygen barrier properties. If the thickness exceeds 5 μm, the intermediate layer removal time during development may increase and the! / ヽ ぅ problem may occur. . As the coating solvent for the intermediate layer, there is no particular limitation as long as the above resin is dissolved. A mixed solvent obtained by mixing the aforementioned water-miscible organic solvent with water is also preferable. Preferable specific examples of the coating solvent for the intermediate layer include the following. Water, water Z methanol = 90 ZlO, water Ζ methanol = 70 Ζ 30, water Ζ methanol = 55 Ζ 45, water Ζ ethanol = 70 Ζ 30, water Zl-propanol = 70 Ζ 30, water Ζ acetone = 90 ZlO, water, methyl ethyl ketone = 95/5 ( Mass ratio).
[0061] 本発明の感光性転写材料を作製するには、支持体に、本発明の感光性を有する 着色組成物の溶液を、例えば、スピナ一 (スピン方式、スリットアンドスピン方式）、ホヮ イラ1 ~"ゝ口1 ~"ラ1 ~"コ1 ~"タ' ~"ゝ力. ~"テ、ノコ' ~"タ' ~"ゝナイフコ1 ~"タ' ~"ゝワイヤ1 ~"ノ 1 ~"コ1 ~"タ' ~"[0061] In order to produce the photosensitive transfer material of the present invention, a solution of the coloring composition having the photosensitive property of the present invention is applied to a support, for example, spinner (spin method, slit and spin method), Ira 1 ~ "Higuchi 1 ~" La 1 ~ "Ko 1 ~" Ta '~ "ゝ 力. ~" Te, Saw' ~ "Ta '~" ゝ Knife Ko 1 ~ "Ta'~" ゝ Wire 1 ~ "ノ1 ~ "コ1 ~" タ '~ "
、エタストルーダー (FAS方式等)等の塗布機を用いて塗布 '乾燥させることにより形 成することができる。熱可塑性榭脂の層を設ける場合には同様にして形成される。 It can be formed by applying and drying using an applicator such as Etastruder (FAS method, etc.). When a thermoplastic resin layer is provided, it is formed in the same manner.
[0062] 本発明の感光性転写材料は、前記のごとき着色組成物から形成される感光性遮光 層を設けているため、これからは、薄膜でかつ光学濃度が高い遮光層を備えた表示 装置用遮光層を作製することができる。 [0062] Since the photosensitive transfer material of the present invention is provided with the photosensitive light-shielding layer formed from the coloring composition as described above, from now on, for a display device having a light-shielding layer that is a thin film and has a high optical density. A light shielding layer can be produced.
[0063] [表示装置用遮光層及びその作製方法] [Light-shielding layer for display device and manufacturing method thereof]
本発明の表示装置用遮光層は、前記着色組成物又は感光性転写材料を用いて作 製される。その膜厚は 0. 1〜2. 0 m程度、好ましくは 0. 1〜0. 9 mである。遮光 層の膜厚 Ι πι当たりの光学濃度は 3. 5以上である。前記表示装置用遮光層は、更 に、銀錫合金部含有粒子を体積分率で 0. 05-0. 7に分散させた層であり、かつ、 遮光層の C光源透過光の ΧΥΖ表色系色度座標 (X, y)と、前記光源の色度座標 (X The light-shielding layer for a display device according to the present invention is made using the colored composition or the photosensitive transfer material. Made. The film thickness is about 0.1 to 2.0 m, preferably 0.1 to 0.9 m. The optical density per film thickness ππι of the light shielding layer is 3.5 or more. The light shielding layer for a display device is a layer in which silver tin alloy part-containing particles are further dispersed in a volume fraction of 0.05 to 0.7, and the color of the light transmitted through the C light source of the light shielding layer System chromaticity coordinates (X, y) and chromaticity coordinates (X
0 0
, y )とが、 (x - x ) 2 + (y-y ) 2≤0. 01の関係を有するものが、前記のごとき薄膜で, y) and (x-x) 2 + (yy) 2 ≤0.01 are thin films as described above.
0 0 0 0 0 0
も十分な光学濃度を有し、また優れた黒色の色相を有し、更に、加熱による色相変化 が小さいか、あるいはないため好ましい。また、薄膜であるので、カラーフィルタを形 成する場合、 RGBなどの画素との重なりが生じにくぐカラーフィルタの平坦性があが る。 Is preferable because it has a sufficient optical density, has an excellent black hue, and has little or no hue change due to heating. In addition, since it is a thin film, when color filters are formed, the flatness of the color filter is less likely to overlap with pixels such as RGB.
感光性を有する着色組成物を用いて表示装置用遮光層を作製する方法は、光透 過性基板に、感光性の着色組成物を塗布して着色組成物の層を形成し (塗布方法 は前記感光性転写材料を作製する際の方法と同様)、常法により、表示装置用遮光 層用フォトマスクを介して露光し、その後現像することにより遮光層を形成する方法で ある。  A method for producing a light-shielding layer for a display device using a photosensitive coloring composition is to apply a photosensitive coloring composition to a light-transmitting substrate to form a colored composition layer (application method is: This is a method for forming a light-shielding layer by exposure through a photomask for a light-shielding layer for a display device, followed by development by a conventional method, similar to the method for producing the photosensitive transfer material.
また、着色組成物が感光性をもたない場合は、光透過性基板に、本発明の銀錫合 金部含有粒子を含有する着色組成物を塗布して着色組成物の層を形成した後、そ の層の上に、現像可能な感光性榭脂組成物からの層を形成し、常法により、表示装 置用遮光層用フォトマスクを介して露光し、次いで、現像、エッチングすることにより遮 光層を形成することができる。  Further, when the colored composition does not have photosensitivity, after the colored composition containing the silver-tin alloy part-containing particles of the present invention is applied to the light-transmitting substrate, the colored composition layer is formed. Then, a layer from a developable photosensitive resin composition is formed on the layer, and is exposed through a photomask for a light-shielding layer for a display device by a conventional method, and then developed and etched. Thus, a light shielding layer can be formed.
前記感光性転写材料を用いる表示装置用遮光層の作製方法は、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〖こ 配置して積層し、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、表示装置用遮光層用フォトマスクを介して前記層を露光した後現像し て表示装置用遮光層を形成する方法である。  In the method for producing a light shielding layer for a display device 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 with the photosensitive transfer material. Next, the support is peeled off from the laminate of the photosensitive transfer material and the light-transmitting substrate, and then the layer is exposed through a photomask for a light-shielding layer for a display device and developed to develop a display device. This is a method of forming a light shielding layer.
本発明の表示装置用遮光層の製造方法は、煩瑣な工程を必要とせず、低コストで ある。  The method for producing a light shielding layer for a display device of the present invention does not require a cumbersome process and is low in cost.
[カラーフイノレタ] [Color Fino Lettera]
本発明のカラーフィルタは、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表示装 置用遮光層により離画されている構成を有し、該表示装置用遮光層は、本発明の前 記着色組成物又は感光性転写材料を用いて作製される。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)及び青（B)の 3つの色相が 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く、 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 つてもよい。 The color filter of the present invention comprises a colored layer on a light transmissive substrate and is different from each other. The pixel group includes two or more pixel groups exhibiting colors, and the pixels constituting the pixel group are separated from each other by a display device light-shielding layer. It is produced using the colored composition or the photosensitive transfer material. The number of pixel groups may be two, three, or four or more. For example, three hues are used: red (R), green (G), and blue (B). When three types of pixel groups of red, green, and blue are arranged, a mosaic type, a triangle type, and the like are preferable. When four or more types of pixel groups are arranged, any arrangement may be used.
前記光透過性基板としては、表面に酸ィ匕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あるいはプラス チックフィルム等が用いられる。  As the light transmissive 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.
カラーフィルタを作製するには、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、前記のようにして表示装置用遮光層を形成しても、或いは最初に表示装 置用遮光層を形成し、その後 2以上の画素群を形成してもよ 、。  In order to produce a color filter, after forming two or more pixel groups on a light-transmitting substrate by a conventional method, a light-shielding layer for a display device is formed as described above, or first a display device is formed. For example, a light shielding layer may be formed, and then two or more pixel groups may be formed.
本発明のカラーフィルタは前記のごとき表示装置用遮光層を備えているため、表示 コントラストが高くまた平坦性に優れている。さらに、表示装置用遮光層の膜厚が小さ いため、カラーフィルタ画素を作製する際に巻き込む気泡の数も少ないかあるいはな い。  Since the color filter of the present invention includes the light shielding layer for a display device as described above, the display contrast is high and the flatness is excellent. Furthermore, since the thickness of the light shielding layer for the display device is small, the number of bubbles entrained when manufacturing the color filter pixel may be small.
