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CN101268151A - Colored composition and photosensitive transfer material - Google Patents

Colored composition and photosensitive transfer material Download PDF

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Publication number
CN101268151A
CN101268151A CNA2006800341739A CN200680034173A CN101268151A CN 101268151 A CN101268151 A CN 101268151A CN A2006800341739 A CNA2006800341739 A CN A2006800341739A CN 200680034173 A CN200680034173 A CN 200680034173A CN 101268151 A CN101268151 A CN 101268151A
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China
Prior art keywords
light shield
shield layer
display unit
silver
layer
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Granted
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CNA2006800341739A
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CN101268151B (en
Inventor
畠山晶
后藤英范
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Fujifilm Corp
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Powder Metallurgy (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

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 [mu]m 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

Coloured composition and photosensitive transfer printing material
Technical field
The present invention relates to their display unit of coloured composition and photosensitive transfer printing material and use and use the substrate of light shield layer with light shield layer and manufacture method, colour filter, liquid crystal display device and band display unit.
Background technology
The colour filter that uses in colour liquid crystal display device etc. forms colored pixels layer (R, G, B) on transparency carrier, then, to show contrast gradient etc. and in the gap of each colored pixels of R, G, B (red, green, blue), form the display unit light shield layer in order to improve.Particularly in the liquid crystal display device of the driven with active matrix mode of using thin film transistor (TFT), the electric current that causes for the light that prevents along with thin film transistor leaks and the reduction of the picture quality that takes place, also needs display unit to have high opacifying property with light shield layer.
As the formation method of display unit, for example comprise the method for metallic membranes such as chromium as light shield layer with light shield layer.Under the situation that is this method, utilize vapour deposition method or sputtering method that metallic film is formed metallic membrane.On this metallic film, apply photo-resist, then use to have the photomask of display unit, the photo-resist layer is carried out exposure imaging with the pattern of light shield layer.Then, the metallic film that etching is exposed at last by the resist layer on the stripping metal film, forms light shield layer (for example with reference to non-patent literature 1).
This method so even thickness is thin, also can obtain shaded effect, on the contrary, must be called as the vacuum film formation operation or the etching work procedure of vapour deposition method or sputtering method owing to use metallic film, can not ignore the problems such as burden to environment when existing cost to uprise.In addition, owing to be metallic membrane, the reflectivity height under strong outer light, shows that contrast gradient is low.As its countermeasure, use low reflective chrome film (by 2 layers of chromium film that constitutes of chromium metal and chromic oxide etc.).But, its countermeasure and then the problem of following cost to improve.
In addition, as display unit other formation methods with light shield layer, also known have use to contain for example method of sooty photosensitive polymer combination of opacifying property pigment.This method is for example to form on transparency carrier after R, G, the B pixel, coating contains the carbon black photosensitive polymer combination on this pixel, and the display unit of carrying out the self-aligned manner of blanket exposure from the non-formation face side of R, G, B pixel of transparency carrier forms method (for example with reference to patent documentation 1) with light shield layer.
This method is compared with the etching method that utilizes of described metallic membrane, although the manufacturing cost step-down, in order to obtain sufficient opacifying property, the thickness thickening.As a result, overlap (staggered floor) between display unit is with light shield layer and R, G, B pixel, the unit interval inequality of liquid crystal display device takes place in the flatness variation of colour filter, causes that look unequal demonstration is bad.
In addition, contain sooty photosensitive polymer combination making display unit light shield layer, form rgb pixel then, then the display unit thickness thickening of light shield layer if on substrate, use at first.Thereby, when forming rgb pixel, defectives such as bubble take place to produce sometimes.
In addition, use the sooty display unit in black tone, to reserve hardly with regard to one with light shield layer.
On the other hand, also known have an inner method (with reference to patent documentation 2) of disperseing the display unit of the metallics that shading uses with light shield layer equably that is produced on.In the method, at first on transparency carrier, form the photosensitivity resist layer that contains hydrophilic resin.Then,, carry out exposure imaging, on transparency carrier, form relief via having the photomask of display unit with the pattern of light shield layer.Then, this transparency carrier is contacted with the aqueous solution of the metallic compound of the catalyzer that becomes electroless plating, in relief, contain metallic compound, drying.After the drying, implement thermal treatment, then, contact with electroless plating liquid by making the relief on the described transparency carrier, can obtain metallics that the shading of particle diameter 0.01～0.05 μ m uses within it portion disperse the display unit light shield layer that forms equably.As described metallics, can enumerate nickel, cobalt, iron, copper, chromium, as concrete example, unique expression nickel.
But, in this method, comprise that the loaded down with trivial details treatment process of the treating water that is called as the giving of relief formation-electroless plating catalyzer-thermal treatment-electroless plating of exposure imaging operation is many.So, can not realize display unit light shield layer with low-cost production.
Non-patent literature 1: upright publication (strain) distribution " colored TFT liquid-crystal display " the 218th～220 page (on April 10th, 1997) altogether
Patent documentation 1: the spy opens clear 62-9301 communique
Patent documentation 2: No. 3318353 communique of patent
Summary of the invention
The present invention proposes in view of aforesaid problem points just, provide a kind of for film and shading performance height, can be with low-cost production,, the display unit that can make black (Achromatic color of non-cohesive color and taste) little coloured composition and photosensitive transfer printing material with light shield layer to the influence of environment.In addition, the present invention also provide the display unit of using described coloured composition or photosensitive transfer printing material with light shield layer and manufacture method thereof, the colour filter and the liquid crystal display device of described display unit usefulness light shield layer are set.And then the present invention also provides and forms display unit is used light shield layer with the band display unit of light shield layer substrate as mentioned above.
Described problem solves with light shield layer and manufacture method, colour filter, liquid crystal display device and the band display unit substrate with light shield layer by following coloured composition and photosensitive transfer printing material, display unit are provided.
(1) a kind of coloured composition is characterized in that,
Contain the metallics with silver-colored tin alloy portion, the optical density(OD) after the film of corresponding per 1 μ m dry film thickness forms is more than 3.5.
(2) according to described (1) described coloured composition, it is characterized in that,
Volume fraction in the solids component of described metallics with silver-colored tin alloy portion is 0.05～0.7, and in the light shield layer that the colored coating composition forms, and illuminant-C sees through the XYZ color specification system tristimulus coordinates of light, and (x is y) with the tristimulus coordinates (x of described light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤ 0.01 relation.
(3) according to described (1) or (2) described coloured composition, it is characterized in that,
Described median size with metallics of silver-colored tin alloy portion is below the 500nm.
(4) according to any described coloured composition in described (1)～(3), it is characterized in that,
Described coloured composition has photosensitivity.
(5) a kind of photosensitive transfer printing material is characterized in that,
The photosensitivity light shield layer that has supporter and on this supporter, be provided with at least, this photosensitivity light shield layer contains the metallics with silver-colored tin alloy portion, the optical density(OD) of the photosensitivity light shield layer of corresponding per 1 μ m dry film thickness is more than 3.5, the volume fraction of the metallics with silver-colored tin alloy portion in the photosensitivity light shield layer is 0.05～0.7, and the illuminant-C of light shield layer sees through the XYZ color specification system tristimulus coordinates of light, and (x is y) with the tristimulus coordinates (x of described light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤ 0.01 relation.
(6) a kind of display unit light shield layer, it is to use any described coloured composition in described (1)～(4) or described (5) described photosensitive transfer printing material and the display unit light shield layer made.
(7) a kind of colour filter is characterized in that,
Constitute by photopermeability substrate and the pixel groups more than 2 that presents different colors from one another that is arranged on this substrate, described pixel groups is made of pigmented layer, each pixel that constitutes this pixel groups is shown device each other to be separated with light shield layer, and this display unit light shield layer is described (6) described display unit light shield layer.
(8) a kind of liquid crystal display device is characterized in that,
At least possess: at least one has 1 pair of substrate of photopermeability; And the colour filter that between this substrate, has, liquid crystal layer and liquid crystal drive mechanism, described colour filter is described (7) described colour filter.
(9) a kind of liquid crystal display device is characterized in that,
At least possess: at least one has the 1 pair of substrate and the colour filter that has, liquid crystal layer and the liquid crystal drive mechanism of photopermeability between this substrate, described liquid crystal drive mechanism has active component, is formed with described (6) described display unit light shield layer between each active component.
(10) a kind of display unit manufacture method of light shield layer wherein, has:
Form the operation of the layer of any described coloured composition in photopermeability substrate and described (1)～(4) on this substrate; And
Via display unit with light shield layer with photomask to described coloured composition the layer expose after, the operation of developing.