[液晶表示素子] [Liquid crystal display element]
本発明の液晶表示素子の 1つは、少なくとも 1つが光透過性を有する 1対の基板と 、その基板の間に、カラーフィルタ、液晶層および液晶駆動手段（単純マトリックス駆 動方式及びアクティブマトリックス駆動方式を含む）を少なくとも備えたものであって、 前記カラーフィルタとして、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、互いに本発明の表示装置用遮光層により離画されて 、るカラーフィルタ を用いるものである。前記カラーフィルタは平坦性が高いため、このカラーフィルタを 備える液晶表示素子は、カラーフィルタと基板との間にセルギャップムラが発生せず 、色ムラ等の表示不良が発生することがない。  One of the liquid crystal display elements of the present invention includes a pair of substrates, at least one of which is light transmissive, and a color filter, a liquid crystal layer, and a liquid crystal driving means (simple matrix driving method and active matrix driving) between the substrates. A plurality of pixel groups as described above as the color filter, and each pixel constituting the pixel group is formed by the light shielding layer for a display device of the present invention. The color filter is used after being separated. Since the color filter has high flatness, the liquid crystal display element including the color filter does not cause cell gap unevenness between the color filter and the substrate, and display defects such as color unevenness do not occur.
また、本発明の液晶表示素子の別の態様のものは、少なくとも 1つが光透過性を有 する 1対の基板と、その基板の間に、カラーフィルタ、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、かつ各ァ クティブ素子の間に本発明の着色組成物又は感光性転写材料を用いて作製される 表示装置用遮光層が形成されているものである。 In another aspect of the liquid crystal display element of the present invention, a pair of substrates, at least one of which has light transmissivity, and a color filter, a liquid crystal layer, and a liquid crystal driving means are provided between the substrates. At least, the liquid crystal driving means has an active element (for example, TFT), and a light-shielding layer for a display device is formed between the active elements using the colored composition or photosensitive transfer material of the present invention. It is what has been.
[0066] [表示装置用遮光層付き基板] [0066] [Substrate with shading layer for display device]
本発明の表示装置用遮光層付き基板は、光透過性基板の上に前述の表示装置用 遮光層を設けたものであり、前記表示装置用遮光層は、該層の膜厚 1 μ m当たり光 学濃度が 3. 5以上であり、銀錫合金部含有粒子を体積分率で 0. 05〜0. 7に分散 含有しており、かつ、 C光源透過光の XYZ表色系色度座標 (X, y)と、前記光源の色 度座標 (x , y )とが、 (x-x ) 2+ (y-y ) 2≤0. 01の関係を有することを特徴とする。 The substrate with a light-shielding layer for a display device according to the present invention is obtained by providing the above-described light-shielding layer for a display device on a light-transmitting substrate. Optical density is 3.5 or more, silver tin alloy part-containing particles are dispersed and contained in a volume fraction of 0.05 to 0.7, and XYZ color system chromaticity coordinates of C light source transmitted light (X, y) and chromaticity coordinates (x, y) of the light source have a relationship of (xx) 2 + (yy) 2 ≤0.01.
0 0 0 0  0 0 0 0
本発明の表示装置用遮光層付き基板は、カラーフィルタの作製のために用いること ができる。そして、薄膜でも十分な光学濃度が達成できるので、表示装置用遮光層 の膜厚が小さくでき、表示装置用遮光層付き基板の上にカラーフィルタ画素を作製 する際に巻き込む気泡の数も少な 、。  The substrate with a light-shielding layer for a display device of the present invention can be used for producing a color filter. Since a sufficient optical density can be achieved even with a thin film, the thickness of the light shielding layer for the display device can be reduced, and the number of bubbles entrained when producing the color filter pixel on the substrate with the light shielding layer for the display device is small. .
実施例  Example
[0067] 以下に実施例により本発明をさらに具体的に説明する力 本発明はこれらの実施 例により限定されるものではない。なお、以下において、「部」および「％」はそれぞれ 「質量部」および「質量％」を意味する。  [0067] The ability of the present invention to be described more specifically with reference to the following examples. The present invention is not limited to these examples. In the following, “parts” and “%” mean “parts by mass” and “% by mass”, respectively.
[0068] (実施例 1〜5)  [0068] (Examples 1 to 5)
<銀錫合金部を有する金属粒子の分散液 (分散液 A1)の調製 >  <Preparation of dispersion of metal particles having silver-tin alloy part (dispersion A1)>
純水 1000mlに、酢酸銀（1) 23. lg、酢酸スズ（Π) 65. lg、ダルコン酸 54g、ピロリ ン酸ナトリウム 45g、ポリエチレングリコール（分子量 3, 000) 2g、及び E735 (ァイエ スピー ·ジャパン (株)製；ビュルピロリドン Z酢酸ビュルコポリマー） 5gを溶解し、溶液 1を得た。  In 1000 ml of pure water, silver acetate (1) 23. lg, tin acetate (Π) 65. lg, dulconic acid 54 g, sodium pyrophosphate 45 g, polyethylene glycol (molecular weight 3,000) 2 g, and E735 (KYSP) 5 g was dissolved to obtain Solution 1.
別途、純水 500mlにヒドロキシアセトン 36. lgを溶解して、溶液 2を得た。  Separately, 36. lg of hydroxyacetone was dissolved in 500 ml of pure water to obtain a solution 2.
[0069] 上記より得た溶液 1を 25°Cに保ちつつ激しく攪拌しながら、これに上記の溶液 2を 2 分間かけて添加し、緩やかに 6時間攪拌を継続した。すると、混合液が黒色に変化し 、銀錫合金部を有する金属粒子 (銀錫合金部含有粒子)を得た。次いで、この液を遠 心分離して銀錫合金部含有粒子を沈殿させた。遠心分離は、 150mlの液量に小分 けして、卓上遠心分離機 H— 103n ( (株)コクサン製）により回転数 2, OOOr.p.m.で 3 0分間行なった。そして、上澄みを捨て全液量が 150mlになるようにし、これに純水 1 350mlを加え、 15分間攪拌して銀錫合金部含有粒子を再び分散させた。この操作 を 2回繰り返して水相の可溶性物質を除去した。 [0069] While the solution 1 obtained above was vigorously stirred while maintaining at 25 ° C, the above solution 2 was added thereto over 2 minutes, and the stirring was continued gently for 6 hours. Then, the mixed liquid turned black, and metal particles having silver-tin alloy parts (silver-tin alloy part-containing particles) were obtained. Next, the liquid was centrifuged to precipitate silver-tin alloy part-containing particles. Centrifugation is performed in a small volume of 150 ml. Then, it was carried out with a table centrifuge H-103n (manufactured by Kokusan Co., Ltd.) at a rotation speed of 2, OOOr.pm for 30 minutes. Then, the supernatant was discarded so that the total liquid volume became 150 ml, 1 350 ml of pure water was added thereto, and the mixture was stirred for 15 minutes to disperse the silver-tin alloy part-containing particles again. This operation was repeated twice to remove soluble substances in the aqueous phase.
[0070] その後、この液に対して更に遠心分離を行な!/、、銀錫合金部含有粒子を再び沈殿 させた。遠心分離は前記同様の条件にて行なった。遠心分離した後、前記同様に上 澄みを捨て全液量が 150mlになるようにし、これに純水 850ml及びアセトン 500ml を加え、さらに 15分間攪拌して銀錫合金部含有粒子を再び分散させた。  [0070] Thereafter, the liquid was further centrifuged! /, And the silver-tin alloy part-containing particles were precipitated again. Centrifugation was performed under the same conditions as described above. After centrifuging, the supernatant was discarded as described above so that the total liquid volume became 150 ml, 850 ml of pure water and 500 ml of acetone were added thereto, and the mixture was further stirred for 15 minutes to disperse the particles containing the silver-tin alloy part again. .
[0071] 再び前記同様にして遠心分離を行な!/、、銀錫合金部含有粒子を沈殿させた後、前 記同様に上澄みを捨て液量が 150mlになるようにし、これに純水 150ml及びァセト ン 1200mlを加えて更に 15分間攪拌し、銀錫合金部含有粒子を再び分散させた。そ して再び、遠心分離を行なった。このときの遠心分離の条件は、時間を 90分に延ば した以外は前記同様である。その後、上澄みを捨て全液量が 70mlになるようにし、こ れにアセトン 30mlをカ卩えた。これをアイガーミル（アイガーミル M— 50型、メディア： 直径 0. 65mmジルコ-ァビーズ 130g、アイガ一 ·ジャパン (株）製）を用いて 6時間 分散し、銀錫合金部含有粒子の分散液 (分散液 A1)を得た。  [0071] Centrifugation was again carried out in the same manner as above! /, After precipitation of the silver-tin alloy part-containing particles, the supernatant was discarded in the same manner as described above so that the liquid volume became 150 ml. Then, 1200 ml of acetone was added and the mixture was further stirred for 15 minutes to disperse the particles containing the silver-tin alloy part again. Again, centrifugation was performed. The centrifugation conditions at this time are the same as described above except that the time is extended to 90 minutes. After that, the supernatant was discarded so that the total liquid volume became 70 ml, and 30 ml of acetone was added thereto. This was dispersed for 6 hours using an Eiger mill (Eiger Mill M-50 type, media: diameter 0.665 mm Zirca beads 130 g, manufactured by Aiga Japan Co., Ltd.), and a dispersion of silver-tin alloy part-containing particles (dispersion) A1) was obtained.
この銀錫合金部含有粒子は、 AgSn合金（2 0 = 39. 5° )と Sn金属（2 Θ = 30. 5 ° )とからなる複合体であることが X線散乱により確認された。ここで、カツコ内の数字 はそれぞれの（ΠΙ)面の散乱角である。この微粒子分散液を透過型電子顕微鏡で観 察した結果、分散平均粒径は数平均粒子サイズで 40nmであった。  It was confirmed by X-ray scattering that the silver-tin alloy part-containing particles were a composite composed of an AgSn alloy (2 0 = 39.5 °) and Sn metal (2 Θ = 30.5 °). Here, the numbers in Katsuko are the scattering angles of each (ΠΙ) plane. As a result of observing this fine particle dispersion with a transmission electron microscope, the number average particle size was 40 nm.
[0072] 尚、数平均粒子サイズの測定は、透過型電子顕微^ [EM— 2010 (日本電子 (株） 製）により得た写真を用い、前述の方法によって行った。  [0072] The number average particle size was measured by the method described above using a photograph obtained by transmission electron microscope [EM-2010 (manufactured by JEOL Ltd.)].
[0073] <感光層塗布液の調製 >  <Preparation of photosensitive layer coating solution>
上記より作製した銀錫合金部含有粒子の分散液 A1に下記の成分を添加し、実施 例 1ないし実施例 5で用いる感光層塗布液を調製した。尚、ジペンタエリスリトールへ キサアタリレートの添加量は、実施例 1ないし実施例 5の銀錫合金部含有粒子の体積 分率が表 1に記載の値となるように調節した。  The following components were added to the dispersion A1 of silver-tin alloy part-containing particles prepared as described above to prepare photosensitive layer coating solutions used in Examples 1 to 5. The amount of dipentaerythritol hexaatalylate was adjusted so that the volume fraction of the silver-tin alloy part-containing particles of Examples 1 to 5 had the values shown in Table 1.
，前記銀錫合金部含有粒子の分散液 (分散液 A1) - 50. 00部 'プロピレングリコールモノメチルエーテルアセテート · '·28. 6部 , Dispersion of said silver-tin alloy part-containing particles (Dispersion A1)-50.00 parts 'Propylene glycol monomethyl ether acetate' · 28. 6 parts
•メチルェチルケトン · '·37. 6部  • Methyl ethyl ketone · '37. 6 parts
'フッ素系界面活性剤 … 0. 2部  'Fluorosurfactant… 0. 2 parts
(F— 780— F、大日本インキ化学工業 (株)製）  (F—780—F, manufactured by Dainippon Ink & Chemicals, Inc.)
'ヒドロキノンモノメチノレエーテノレ … 0. 001咅  'Hydroquinone Monomethinoleetenole… 0. 001 咅
•スチレン Ζアクリル酸共重合体 … 9. 6部  • StyreneΖAcrylic acid copolymer… 9.6 parts
(モル比 = 56Ζ44、重量平均分子量 30, 000)  (Molar ratio = 56Ζ44, weight average molecular weight 30,000)
'ジペンタエリスリトールへキサアタリレート …（銀錫合金部含有粒子の体積分 率が表 1の値になるよう添加）  'Dipentaerythritol hexaatalylate… (added so that the volume fraction of the silver-tin alloy part-containing particles is the value shown in Table 1)
(KAYARAD DPHA、 日本化薬社製）  (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
'ビス [4— [N— [4— (4, 6—ビストリクロロメチル一 s—トリァジン一 2—ィル）フエ-ル ]力ルバモイル]フエニル]セバケート  'Bis [4— [N— [4— (4, 6-bistrichloromethyl 1 s-triazine 1-yl) phenol] force rubermoyl] phenyl] sebacate
… 0. 5部  … 0.5 part
[0074] <保護層塗布液の調製 >  [0074] <Preparation of protective layer coating solution>
ポリビュルアルコール（（株）クラレ製 PVA205) 3. 0部  Polybur alcohol (PVA205, Kuraray Co., Ltd.) 3.0
ポリビュルピロリドン（アイエスピ一'ジャパン (株）製 PVP— K30)  Polybylpyrrolidone (PVP—K30 manufactured by ISPI Japan)
1. 3部  1. Part 3
蒸留水 50. 7部  Distilled water 50. 7 parts
メチノレアノレコーノレ 45. 0咅  Methino Reno Reconnare 45. 0 咅
[0075] <感光材料の作製 >  [0075] <Production of photosensitive material>
無アルカリガラス基板を、 UV洗浄装置で洗浄後、洗浄剤を用いてブラシ洗浄し、 更に超純水で超音波洗浄した。該基板を 120°Cで 3分熱処理して表面状態を安定 化させた。  The alkali-free glass substrate was cleaned with a UV cleaning device, brushed with a cleaning agent, and then ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C for 3 minutes to stabilize the surface state.
該基板を冷却し 23°Cに温調後、スリット状ノズルを有すガラス基板用コーター（平田 機ェ (株)製）にて、各実施例の感光層塗布液をそれぞれ塗布した。引き続き VCD ( 真空乾燥装置;東京応化工業 (株)製)で 30秒間、溶媒の一部を乾燥して塗布層の 流動性を無くした。次いで、この上にスピンコーターを用いて保護層塗布液を乾燥膜 厚が 1. 5 mになるように塗布して 100°Cで 5分間乾燥し、感光性榭脂層 K1を得た [0076] <表示装置用遮光層の作製 > After cooling the substrate and adjusting the temperature to 23 ° C., the photosensitive layer coating solution of each example was applied with a glass substrate coater (manufactured by Hirata Machine Co., Ltd.) having a slit nozzle. Subsequently, part of the solvent was dried for 30 seconds with a VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) to eliminate the fluidity of the coating layer. Next, the coating solution for the protective layer was applied on this using a spin coater so that the dry film thickness was 1.5 m and dried at 100 ° C for 5 minutes to obtain a photosensitive resin layer K1. <Fabrication of light shielding layer for display device>
超高圧水銀灯を有すプロキシミティー型露光機（日立ハイテク電子エンジニアリン グ (株)製)で、基板とマスク (画像パターンを有す石英露光マスク）を垂直に立てた状 態で、露光マスク面と該感光性榭脂層の間の距離を 200 mに設定し、露光量 70m j/cm2でパターン露光した。 With a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, the exposure mask surface with the substrate and mask (quartz exposure mask with image pattern) standing vertically The distance between the photosensitive resin layer and the photosensitive resin layer was set to 200 m, and pattern exposure was performed with an exposure amount of 70 m j / cm 2 .
次に、純水をシャワーノズルにて噴霧して、該感光性榭脂層 K1の表面を均一に湿 らせた後、 KOH系現像液 (KOH、ノ-オン界面活性剤含有、商品名： CDK— 1、富 士フィルムエレクト口-クスマテリアルズ）にて 23°C80秒、フラットノズル圧力 0. 04M Paでシャワー現像しパターユング画像を得た。引き続き、超純水を、超高圧洗浄ノズ ルにて 9. 8MPaの圧力で噴射して残渣除去を行い、更に超純水をシャワーノズルで 両面から吹き付けて、付着している現像液や前記感光性榭脂層溶解物を除去し、ェ ァーナイフにて液切りを行い、ガラス基板の上に表示装置用遮光層が形成された実 施例 1ないし実施例 5の表示装置用遮光層付き基板を得た。  Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, and then a KOH developer (KOH, containing a nonionic surfactant, trade name: CDK-1 and Fujifilm Elect Kokuku Materials Co., Ltd.) were developed at 23 ° C for 80 seconds at a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water is sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, and ultrapure water is sprayed from both sides with a shower nozzle, and the attached developer and the photosensitive The substrate with the light-shielding layer for display devices of Examples 1 to 5 in which the light-soluble resin layer dissolved material was removed, the liquid was removed with an air knife, and the light-shielding layer for display devices was formed on the glass substrate. Obtained.