(11) a kind of display unit manufacture method of light shield layer wherein, has:
On the photopermeability substrate, be laminated to few described (5) described photosensitive transfer printing material that the photosensitivity light shield layer forms and operation that it is contacted with described photosensitivity light shield layer of on supporter, being provided with;
Peel off the operation of supporter from the duplexer of described photosensitive transfer printing material and photopermeability substrate; And
After described photosensitivity light shield layer being exposed with photomask with light shield layer via display unit, the operation of developing.
(12) a kind of substrate with display unit usefulness light shield layer is characterized in that,
Have photopermeability substrate and the display unit light shield layer on this substrate, the metallics that has silver-colored tin alloy portion in this display unit in light shield layer disperses with volume fraction 0.05～0.7, the display unit of the per 1 μ m of corresponding dry film thickness is more than 3.5 with the optical density(OD) of light shield layer, and display unit sees through the XYZ color specification system tristimulus coordinates of light with illuminant-C in the light shield layer, and (x is y) with the tristimulus coordinates (x of described light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤ 0.01 relation.
The coloured composition of the application of the invention can obtain being film and the high and low cost of shading performance,, black (Achromatic color of non-cohesive color and taste) tone outstanding display unit light shield layer little to the influence of environment.In addition, utilize tonal variation that display unit that the present invention obtains do not cause because of heating with light shield layer or considerably less.
In addition, use this display unit outstanding, when forming rgb pixel, can not sneak into bubble or considerably less with the flatness of the colour filter of light shield layer.And then the liquid crystal indicator of assembling this colour filter can generating unit spacing inequality between colour filter and substrate, and it is bad that look unequal demonstration can not take place.
Embodiment
[coloured composition]
Coloured composition of the present invention is characterised in that, contains metallics with silver-colored tin alloy portion (being designated hereinafter simply as " silver-colored tin alloy portion contain particle "), corresponding per 1 μ m dry film thickness, and the optical density(OD) that applies the layer that this coloured composition forms is more than 3.5.Such coloured composition is preferred: the volume fraction that particle is contained in the silver-colored tin alloy portion in the solids component is 0.05～0.7, and in the light shield layer that the described coloured composition of coating forms, illuminant-C sees through the XYZ color specification system tristimulus coordinates of light, and (x is y) with the tristimulus coordinates (x of described light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤ 0.01 relation.
Described " volume fraction of particle is contained in the silver-colored tin alloy portion in the solids component " is meant that the silver-colored tin alloy portion of containing in the light shield layer (described coloured composition has under the photosensitive situation, the layer after colored coating composition and exposure are solidified) that obtains at the dry described coloured composition of coating contains the volume fraction of particle.In addition, described volume fraction refers to that also the silver-colored tin alloy portion of containing in light shield layer in display unit contains the volume fraction of particle (in coloured composition, except particle is contained in silver-colored tin alloy portion, contain as the polymkeric substance of tackiness agent or monomer, polymerization starter, other any compositions, and in the formation of light shield layer, the part of these compositions disappears in operations such as coating, heat drying sometimes, so define in this wise).
At this, based on the mensuration of carrying out volume fraction with following formula.
The volume fraction of particle=(silver-colored tin alloy portion contains the amount of being coated with of particle/silver-colored tin alloy portion and contains Particle Density)/thickness is contained in silver tin alloy portion
Wherein, the amount of being coated with g/m 2Expression, density g/cm 3Expression, thickness (light shield layer or display unit with the thickness of light shield layer) is represented with μ m, in described formula, (silver-colored tin alloy portion contains the amount of being coated with of particle/silver-colored tin alloy portion and contains Particle Density), to be coated with the value of the thickness gained when being set as uniform film consistent with μ m unit representation particle being contained in silver-colored tin alloy portion.In addition, use the fluorescent X-ray device to measure the amount of being coated with that particle is contained in silver-colored tin alloy portion.
In addition, can contain Particle Density by the following silver-colored tin alloy portion of calculating.
At first, particle solution is contained in silver-colored tin alloy portion move in the furnace pot etc., seasoning, the tunicle of particle is contained in the exsiccant silver tin alloy portion of peelling off then, and it is broken to carry out fine powder, and preparation is measured and is used powdered sample.And then, in moisture eliminator, carry out vacuum-drying in 1 hour, in the glass specific gravity hydrometer (W1g) that essence claims, add exsiccant sample then, the quality (W2g) that claims to calculate sample by essence, sample is added in gap at specific gravity hydrometer, can fully bury the liquid of known proportion (D1g) until sample integral body, use ultrasonic wave to carry out deaeration.After powdered sample fully precipitates, and then replenish described liquid, filling liquid fully in specific gravity hydrometer with temperature regulation to 25 ℃, covers specific gravity hydrometer, the smart total quality (W3g) that claims.Like this, can calculate the quality of described liquid, use proportion that it is transformed into volume, use following (1) formula, obtain density.In addition, the capacity with specific gravity hydrometer at this moment is made as V1ml.