[0077] (感光層膜厚測定） [0077] (Photosensitive layer thickness measurement)
次の方法で感光層の膜厚を測定した。ガラス基板に前記 (感光材料の作製）にお いて塗布した各感光層塗布液と同じ塗布量で塗布した感光層膜を作製し、これに超 高圧水銀灯を用いて塗布面側力も 70miZcm2の露光を行った感光層膜を測定試 料として用 ヽた。この測定試料の膜厚を触針式表面粗さ計 P - 1 (TENKOR社製)を 用いて測定した。 The film thickness of the photosensitive layer was measured by the following method. A photosensitive layer film was prepared by coating the glass substrate with the same coating amount as each photosensitive layer coating solution applied in the above (Preparation of photosensitive material), and using this ultra high pressure mercury lamp, the coating surface side force was also 70 miZcm 2 . The photosensitive layer film was used as a measurement sample. The film thickness of this measurement sample was measured using a stylus type surface roughness meter P-1 (manufactured by TENKOR).
この測定試料の膜厚を表 1に示す。  Table 1 shows the film thickness of this measurement sample.
[0078] (光学濃度の測定） [0078] (Measurement of optical density)
膜の光学濃度は、前記の膜厚測定で用いた各測定試料を用いた。この各測定試 料の光学濃度をマクベス濃度計 (マクベス社製 TD— 904)を用いて測定した (OD)。 別途ガラス基板の光学濃度を同様の方法で測定した (OD )。 ODから ODを差し引  As the optical density of the film, each measurement sample used in the film thickness measurement was used. The optical density of each measurement sample was measured using a Macbeth densitometer (TD-904 manufactured by Macbeth) (OD). Separately, the optical density of the glass substrate was measured by the same method (OD). Subtract OD from OD
0 0  0 0
V、た値を膜の光学濃度とする。各測定試料の光学濃度を表 1に示す。  The value of V is the optical density of the film. Table 1 shows the optical density of each measurement sample.
[0079] (体積分率の測定） [0079] (Measurement of volume fraction)
まず銀錫合金部含有粒子の塗設量の測定は、前記の膜厚測定で用いた各測定試 料を用い、この各測定試料における塗設量を蛍光 X線装置 3370E ( (株)理学製)を 用いて測定した。 First, the measurement of the coating amount of the silver-tin alloy part-containing particles is carried out by using each measurement test used in the film thickness measurement. The coating amount in each measurement sample was measured using a fluorescent X-ray apparatus 3370E (manufactured by Rigaku Corporation).
この値と、上で測定した膜厚を用いて、下記式により体積分率を計算した。各測定 試料の体積分率を表 1に示す。  Using this value and the film thickness measured above, the volume fraction was calculated by the following formula. Table 1 shows the volume fraction of each measurement sample.
銀錫合金部含有粒子の体積分率 = (銀錫合金部含有粒子の塗設量 Z  Volume fraction of silver-tin alloy part-containing particles = (coating amount Z of silver-tin alloy part-containing particles Z
銀錫合金部含有粒子の密度) Z膜厚  (Density of silver-tin alloy part-containing particles) Z film thickness
尚、銀錫合金部含有粒子の密度は、前述の方法により算出した。  In addition, the density of the silver tin alloy part containing particle | grains was computed by the above-mentioned method.
[0080] (XYZ表色色度座標 (X, y)の測定） [0080] (Measurement of XYZ color coordinate (X, y))
XYZ表色色度座標 (X, y)の測定は、分光光度計 OSP— SP200 (OLYMPUS (株)製 )を用い、前記のようにして行った。  Measurement of the XYZ color chromaticity coordinates (X, y) was performed as described above using a spectrophotometer OSP-SP200 (manufactured by OLYMPUS).
[0081] (青、赤、緑色画素の形成と画素の気泡の評価） [0081] (Formation of blue, red and green pixels and evaluation of bubbles in the pixels)
前記表示装置用遮光層付き基板の上に特開 2002— 341127号公報の段落 003 0から 0036に記載の R (R1)、 G (G1)、 B (B1)画素形成用感光性転写材料を用い る方法を用いて各色の画素を形成した。  R (R1), G (G1), and B (B1) pixel forming photosensitive transfer materials described in paragraphs 003 0 to 0036 of JP-A-2002-341127 are used on the substrate with a light shielding layer for the display device. Each color pixel was formed using the method described above.
表示装置用遮光層の凹凸の上に各色の画素を形成するので、ガラス基板と各色画 素の間に気泡が入る場合がある。この気泡発生程度を下記の方法で測定した。 このガラス基板の 3色の画素各 100個ずつ、合計 300個の画素について光学顕微 鏡を用いて目視で気泡の数を数えた。結果を表 1に示す。  Since the pixels of each color are formed on the unevenness of the light-shielding layer for the display device, bubbles may enter between the glass substrate and each color pixel. The degree of bubble generation was measured by the following method. The number of bubbles was counted visually using an optical microscope for a total of 300 pixels, 100 pixels of each of the three colors on this glass substrate. The results are shown in Table 1.
[0082] (加熱による表示装置用遮光層の色相変化） [0082] (Hue change of light shielding layer for display device by heating)
前記表示装置用遮光層付き基板を 220°Cで 2時間熱処理して、その熱処理前後の 表示装置用遮光層の色相の変化を目視で評価した。  The substrate with the light shielding layer for display device was heat-treated at 220 ° C. for 2 hours, and the change in hue of the light shielding layer for display device before and after the heat treatment was visually evaluated.
全く変化が見られないもの A  No change at all A
ごく僅かに金属光沢があるもの B  Slightly metallic luster B
僅かな金属光沢がある力 実用上許容されるもの C  Slight metallic luster power Practically acceptable C
実用使用で障害になる程度に金属光沢があるもの D  Metal luster that is an obstacle to practical use D
完全な金属光沢があるもの E  Full metal shine E
この中で実用上許容されるのは A〜Cのものである。結果を表 1に示す。  Among these, those that are practically acceptable are those of A to C. The results are shown in Table 1.
[0083] (色相の評価） 気泡評価に用いたカラーフィルタを後方力 液晶表示装置に組み込んで、黒色と 白色を表示した時のコントラスト差を目視で観察して下記のように分類した。 [0083] (Evaluation of hue) The color filter used for the bubble evaluation was incorporated into a rear force liquid crystal display device, and the contrast difference when displaying black and white was visually observed and classified as follows.
非常にコントラストが高く高品位 A  Very high contrast and high quality A
コントラストが高くかなり高品位 B  High contrast and high quality B
コントラストが低く中品位 C  Low contrast and medium quality C
コントラストが非常に低く低品位 D  Very low contrast and low quality D
結果を表 1に示す。  The results are shown in Table 1.
[0084] (比較例 1及び 2) [0084] (Comparative Examples 1 and 2)
実施例 1にて用いた銀錫合金部含有粒子の分散液 (分散液 A1)を、下記より得た 銀微粒子の分散液 (A2)に変更し、且つ感光層塗布液を下記処方のものに変更した 他は、実施例 1と同様にして表示装置用遮光層を作製した。結果を表 1に示す。  The silver tin alloy part-containing particle dispersion (dispersion A1) used in Example 1 was changed to the silver fine particle dispersion (A2) obtained from the following, and the photosensitive layer coating liquid was changed to the following formulation: A light shielding layer for a display device was produced in the same manner as in Example 1 except for the change. The results are shown in Table 1.
[0085] <銀微粒子の分散液 (A2)の調製 > [0085] <Preparation of silver fine particle dispersion (A2)>
(A液の調製）  (Preparation of solution A)
脱灰ゼラチン 50gに、蒸留水 1950gを添加し、得られた混合物を約 40°Cまで加熱 してゼラチンを溶解した。これを 5%NaOH水溶液で pH9. 2に調整し、 40°Cに保温 した。  1950 g of distilled water was added to 50 g of demineralized gelatin, and the resulting mixture was heated to about 40 ° C. to dissolve the gelatin. This was adjusted to pH 9.2 with 5% NaOH aqueous solution and kept at 40 ° C.
(B液の調製）  (Preparation of solution B)
脱灰ゼラチン 150gに、蒸留水 1350gを添加し、得られた混合物を約 40°Cまでカロ 熱してゼラチンを溶解した。これを 5%NaOH水溶液で pH9. 2に調整した。酢酸力 ルシゥム 16. Ogと蒸留水 320ccに溶解した硝酸銀 160gを攪拌して溶解し、蒸留水 を添加して、最終容積を 2000ccに調整し、 40°Cに保温した。  1350 g of distilled water was added to 150 g of demineralized gelatin, and the resulting mixture was heated to about 40 ° C. to dissolve the gelatin. This was adjusted to pH 9.2 with 5% NaOH aqueous solution. Acetic acid power Lucium 16. Og and 160 g of silver nitrate dissolved in 320 cc of distilled water were dissolved by stirring, distilled water was added to adjust the final volume to 2000 cc, and the temperature was kept at 40 ° C.
(C液の調製）  (Preparation of solution C)
亜硫酸ナトリウム（無水） l lOgを蒸留水 700ccに溶解し、これにハイドロキノン 80g をメタノール 70ccと水 80ccに溶解したものを混合し、さらに蒸留水を添加して、最終 容積を 2000cc【こ調整し、 40oG【こ保温した。 Sodium sulfite (anhydrous) l lOg dissolved in 700 cc distilled water, mixed with 80 cc hydroquinone dissolved in 70 cc methanol and 80 cc water, and further added distilled water to a final volume of 2000 cc 40 o G [This was kept warm.
[0086] 前記 A液を急速に攪拌しながら B液と C液を同時に 10秒かけて添加した。 10分後、 無水硫酸ナトリウム 1600gを濃塩酸 70ccと蒸留水 8000ccで溶解した溶液を添加し て、 80分攪拌した後、沈降させ、冷却した。上澄みを除去した後、 Br塩溶液を添加し ても沈殿ができなくなるまで、直ちに蒸留水でリンスした。水切り後、 40°Cで再溶解し た後、次いで生成物をゲルイ匕温度近くまで冷却し、そして小さな穴を通過させて冷却 した水の中へ入れ、それにより非常に微細なヌードルを形成した。 [0086] While rapidly stirring the solution A, the solution B and the solution C were added simultaneously over 10 seconds. After 10 minutes, a solution prepared by dissolving 1600 g of anhydrous sodium sulfate in 70 cc of concentrated hydrochloric acid and 8000 cc of distilled water was added and stirred for 80 minutes, and then allowed to settle and cooled. After removing the supernatant, add Br salt solution. Rinse immediately with distilled water until no precipitation was possible. After draining, after re-dissolving at 40 ° C, the product was then cooled to near the gel temperature and passed through a small hole into the cooled water, thereby forming a very fine noodle .
これを、亜硫酸ナトリウム（無水） 20g、 NaOHO. 6gを蒸留水 2000ccに溶解した溶 液で洗浄し、さらに氷酢酸 20gを蒸留水 2000ccに溶解した溶液で洗浄した。得られ た黒色スラリー粒子を、ナイロンメッシュバック中でスラリーを介して水道水を通過させ 、約 30分間洗浄水がバックを通過するようにして洗浄し、すべての塩を洗い流した。 ゲルスラリーに分散させ洗浄した黒色銀を、溶融した場合に 1. 5%の濃度の銀を有 する黒色銀分散体が得られるように、生成物の水気を切った。  This was washed with a solution of 20 g of sodium sulfite (anhydrous) and 6 g of NaOHO. In 2000 cc of distilled water, and further washed with a solution of 20 g of glacial acetic acid in 2000 cc of distilled water. The resulting black slurry particles were passed through the slurry in a nylon mesh bag through the tap water and washed for about 30 minutes with the wash water passing through the bag to wash away all the salt. The product was drained so that when the black silver dispersed and washed in the gel slurry was melted, a black silver dispersion with a concentration of 1.5% silver was obtained.
[0087] (銀微粒子分散液 A2の作製） [0087] (Preparation of silver fine particle dispersion A2)
上記の如くして得られた銀分散スラリー 5000gに、分散剤（ラピゾール B— 90、日 本油脂 (株)製） 25gとパパイン 5%水溶液 lOOOgを添加し、 37°Cで 24時間保存した 。この液を 2000rpmで 5分間遠心分離し、銀微粒子を沈降させた。上澄みを棄てた 後蒸留水で洗浄して、酵素で分解されたゼラチン分解物を除いた。次いで銀微粒子 沈降物をメチルアルコールで洗浄してカゝら乾燥させた。約 85gの銀微粒子の凝集物 が得られた。この凝集物 73. 5gにソルスパース 20000 (アビシァ (株)製 分散剤） 1. 05gとメチルェチルケトン 16. 4gを混合した。これをビーズ分散機（ジルコ-ァビーズ 0. 3mm)を用いて平均粒径 30nmの銀微粒子分散液 A2を得た。  To 5000 g of the silver dispersion slurry obtained as described above, 25 g of a dispersant (Lapisol B-90, manufactured by Nippon Oil & Fats Co., Ltd.) and lOOOg of a 5% papain aqueous solution were added and stored at 37 ° C. for 24 hours. This solution was centrifuged at 2000 rpm for 5 minutes to precipitate silver fine particles. After discarding the supernatant, it was washed with distilled water to remove the gelatin degradation product degraded by the enzyme. Next, the silver fine particle sediment was washed with methyl alcohol and dried. Approximately 85 g of silver fine particle agglomerates were obtained. 10.5 g of Solsperse 20000 (Abisia Co., Ltd. dispersant) and 16.4 g of methyl ethyl ketone were mixed with 73.5 g of this aggregate. This was used to obtain a silver fine particle dispersion A2 having an average particle size of 30 nm using a bead disperser (Zircoa beads 0.3 mm).
[0088] <感光層塗布液の調製 > <Preparation of photosensitive layer coating solution>
上記より作製した銀微粒子分散液 A2に下記の成分を添加し、比較例 1及び比較 例 2で用いる感光層塗布液を調製した。尚、実施例 1と同様に、ジペンタエリスリトー ルへキサアタリレートの添加量は、体積分率が表 1に記載の値となるように調節した。 '銀微粒子分散液 A2 40. Og  The following components were added to the silver fine particle dispersion A2 prepared as described above to prepare photosensitive layer coating solutions used in Comparative Examples 1 and 2. In the same manner as in Example 1, the amount of dipentaerythritol hexaatalylate added was adjusted so that the volume fraction became the value shown in Table 1. 'Silver fine particle dispersion A2 40. Og
•プロピレングリコールモノメチルエーテルアセテート 40. 0g  Propylene glycol monomethyl ether acetate 40.0 g
•メチルェチルケトン 37. 6g  • Methyl ethyl ketone 37. 6g
• F— 780—F (大日本インキ化学工業 (株)製、  • F—780—F (Dainippon Ink Chemical Co., Ltd.,
30%メチルェチルケトン溶液） 0. 2g  30% methyl ethyl ketone solution) 0.2 g
'ヒドロキノンモノメチルエーテル 0. 001g .ジペンタエリスリトールへキサアタリレート 'Hydroquinone monomethyl ether 0.001 g Dipentaerythritol hexaatalylate
銀微粒子の体積分率が表 1記載の値となるよう添カロ  Add the calorie content so that the volume fraction of the silver particles
'ビス [4— [N— [4— (4、 6—ビストリクロロメチル一 s—トリァジン一 2—ィル）フエ-ル ]力ルバモイル]フエ-ル]セバケート 0. lg  'Bis [4— [N— [4— (4, 6-bistrichloromethyl 1 s-triazine 1 2-yl) file] force rubermoyl] file] sebacate 0. lg
[0089] (比較例 3) [0089] (Comparative Example 3)
実施例 3において銀錫合金部含有粒子の体積分率を一定 (0. 39)のままにし、銀 錫合金部含有粒子を分散した銀錫合金部含有粒子分散液 A1の代わりに、平均粒 径 30nmのカーボン微粒子を分散したカーボン微粒子分散液を用いた他は、実施例 3と同様にして表示装置用遮光層を作製した。結果を表 1に示す。  Instead of the silver-tin alloy part-containing particle dispersion A1 in which the volume fraction of the silver-tin alloy part-containing particles was kept constant (0.39) in Example 3 and the silver-tin alloy part-containing particles were dispersed, the average particle diameter was changed. A light shielding layer for a display device was produced in the same manner as in Example 3 except that a carbon fine particle dispersion in which 30 nm carbon fine particles were dispersed was used. The results are shown in Table 1.
カーボンブラックを用いたこの比較例では、気泡の数が増加し、実用レベルではな かった。  In this comparative example using carbon black, the number of bubbles increased and was not at a practical level.
[0090] [表 1] [0090] [Table 1]
Figure imgf000031_0001
Figure imgf000031_0001
[0091] 表 1に示すように、実施例の表示装置用遮光層は、 1 μ m以下の薄膜であっても高 い光学濃度を有し、黒の色相に優れ、また該色相は加熱によって変化せず、更に、 カラーフィルタを作製した際にも気泡の発生がなくあるいは少なぐ全体的に優れた 特性を有し、実用レベルを満たしていた。 [0091] As shown in Table 1, the light-shielding layer for the display device of the example has a high optical density even in a thin film of 1 μm or less, excellent in a black hue, and the hue is obtained by heating. In addition, even when a color filter was produced, it had excellent characteristics as a whole with little or no generation of bubbles, and met the practical level.
一方、銀錫合金部含有粒子の代わりに銀微粒子を用い、体積分率が 0. 02の比較 例 1では気泡の数が増加し、体積分率が 0. 73の比較例 2では加熱後の色相が大き く変化し、両方とも実用レベルではな力 た。また、カーボンブラックを用いた比較例 3では、気泡の数が増加し、実用レベルではなかった。  On the other hand, instead of the silver-tin alloy part-containing particles, silver fine particles were used. In Comparative Example 1 with a volume fraction of 0.02, the number of bubbles increased, and in Comparative Example 2 with a volume fraction of 0.73, Hue changed greatly, both of which were not practical. In Comparative Example 3 using carbon black, the number of bubbles increased and was not at a practical level.