Particle Density=W2/{V1-(W3-W1-W2)/D1} is contained in silver tin alloy portion
(1) formula
The illuminant-C of light shield layer sees through the XYZ color specification system tristimulus coordinates (x, y) of light and carries out spectrometry with spectrophotometer or microspectrophotometer, by calculate primary stimuli value X, Y, the Z the illuminant-C from this spectrum, tries to achieve tristimulus coordinates.In addition, the XYZ color specification system tristimulus coordinates (x of the illuminant-C that uses in the present invention 0, y 0) in, x 0Be 0.3100, y 0Be 0.3164.
As commercially available spectrophotometer, the MCPD-1000 of big tomb electronics (strain) system as microspectrophotometer, can be used the OSP-SP100 of OLYMPUS system and OSP-SP200 etc.
In coloured composition of the present invention, if containing the median size and the volume fraction of particle, described silver-colored tin alloy portion satisfies condition of the present invention, then in the light shield layer that is formed by said composition, illuminant-C sees through the XYZ color specification system tristimulus coordinates of light, and (x is y) with the tristimulus coordinates (x of described light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤ 0.01 relation.
Described illuminant-C have with liquid crystal indicator in the proximate characteristic of backlight light source used, by satisfying described condition, then show can not be subjected to the transmission display device with the influence of the light of light shield layer the tone variation of black part.Described condition demonstrates tristimulus coordinates through light, and (x is y) with the tristimulus coordinates (x of illuminant-C 0, y 0) approaching.But (x is y) with the tristimulus coordinates (x of illuminant-C for the tristimulus coordinates of certain light 0, y 0) near being meant that this light is near Achromatic color.So, satisfy described condition and show, in black, do not add other colors and tastes, black tone is outstanding.In addition, surround lighting (reflected light) that can be when seeing through light and similarly consider to use liquid crystal indicator is to the influence of the tone of black part, so can be because of reflected light tone variation.
-have the metallics of silver-colored tin alloy portion-
Metallics (silver-colored tin alloy portion contain particle) with the silver-colored tin alloy portion among the present invention comprising: the metallics that each particle is made of silver-colored tin alloy, metallics that partly is made of silver-colored tin alloy part and other metals and the metallics that partly is made of silver-colored tin alloy part and other alloys.
In the present invention, for the definition of metal, learn middle record of dictionary the 4th edition (1987, the distribution of rock ripple bookstore) as rock ripple physics and chemistry.Silver-colored tin alloy among the present invention is the silver-colored tin alloy that forms at atomic level combined silver and tin, comprises sosoloid, eutectic, compound, intermetallic compound etc.Wherein, for alloy, for example learn in the dictionary the 4th edition (1987, the distribution of rock ripple bookstore) and put down in writing at rock ripple physics and chemistry.
At least a portion that particle is contained in silver-colored tin alloy portion among the present invention is made of silver-colored tin alloy.This configuration example is confirmed as the EDS (energy dispersion type x-ray analysis equipment) of the HD-2300 that can use (strain) Hitachi system and Noran corporate system.Its condition determination is the spectrum in each the 15nm zone, particle center under the acceleration voltage 200kV.
The black concentration height of particle is contained in silver tin alloy portion, can be with luminescent properties a small amount of or that film does well, and have high thermal stability.Thereby, can Bu Po Huai ?concentration and under high temperature (for example more than 200 ℃), heat-treating, can stably guarantee the opacifying property of height.For example, at the opacifying property that requires height, usually implement to cure photomask (so-called black matrix) that the colour filter of processing uses wait in preferably.
It is that to make the ratio of silver (Ag) be the particle that 30～80 moles of %, compoundization Ag and tin (Sn) (for example alloying) obtain that particle is contained in silver-colored tin alloy portion among the present invention.Ratio by making Ag especially in described scope, can obtain under high-temperature area the thermostability height, suppress reflection of light rate De Gao ?concentration.