[0092] (実施例 6〜： L0)  [0092] (Example 6-: L0)
実施例 3にて用いた銀錫合金部含有粒子分散液 A1中の銀錫合金部含有粒子の 平均粒子サイズを、それぞれ 20nm、 60nm、 100nm、 250nm及び 500nmのものと した他は、実施例 3と同様にして表示装置用遮光層を形成した。結果を表 2に示す。 光学濃度、膜厚、黒の色相、色相の加熱変化、気泡の点において、実用レベルを 満たしていた。  Example 3 except that the average particle size of the silver-tin alloy part-containing particles in the silver-tin alloy part-containing particle dispersion A1 used in Example 3 was 20 nm, 60 nm, 100 nm, 250 nm, and 500 nm, respectively. In the same manner, a light shielding layer for a display device was formed. The results are shown in Table 2. The optical density, film thickness, black hue, heating change of hue, and bubbles were met with practical levels.
[0093] [表 2] [0093] [Table 2]
Figure imgf000033_0001
Figure imgf000033_0001
[0094] (実施例 11〜20) [0094] (Examples 11 to 20)
実施例 1〜10において、感光層の上に保護層を設けない他は、それぞれ実施例 1 〜10と同様にして、表示装置用遮光層を作製した。これらの試料は超高圧水銀灯を 用いた 70miZcm2の露光では表示装置用遮光層が形成できな力つた力 500mi/ cm2の露光で良好な表示装置用遮光層が得られた。そのため、膜厚測定、光学濃度 の測定及び体積分率の測定に用いる試料を作製する際にも、露光条件を 70mjZc m2から 500mj/cm2に変更した。結果を表 3に示す。 In Examples 1 to 10, display device light-shielding layers were prepared in the same manner as in Examples 1 to 10 except that no protective layer was provided on the photosensitive layer. In these samples, a good light-shielding layer for a display device was obtained by exposure at a force of 500 mi / cm 2 , which was impossible to form a light-shielding layer for a display device by exposure at 70 miZcm 2 using an ultra-high pressure mercury lamp. Therefore, the exposure conditions were changed from 70 mjZcm 2 to 500 mj / cm 2 when preparing samples used for film thickness measurement, optical density measurement and volume fraction measurement. The results are shown in Table 3.
[0095] (比較例 4〜6)  [0095] (Comparative Examples 4 to 6)
比較例 1〜3において、感光層の上に保護層を設けない他は、それぞれ比較例 1 〜3と同様にして表示装置用遮光層を作製した。これらの試料は超高圧水銀灯を用 いた 70miZcm2の露光では表示装置用遮光層が形成できなかった力 500mi/c m2の露光では表示装置用遮光層が得られた。そのため、膜厚測定、光学濃度の測 定及び体積分率の測定も 70mj/cm2から 500mj/cm2の露光に変更して同様に測 定した。比較例 4〜6から製作された表示用遮光層は、比較例 1〜3と同様に実用レ ベルではなカゝつた。結果を表 3に示す。 In Comparative Examples 1 to 3, display device light-shielding layers were prepared in the same manner as Comparative Examples 1 to 3, except that no protective layer was provided on the photosensitive layer. In these samples, a shading layer for a display device could not be formed by an exposure of 70 miZcm 2 using an ultra-high pressure mercury lamp, and a shading layer for a display device was obtained by exposure at a force of 500 mi / cm 2 . Therefore, film thickness measurement, optical density measurement, and volume fraction measurement were also performed by changing from 70 mj / cm 2 to 500 mj / cm 2 exposure. The display light-shielding layers produced from Comparative Examples 4 to 6 were not practical at the same level as Comparative Examples 1 to 3. The results are shown in Table 3.
[0096] [表 3] [0096] [Table 3]
Figure imgf000035_0001
Figure imgf000035_0001
[0097] (実施例 21〜30) [0097] (Examples 21 to 30)
これらの各実施例においては、感光性転写材料を用 、て表示装置用遮光層を作 製した。  In each of these Examples, a photosensitive transfer material was used to produce a light shielding layer for a display device.
[感光性転写材料の作製]  [Preparation of photosensitive transfer material]
感光性転写材料は、 2軸延伸した 75 m厚みのポリエチレンテレフタレート支持体 にスライドコーターを用いて乾燥膜厚が Ιδ πιになるように下記熱可塑性榭脂層塗 布液を塗布して 100°Cで 5分間乾燥した。次いで、この膜の上に中間層塗布液を乾 燥膜厚が 1. になるように塗布して 100°Cで 5分間乾燥し、さらに感光層塗布液 を塗布して 100°Cで 5分間乾燥した。  The photosensitive transfer material is a biaxially stretched 75 m thick polyethylene terephthalate support using a slide coater to apply the following thermoplastic resin layer coating solution to a dry film thickness of Ιδ πι at 100 ° C. And dried for 5 minutes. Next, an intermediate layer coating solution is applied onto this film so that the dry film thickness is 1. The coating solution is dried at 100 ° C for 5 minutes, and further a photosensitive layer coating solution is applied at 100 ° C for 5 minutes. Dried.
実施例 21〜30における感光層塗布液は、実施例 1〜10に各々対応する同じ組成 の感光層塗布液を用いた。また、中間層塗布液処方は、実施例 1の保護層塗布液と 同じ組成の塗布液を用いた。以下に、熱可塑性榭脂層塗布液の組成を示す。  As the photosensitive layer coating solutions in Examples 21 to 30, photosensitive layer coating solutions having the same compositions corresponding to Examples 1 to 10, respectively, were used. In addition, as the intermediate layer coating solution formulation, a coating solution having the same composition as that of the protective layer coating solution of Example 1 was used. The composition of the thermoplastic resin layer coating solution is shown below.
[0098] (熱可塑性榭脂層塗布液） [0098] (Thermoplastic resin layer coating solution)
•メチルメタタリレート /2—ェチルへキシルアタリレート/ベンジルメタタリレート/メタ クリル酸共重合体 (共重合組成比（モル比） =55Zll. 7/4. 5/28. 8、分子量 = 9万、 Tg 70。C) 58咅  • Methyl methacrylate / 2-ethyl etherylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55Zll. 7/4. 5 / 28.8, molecular weight = 9 10,000, Tg 70. C) 58 咅
•スチレン Zアクリル酸 = 70Z30の共重合体 (共重合組成比（モル比）  • Copolymer of styrene Z acrylic acid = 70Z30 (copolymerization composition ratio (molar ratio)
= 63,37、分子量 = 1万、 Tg 100。 136部  = 63,37, molecular weight = 10,000, Tg 100. 136 copies
•2, 2—ビス [4— (メタクリロキシポリエトキシ）フエ-ル]プロパン  • 2, 2-bis [4- (methacryloxypolyethoxy) phenol] propane
(新中村化学株製、多官能アタリレート） 90部 •F— 780— F (大日本インキ化学工業 (株)製、フッ素系界面活性剤） 1部 (Shin-Nakamura Chemical Co., Ltd., polyfunctional acrylate) 90 parts • F— 780— F (Dainippon Ink & Chemicals, Fluorosurfactant) 1 part
•メチルェチルケトン 541部 • Methyl ethyl ketone 541 parts
•1—メトキシ一 2—プロパノール 63部  • 1-Methoxy-1-2-propanol 63 parts
'メチルアルコール 111部  'Methyl alcohol 111 parts
[0099] [表示装置用遮光層の作製] [0099] [Preparation of light shielding layer for display device]
無アルカリガラス基板を、 25°Cに調整したガラス洗浄剤液をシャワーにより 20秒間 吹き付けながらナイロン毛を有する回転ブラシで洗浄し、純水シャワー洗浄後、シラ ンカップリング液 (N— β (アミノエチル） γ—ァミノプロピルトリメトキシシラン 0. 3質量 %水溶液、商品名： KBM603、信越ィ匕学工業 (株)製)をシャワーにより 20秒間吹き 付け、純水シャワー洗浄した。この基板を基板予備加熱装置で 100°C2分加熱して 次のラミネーターに送った。 A non-alkali glass substrate is cleaned with a rotating brush with nylon bristles while spraying a glass detergent solution adjusted to 25 ° C for 20 seconds with a shower. After pure water shower cleaning, the silane coupling solution (N-β (amino Ethyl) γ -aminopropyltrimethoxysilane 0.3 mass % Aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C for 2 minutes with a substrate preheating device and sent to the next laminator.
前記ガラス基板と銀錫合金部含有粒子含有層（即ち、感光層）が接触するようにガ ラス基板と前記感光性転写材料を重ね合わせ、ラミネーター（(株）日立インダストリィ ズ製 (LamicII型)）を用いて両者を貼り合わせた。ラミネートは、 100°Cに加熱した基 板に、ゴムローラー温度 130°C、線圧 100NZcm、搬送速度 2. 2mZ分でラミネート した。その後ポリエチレンテレフタレート支持体を剥離した。  The glass substrate and the photosensitive transfer material are overlapped so that the glass substrate and the silver tin alloy part-containing particle-containing layer (ie, photosensitive layer) are in contact with each other, and a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) ) Were used to bond them together. Lamination was performed on a substrate heated to 100 ° C at a rubber roller temperature of 130 ° C, a linear pressure of 100 NZcm, and a conveyance speed of 2.2 mZ. Thereafter, the polyethylene terephthalate support was peeled off.
[0100] 仮支持体を熱可塑性榭脂層との界面で剥離後、超高圧水銀灯を有するプロキシミ ティー型露光機 (日立ハイテク電子エンジニアリング (株)製)で、基板とマスク (画像 パターンを有す石英露光マスク）を垂直に立てた状態で、露光マスク面と該熱可塑性 榭脂層の間の距離を 200 mに設定し、露光量 70miZcm2でパターン露光した。 [0100] After the temporary support is peeled off at the interface with the thermoplastic resin layer, the substrate and mask (with image pattern) are used with a proximity-type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp With the quartz exposure mask standing vertically, the distance between the exposure mask surface and the thermoplastic resin layer was set to 200 m, and pattern exposure was performed at an exposure dose of 70 miZcm 2 .
[0101] 次に、トリエタノールアミン系現像液（2. 5%のトリエタノールァミン含有、ノ-オン界 面活性剤含有、ポリプロピレン系消泡剤含有、商品名： T PD1、富士写真フィルム ( 株)製を純水で 12倍に希釈した液）にて 30°C50秒、フラットノズル圧力 0. 04MPaで シャワー現像し熱可塑性榭脂層と中間層を除去した。 [0101] Next, a triethanolamine developer (containing 2.5% triethanolamine, containing a non-ionic surfactant, containing a polypropylene antifoaming agent, trade name: TPD1, Fuji Photo Film ( Shown and developed at 30 ° C for 50 seconds with a flat nozzle pressure of 0.04 MPa, and the thermoplastic resin layer and the intermediate layer were removed.
引き続き炭酸 Na系現像液 (0. 06モル Zリットルの炭酸水素ナトリウム、同濃度の炭 酸ナトリウム、 1%のジブチルナフタレンスルホン酸ナトリウム、ァ-オン界面活性剤、 消泡剤、安定剤含有、商品名： T CD1、富士写真フィルム (株)製を純水で 5倍に 希釈した液）を用い、 29°C30秒、コーン型ノズル圧力 0. 15MPaでシャワー現像し 感光性榭脂層を現像しパターユング画像を得た。  Subsequently, sodium carbonate developer (0.06 mol Z liters of sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, char-on surfactant, antifoaming agent, stabilizer, product Name: TCD1, Fuji Photo Film Co., Ltd. (diluted 5 times with pure water), shower developed at 29 ° C for 30 seconds and cone type nozzle pressure 0.15 MPa to develop the photosensitive resin layer I got a Patterung image.
弓 Iき続き洗浄剤 (燐酸塩 ·珪酸塩 ·ノ-オン界面活性剤 ·消泡剤 ·安定剤含有、商品 名「T—SD1 (富士写真フィルム (株)製を純水で 10倍に希釈した液)を用い、 33°C で 20秒、コーン型ノズル圧力 0. 02MPaでシャワーとナイロン毛を有す回転ブラシに より残渣除去を行い、ブラック (K)の画像を得た。その後更に、該基板に対して該榭 脂層の側力も超高圧水銀灯で 500miZcm2の光でポスト露光後、 220°Cで 15分熱 処理し、遮光層を形成した。 Bow I Continued Detergent (Phosphate · Silicate · Nonionic Surfactant · Antifoam · Stabilizer Contained, Product Name "T-SD1" (Fuji Photo Film Co., Ltd. diluted 10 times with pure water) The residue was removed using a rotating brush with a shower and nylon bristles at a cone-type nozzle pressure of 0.02 MPa at 33 ° C for 20 seconds to obtain a black (K) image. The lateral force of the resin layer with respect to the substrate was post-exposure with an ultrahigh pressure mercury lamp with light of 500 miZcm 2 and then heat-treated at 220 ° C. for 15 minutes to form a light shielding layer.
[0102] 膜厚測定、光学濃度の測定及び体積分率の測定に用いる試料を作製する際の露 光条件も同様に 70mj/cm2とした。結果を表 4に示す。 [0102] Dew when producing samples used for film thickness measurement, optical density measurement and volume fraction measurement Similarly, the light conditions were set to 70 mj / cm 2 . The results are shown in Table 4.
[0103] (比較例 7〜9) [0103] (Comparative Examples 7 to 9)
実施例 21の表示装置用遮光層の作製において、感光層塗布液として用いた実施 例 1の感光層塗布液の代わりに、比較例 1〜3で用いた感光層塗布液をそれぞれ用 いた他は、実施例 21と同様にして表示装置用遮光層を作製した。結果を表 4に示す 比較例 7〜9から得られた表示装置用遮光層は、比較例 1〜3と同様、実用レベル ではなかった。  In the production of the light-shielding layer for display device of Example 21, the photosensitive layer coating solution used in Comparative Examples 1 to 3 was used instead of the photosensitive layer coating solution of Example 1 used as the photosensitive layer coating solution, respectively. Then, a light shielding layer for a display device was produced in the same manner as in Example 21. The results are shown in Table 4. The light-shielding layers for display devices obtained from Comparative Examples 7 to 9 were not at a practical level as in Comparative Examples 1 to 3.
[0104] [表 4] [0104] [Table 4]
Figure imgf000039_0001
Figure imgf000039_0001
[0105] 表 1ないし表 4が示すように、本発明の要件を満たす着色組成物からは、 0. 1 m に近い非常に薄い層でも光学濃度が高ぐ黒の色相に優れ、また加熱を受けた場合 でも色相変化が小さい表示装置用遮光層が得られる。また、必要な光学濃度を得る ための表示装置用遮光層の膜厚が小さいため、表示装置用遮光層付き基板の上に カラーフィルタ画素を作製する際に巻き込む気泡の数も少ない。 [0105] As shown in Tables 1 to 4, the coloring composition satisfying the requirements of the present invention is excellent in black hue with high optical density even in a very thin layer close to 0.1 m, and is heated. Even when it is received, a light shielding layer for a display device having a small hue change can be obtained. In addition, since the thickness of the light shielding layer for a display device for obtaining a necessary optical density is small, the number of bubbles entrained when a color filter pixel is formed on a substrate with a light shielding layer for a display device is small.
これに対し、黒色顔料としてカーボンブラックを用いた場合、その平均粒径及び体 積分率を本件発明と同じにしても、 C光源透過光の XYZ表色系色度座標に関する 条件を達成することができず、その結果、表示装置用遮光層の色相が劣るものとなり 、また、同じ光学濃度を達成するための膜厚も大きくなる。  On the other hand, when carbon black is used as the black pigment, the condition regarding the XYZ color system chromaticity coordinates of the C light source transmitted light can be achieved even if the average particle size and volume fraction are the same as in the present invention. As a result, the hue of the light shielding layer for the display device is inferior, and the film thickness for achieving the same optical density is also increased.
上記で作製した表示装置用遮光層を用いて、 WO2006 - 38731の実施例 1に記 載の方法により RGB画素を形成し、次 、で液晶表示装置を作製した。  Using the light shielding layer for a display device produced above, RGB pixels were formed by the method described in Example 1 of WO2006-38731, and then a liquid crystal display device was produced.
実施例で作製した表示装置用遮光層を用いた液晶表示装置は、比較例で作製した 表示装置用遮光層を用いた液晶表示装置に比べて色ムラもなく高表示品位であつ た。  The liquid crystal display device using the light-shielding layer for display device produced in the example was high in display quality without color unevenness compared with the liquid crystal display device using the light-shielding layer for display device produced in the comparative example.
産業上の利用可能性  Industrial applicability
[0106] 本発明の着色組成物は、薄膜で遮光性能が高ぐ低コストで、環境への影響が少 なぐ黒色 (色味がつかず無彩色)の色相に優れた表示装置用遮光層の作製に有用 である。また、本発明により得られる表示装置用遮光層は、加熱による色相変化もな いか非常に少ないので、平坦性に優れ、 RGB画素を形成する際に気泡が混入する ことがな 、かある!/、は非常に少な 、カラーフィルタを作製することが可能である。さら に、このカラーフィルタは、液晶表示装置の作製にも用いられる。 [0106] The colored composition of the present invention is a light-shielding layer for a display device having a thin film, high light-shielding performance, low cost, and low black environmental impact (colorless and achromatic). Useful for production. In addition, the light-shielding layer for a display device obtained according to the present invention has very little or no hue change due to heating, so it has excellent flatness, and bubbles may not be mixed in forming RGB pixels! / It is possible to produce a color filter with very little. Furthermore, this color filter is also used for manufacturing a liquid crystal display device.