In other words, if the ratio of Ag less than 30 moles of %, then thermal distortion takes place in fusing point step-down easily, thermostability reduces.In addition, if the ratio of Ag surpasses 80 moles of %, then the reflection of light rate uprises.Wherein, the ratio of Ag is preferably 40～75 moles of %, most preferably is 50～75 moles of %.
Particularly the ratio of Ag is that the particle of 75 moles of % is that the making of AgSn alloy particle is easy, and the particle that obtains is also stable, so preferred.
Coloured composition of the present invention can contain independent a kind of silver-colored tin alloy portion and contain particle and constitute, and also can and contain particle and constitutes with the ratio of the Ag different two or more silver-colored tin alloy portion in described scope.
The manufacturing that particle is contained in silver-colored tin alloy portion among the present invention can wait and forms by utilizing usual methods such as heating, melting mixing formation to carry out alloying in crucible etc.The fusing point of Ag is near 900 ℃, and the fusing point of Sn is near 200 ℃.Thereby the fusing point of the two exists big poor, and needs the micronize operation after unnecessary compoundization (for example alloying), so preferably utilize the particle reduction method.For example, mix Ag compound and Sn compound, with its reduction.For example, metal A g and metal Sn are separated out simultaneously, realized compoundization (for example alloying) and micronized method simultaneously in approaching position.Ag is reduced easily, has the trend of separating out more earlier than Sn, so preferably by making Ag and/or Sn become complex salt, control the time of separating out.
As described Ag compound, can preferably enumerate Silver Nitrate (AgNO 3), Silver monoacetate (Ag (CH 3COO)), silver perchlorate (AgClO 4H 2O) etc.Wherein, preferred especially Silver monoacetate.
As described Sn compound, can preferably enumerate tin protochloride (SnCl 2), tin chloride (SnCl 4), stannous acetate (Sn (CH 3COO) 2) etc.Wherein, preferred especially stannous acetate.
Method of reducing can be enumerated the method for using reductive agent, utilize the method for electrolytic reduction etc.Wherein, from can obtaining the point of fine particle, preferred the former method of using reductive agent of utilizing.As described reductive agent, can enumerate quinhydrones, catechol, p-aminophenol, Ursol D, pyruvic alcohol etc.Wherein, volatile calmly, bring dysgenic point to set out to display unit, preferred especially pyruvic alcohol.
Silver-colored tin alloy portion among the present invention contains particle and preferably has physical properties shown below or median size (size of particles), particle shape etc.
Silver-colored tin alloy portion among the present invention contains particle and is preferably the particle that has 240～400 ℃ fusing point in the mensuration of utilizing differential scanning calorimetry (DSC:Differential Scanning Calorimetry).Because fusing point in this scope, is compared with metal A g (fusing point: 950 ℃) or metal Sn (fusing point: 230 ℃), demonstrates good thermostability.
Particularly, measure the fusion (fusing point) of AgSn alloy as described below, promptly, the 20mgAgSn alloy is positioned over DSC (SSC/5200 as sample, Seiko instrument (セ ィ コ one ィ Application ス ッ Le) (strain) system) in the mensuration groove (cell), with 10 ℃/minute cooling rate, be cooled to room temperature from 200 ℃, measure the decrease temperature crystalline peak that utilizes DSC.
The preferred median size of particle (number average size of particles) is contained for below the 500nm in silver-colored tin alloy portion among the present invention, and in addition, more preferably lower value is more than the 2nm.And then this median size is 20～200nm more preferably, is preferably 30～100nm especially.If particularly in described scope, then different with the particle of metal, particle diameter all has black tone to the number average size of particles arbitrarily.Wherein, if the number average size of particles surpasses 500nm, the planar variation during film forming sometimes then, if less than 2nm, then black lowers, sometimes the yellow flavor of band.
Described number average size of particles uses the photo that utilizes transmission electron microscope JEM-2010 (NEC (strain) system) to obtain, and measures as described below.
Select 100 particles, will be made as particle diameter, the particle diameter of 100 particles on average is made as the number average size of particles with the circular diameter of each particle image area identical.Wherein, the photo that uses 100,000 times of multiplying powers, acceleration voltage to take down as 200kV.
Particle shape as " silver-colored tin alloy portion contain particle " among the present invention is not particularly limited, and can be arbitrary shapes such as cubic, high aspect ratio, middle aspect ratio, needle-like.
Contain in the particle in silver-colored tin alloy portion, except Ag and Sn, and then also can contain salt or organism, other elements (Ca, P, Na etc.) etc.Wherein, even in this case, also preferably have described physical properties, size of particles, particle shape, and be maintained.
Contain the amount in the coloured composition of the present invention of particle as silver-colored tin alloy portion, as long as corresponding purpose or purposes are suitably selected.From obtaining the viewpoint of opacifying property highly, all solids composition (volume) that the relative composition of amount of particle is contained in this silver tin alloy portion is preferably 5～70 volume %, and more preferably 10～66 volume % most preferably are 15～60 volume %.If the amount that particle is contained in silver-colored tin alloy portion particularly in described scope, then can suppress reflection of light Shuai ， ?the concentration height, for film and can obtain high opacifying property.Particularly under situation, can obtain high-contrast and display image clearly as the light screening material of the image display area such as black matrix of colour filter.Wherein, the amount that particle is contained in silver-colored tin alloy portion is during less than 5 volume %, and the thickness during film forming is thicker than 1.0 μ m sometimes, and when surpassing 70 volume %, the reflectivity height destroys sometimes and shows contrast gradient.
(having photosensitive coloured composition)
Coloured composition among the present invention preferably has photosensitivity.In order to give photosensitivity, in described coloured composition, add photosensitive polymer combination.Photosensitive polymer combination contains binder polymer, has the monomer that carries out addition polymerization under the irradiation of light of ethene unsaturated double-bond, Photoepolymerizationinitiater initiater etc.
Photosensitive polymer combination comprises can carry out alkali aqueous solution composition that develops and the composition that can develop in organic solvent.As photosensitive polymer combination,, preferably can carry out the composition that alkali aqueous solution develops from the point of the cost of security and developing solution.
Photosensitive polymer combination can be for accepting the part generation solidified minus of light, electron rays isoradial, also can be radioactive rays receiving portion solidified eurymeric not.
Normal Photosensitive resin can be enumerated the resin of phenolic varnish system.For example, can use the spy and open the alkali-soluble novolac resin system that puts down in writing in the flat 7-43899 communique.In addition, can also use the spy open the positive-working photosensitive resin layer of putting down in writing in the flat 6-148888 communique promptly contain the resin put down in writing in this communique with as 1 of sensitizer, the photo-sensitive resin of the mixture of the thermal curing agents of putting down in writing in 2-naphthalene quinone di-azide sulfonic acid ester and this communique.In addition, also can use the spy to open the composition of putting down in writing in the flat 5-262850 communique.
As the negative-type photosensitive resin, can enumerate the photosensitive polymer combination, cassia bark acid type photosensitive polymer combination of photoresist that minus diazo resin and tackiness agent constitute, optical polymerism composition, triazo-compound and tackiness agent formation etc.Wherein, especially preferably contain the photoresist that Photoepolymerizationinitiater initiater, photopolymerization monomer and tackiness agent are basic constituent element." polymerizable compound B " " polymerization starter C " " tensio-active agent " " bonding auxiliary agent " or other compositions that this photo-sensitive resin can utilize the spy to open to put down in writing in the flat 11-133600 communique.
For example, for the negative-type photosensitive resin and can carry out the photoresist that alkali aqueous solution develops and contain carboxylic acid group's tackiness agent (thermoplastic resin described later etc.) and can contain monomer and Photoepolymerizationinitiater initiater at the ethene unsaturated double-bond of addition polymerization under the rayed as main component.
As tackiness agent, can enumerate the polymkeric substance that has the carboxylic acid group at side chain, for example special clear 59-44615 communique, special public clear 54-34327 communique, special public clear 58-12577 communique, special public clear 54-25957 communique, spy opened opened clear 59-53836 communique and the special Sipacril 2739OF put down in writing in the clear 59-71048 communique, acrylic copolymer, itaconic acid copolymer, Ba Dousuan multipolymer, maleic acid, the partial esterification maleic acid etc. opened.In addition, also can enumerate the derivatived cellulose that side chain has the carboxylic acid group.In addition, also can preferably use material to polymkeric substance addition cyclic acid anhydride with hydroxyl.In addition, as more preferred example, can also enumerate (methyl) vinylformic acid benzyl ester and (methyl) acrylic acid multipolymer put down in writing in No. 4139391 specification sheets of United States Patent (USP), or (methyl) vinylformic acid benzyl ester and (methyl) vinylformic acid and other monomeric multiple copolymers.