Claims

請求の範囲 The scope of the claims
[I] 銀錫合金部を有する金属粒子を含有し、膜形成後の光学濃度が、乾燥膜厚 1 μ m 当たり 3. 5以上であることを特徴とする着色組成物。  [I] A coloring composition comprising metal particles having a silver-tin alloy part and having an optical density after film formation of 3.5 or more per 1 μm of dry film thickness.
[2] 前記銀錫合金部を有する金属粒子の固形分中の体積分率が 0. 05〜0. 7であり、 かつ着色組成物を塗布して形成される遮光層にお ヽて、 C光源透過光の XYZ表色 系色度座標 (X, y)と、前記光源の色度座標 (X , y )  [2] The volume fraction in the solid content of the metal particles having the silver-tin alloy portion is 0.05 to 0.7, and in the light-shielding layer formed by applying the coloring composition, C XYZ color system chromaticity coordinates (X, y) of transmitted light and chromaticity coordinates (X, y) of the light source
0 0と力 (x - x ) 2 + (y-y ) 2≤0. 0 0 and force (x-x) 2 + (yy) 2 ≤0.
0 0 0 0
01の関係を有することを特徴とする請求項 1に記載の着色組成物。 The coloring composition according to claim 1, which has a relationship of 01.
[3] 前記銀錫合金部を有する金属粒子の平均粒径が 500nm以下であることを特徴と する請求項 1に記載の着色組成物。 [3] The colored composition according to [1], wherein the metal particles having the silver-tin alloy part have an average particle size of 500 nm or less.
[4] 前記銀錫合金部を有する金属粒子の平均粒径が 500nm以下であることを特徴とす る請求項 2に記載の着色組成物。 [4] The colored composition according to claim 2, wherein an average particle diameter of the metal particles having the silver-tin alloy part is 500 nm or less.
[5] 感光性を有することを特徴とする請求項 1に記載の着色組成物。 [5] The colored composition according to claim 1, which has photosensitivity.
[6] 感光性を有することを特徴とする請求項 2に記載の着色組成物。 6. The colored composition according to claim 2, which has photosensitivity.
[7] 支持体と、その支持体上に少なくとも感光性遮光層を設けており、該感光性遮光層 が銀錫合金部を有する金属粒子を含み、感光性遮光層の光学濃度が、乾燥膜厚 1 μ m当たり 3. 5以上であり、感光性遮光層中の銀錫合金部を有する金属粒子の体 積分率が 0. 05-0. 7であり、かつ遮光層の C光源透過光の XYZ表色系色度座標（ X, y)と、前記光源の色度座標 (X , y )とが、 (x - x ) 2 + (y-y ) 2≤0. 01の関係を [7] A support, and at least a photosensitive light-shielding layer provided on the support, the photosensitive light-shielding layer containing metal particles having a silver-tin alloy part, and the optical density of the photosensitive light-shielding layer being a dry film The volume fraction of metal particles having a silver-tin alloy part in the photosensitive light-shielding layer is 3.5 or more per 1 μm, and 0.05-0.7. The XYZ color system chromaticity coordinates (X, y) and the chromaticity coordinates (X, y) of the light source satisfy the relationship of (x-x) 2 + (yy) 2 ≤0.01
0 0 0 0  0 0 0 0
有することを特徴とする感光性転写材料。  A photosensitive transfer material comprising:
[8] 請求項 1に記載の着色組成物を用いて作製される表示装置用遮光層。  [8] A light-shielding layer for a display device, produced using the colored composition according to claim 1.
[9] 請求項 2に記載の着色組成物を用いて作製される表示装置用遮光層。 [9] A light-shielding layer for a display device, produced using the colored composition according to claim 2.
[10] 請求項 5に記載の着色組成物を用いて作製される表示装置用遮光層。 [10] A light-shielding layer for a display device produced using the colored composition according to claim 5.
[II] 請求項 6に記載の着色組成物を用いて作製される表示装置用遮光層。  [II] A light-shielding layer for a display device produced using the colored composition according to claim 6.
[12] 請求項 7に記載の感光性転写材料を用いて作製される表示装置用遮光層。 [12] A light shielding layer for a display device, produced using the photosensitive transfer material according to claim 7.
[13] 光透過性基板と、この基板上に、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表示装置用遮光層により 離画され、前記表示装置用遮光層が請求項 8に記載の表示装置用遮光層であること を特徴とするカラーフィルタ。 [13] A light-transmitting substrate and two or more pixel groups that are formed of a colored layer on the substrate and exhibit different colors, and each pixel constituting the pixel group is separated from each other by a light-shielding layer for a display device. A color filter, wherein the display device light-shielding layer is the display device light-shielding layer according to claim 8.
[14] 少なくとも 1つが光透過性を有する 1対の基板と、その基板の間に、カラーフィルタ、 液晶層および液晶駆動手段を少なくとも備え、前記カラーフィルタ力 請求項 13に記 載のカラーフィルタであることを特徴とする液晶表示素子。 [14] The color filter according to claim 13, comprising at least one pair of substrates having light transparency, and at least a color filter, a liquid crystal layer, and a liquid crystal driving means between the substrates. There is a liquid crystal display element.
[15] 少なくとも 1つが光透過性を有する 1対の基板と、その基板の間に、カラーフィルタ、 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 を有し、各アクティブ素子の間に請求項 8に記載の表示装置用遮光層が形成されて V、ることを特徴とする液晶表示素子。  [15] A pair of substrates, at least one of which is light transmissive, and at least a color filter, a liquid crystal layer, and a liquid crystal driving unit between the substrates, wherein the liquid crystal driving unit includes an active element, and each active element A liquid crystal display element, wherein the light-shielding layer for a display device according to claim 8 is formed between them.
[16] 光透過性基板の上に、請求項 1に記載の着色組成物力 の層を形成する工程、及 び表示装置用遮光層用フォトマスクを介して前記層を露光した後現像する工程を有 する表示装置用遮光層の製造方法。  [16] A step of forming a colored composition strength layer according to claim 1 on a light-transmitting substrate, and a step of developing the layer after exposure through a photomask for a light-shielding layer for a display device A method for producing a light shielding layer for a display device.
[17] 光透過性基板の上に、請求項 2に記載の着色組成物力 の層を形成する工程、及 び表示装置用遮光層用フォトマスクを介して前記層を露光した後現像する工程を有 する表示装置用遮光層の製造方法。  [17] A step of forming a colored composition strength layer according to claim 2 on a light-transmitting substrate, and a step of developing the layer after exposure through a photomask for a light-shielding layer for a display device A method for producing a light shielding layer for a display device.
[18] 光透過性基板の上に、支持体に少なくとも感光性遮光層を設けた請求項 7に記載 の感光性転写材料を、前記感光性遮光層が接するように積層する工程、前記感光 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する工程、及び表示装置 用遮光層用フォトマスクを介して前記感光性遮光層を露光した後現像する工程を有 する表示装置用遮光層の製造方法。  [18] The step of laminating the photosensitive transfer material according to claim 7, wherein at least a photosensitive light-shielding layer is provided on a support on a light-transmitting substrate, so that the photosensitive light-shielding layer is in contact with the photosensitive material. Light shielding for a display device, comprising a step of peeling a support from a laminate of a transfer material and a light transmissive substrate, and a step of developing after exposing the photosensitive light shielding layer through a photomask for the light shielding layer for a display device. Layer manufacturing method.
[19] 光透過性基板及び該基板の上に設けられた表示装置用遮光層を有し、前記表示 装置用遮光層中に銀錫合金部を有する金属粒子が体積分率 0. 05〜0. 7で分散さ れており、表示装置用遮光層 1 m当たりの光学濃度が 3. 5以上であり、かつ、表示 装置用遮光層の C光源透過光の XYZ表色系色度座標 (X, y)と、前記光源の色度座 標 (x , y )とが、 (x-x ) 2+ (y-y ) 2≤0. 01の関係を有することを特徴とする表示[19] A light-transmitting substrate and a light-shielding layer for a display device provided on the substrate, and the metal particles having a silver-tin alloy portion in the light-shielding layer for a display device are in a volume fraction of 0.05 to 0 XYZ color system chromaticity coordinates (X) of the light transmitted through the C light source of the light shielding layer for the display device, and the optical density per meter of the light shielding layer for the display device is 3.5 or more. , y) and the chromaticity coordinates (x, y) of the light source have a relationship of (xx) 2 + (yy) 2 ≤0.01
0 0 0 0 0 0 0 0
装置用遮光層付き基板。  Substrate with light shielding layer for equipment.
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