The tackiness agent that uses in photo-sensitive resin can be selected to use from the tackiness agent of the weight-average molecular weight of the scope of the acid number of scope with 30～400mgKOH/g and 1000～300000.In addition, for example solidify film strength,, can add the insoluble polymkeric substance of alkali bringing in the dysgenic scope for development etc. in order to improve various performances.As these polymkeric substance, can enumerate alcohol soluble nylon or Resins, epoxy.
Tackiness agent has all solids composition of photosensitive coloured composition relatively, is generally 10～95 quality %, and then is preferably 20～90 quality %.In the scope that is 10～95 quality %, the binding property of photo-sensitive resin can be not too high yet, and the intensity and the luminous sensitivity of the layer of formation can variation yet.
As Photoepolymerizationinitiater initiater, can enumerate disclosed vicinal polyketals (Polyketaldonyl) compound in No. 2367660 specification sheets of United States Patent (USP), the accidental cause ether compound of putting down in writing in No. 2448828 specification sheets of United States Patent (USP), the aromatic series accidental cause compound of putting down in writing in No. 2722512 specification sheets of United States Patent (USP) with α-hydrocarbon replacement, the polynucleation quinone compound of putting down in writing in No. 3046127 specification sheets of United States Patent (USP) and No. 2951758 specification sheets of United States Patent (USP), the triarylimidazoles dimer of putting down in writing in No. 3549367 specification sheets of United States Patent (USP) and the combination of p-keto-amine, benzothiazole compound and the trihalomethyl group-s-triaizine compounds put down in writing in the special public clear 51-48516 communique, trihalomethyl group-s-triaizine compounds of putting down in writing in No. 4239850 specification sheets of United States Patent (USP), the San Lu that puts down in writing in No. 4212976 specification sheets of United States Patent (USP) is for Jia oxadiazole compound etc.Preferred especially trihalomethyl group-s-triaizine compounds, San Lu are for Jia oxadiazole, triarylimidazoles dimer.
In having photosensitive coloured composition, the relative all solids composition of the content of Photoepolymerizationinitiater initiater is generally 0.5～20 quality %, is preferably 1～15 quality %.During less than 0.5 quality %, the intensity of luminous sensitivity or image is low, when surpassing 20 quality %, even add, the effect of performance also can not occur improving.
As can be under the irradiation of light addition polymerization contain ethene unsaturated double-bond monomer (being designated hereinafter simply as " monomer "), can enumerate boiling point and be the compound more than 100 ℃ under normal pressure.For example can enumerate simple function (methyl) acrylate such as polyoxyethylene glycol one (methyl) acrylate, polypropylene glycol one (methyl) acrylate and (methyl) vinylformic acid phenoxy group ethyl ester; Polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the trimethylolethane trimethacrylate acrylate, Viscoat 295, trimethylolpropane diacrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, hexylene glycol two (methyl) acrylate, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) chlorinated isocyanurates, three (acryloxy ethyl) cyanurate, glycerine three (methyl) acrylate, on polyfunctional alcohols such as TriMethylolPropane(TMP) or glycerine after addition of ethylene oxide or the propylene oxide, multifunctional (methyl) acrylate such as material of (methyl) acroleic acid esterification again.
And then can also enumerate special public clear 48-41708 number, special public clear 50-6034 number and spy and open disclosed urethane acrylate class in the clear 51-37193 communique; The spy opens disclosed polyester acrylate class in clear 48-64183 number, special public clear 49-43191 number and special public clear 52-30490 communique; As polyfunctional acrylic ester or the methacrylic esters such as epoxy acrylate class of Resins, epoxy with (methyl) acrylic acid reaction product.Wherein, preferred trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate.These monomers can use or mix two or more uses separately.The content that this monomer has all solids composition of photosensitive coloured composition relatively is generally 5～50 quality %, is preferably 10～40 quality %.If this monomeric content is in the scope of 5～50 quality %, then the intensity of luminous sensitivity or image can not reduce yet, and it is superfluous that the binding property of photosensitivity light shield layer can not become yet.
Photosensitive polymer combination is except described composition, and is preferred and then contain thermopolymerization and prevent agent.Prevent agent as thermopolymerization, for example can enumerate quinhydrones, p-methoxyphenol, p-tert-butyl catechol, 2, aromatic hydroxy compounds such as 6-two-tertiary butyl-p-cresols, 2-Naphthol, pyrogallol, quinones such as benzoquinones, p-toluquinone, amines such as naphthylamines, pyridine, p-Tolylamine, thiodiphenylamine, the aluminium salt or the ammonium salt of N-nitroso-group phenyl oxyamine, chloranil, oil of mirbane, 4,4 ' _-thiobis (3 methy 6 tert butyl phenol), 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole etc.
Photosensitive polymer combination also can and then add known additive as required, for example softening agent, tensio-active agent, tackifier, dispersion agent, softening agent, anti-sag agent, flow agent, defoamer, fire retardant, brightening agent, solvent etc.
As tackifier, for example can enumerate petroleum resin, silane coupling agent of alkylphenol/formaldehyde phenolic resin varnish, polyethylene ethyl ether, PVI polyvinyl isobutyl ether, polyvinyl butyral acetal, polyisobutene, styrene-butadiene copolymer rubber, isoprene-isobutylene rubber, vinyl chloride-vinyl acetate copolymer, chlorinated rubber, acrylic resin tackiness agent, fragrant family, fatty family or alicyclic ring family etc.
In addition, when particle is contained as water dispersion in silver-colored tin alloy portion, as described photosensitive polymer combination, the composition of essential water system.As such photosensitive polymer combination, except the spy opens the composition of record in the paragraph 0015～0023 of flat 8-271727 communique,, can enumerate " SPP-M20 " of Japan's compound probability (strain) system etc. as commercially available composition.
(not having photosensitive coloured composition)
Do not have photosensitive coloured composition in the present invention except particle is contained in aforesaid silver-colored tin alloy portion, contain tackiness agent, dispersion agent, solvent etc. as required.As tackiness agent, can suitably use soluble polymer resin tackiness agent or non-water-soluble resin tackiness agent.
The soluble polymer resin tackiness agent preferably has the polymkeric substance of protective colloid.The soluble polymer resin tackiness agent for example can be enumerated gelatin, polyvinyl alcohol, methylcellulose gum, hydroxypropylcellulose, poly-alkylamine, polyacrylic part alkyl ester etc.In addition, can also enumerate the tackiness agent of record in " topical reference book of pigment (her rattan is levied the youth of department and compiles, and (strain) was towards storehouse academy distribution 2000) ".
In addition, as the non-soluble polymer tackiness agent, can also (Japanese plastics industry connects alliance from " plastics performance brief guide ", all Japan plastics forming industry Colaesce meeting is write, the census of manufacturing can be issued, October 25 nineteen sixty-eight distribution) in select one at least in the organic solvent soluble polymer tackiness agent of record.
Preferred concrete example as the non-soluble polymer tackiness agent, can enumerate as polyolefine such as polymeric amide, polyester, polystyrene, resol, polyethylene, polycarbonate, silicone resin, urethane, polyacid acid anhydride, polysulfones, poly-imines, polysulfide, polyacrylonitrile, nylon, polyvinyl acetate (PVA), polyvinyl ether, polyacrylic acid and polymethyl acrylic acid and their ester and then their multipolymer or modification body, soluble tackiness agent in organic solvent.
In addition, as the non-soluble polymer tackiness agent, from can be water the blended viewpoint, also can use polymer emulsion.Polymer emulsion is meant that water-insoluble polymer particulates disperses the material that forms in water.Water-insoluble polymkeric substance can be enumerated aforesaid non-soluble polymer.Particularly, for example in " chemistry of high molecular emulsion " (chamber well ancestor one work, polymer publication can distribution, clear and 48 years), put down in writing.
As described polymer emulsion, for example can enumerate the polymer emulsion that constitutes by polyester, urethane, polyureas/carbamate, SBR (phenylethylene/butadiene system), MBR (MMA/ divinyl, vinylformic acid/divinyl), NBR (acrylonitrile/butadiene), NR (natural rubber), BR (divinyl rubber), CR (neoprene), IR (polyisoprene rubber), VP (SBR/ divinyl pyridine) and their multipolymer.
In addition, can also and use diverse polymer emulsion in described polymer emulsion.As can and the polymer emulsion of usefulness, the different material of nitro amount of for example preferred SBR and NR, IR and NR, CR and NR, NBR, the different material of vinylbenzene amount of SBR, SBR and VP, NBR and MBR, SBR and NBR, SBR and MBR, BR and CR, NBR and VP, CR and VP etc. are not the materials of combination of the material of the material of anionic property and cationic.
As the material of anionic property, comprise the material of having introduced carboxyl, as the material of cationic, comprise the material of having introduced amino or ammonium.
Usage quantity as the polymkeric substance of described tackiness agent in not having photosensitive coloured composition, is preferably 3～50 quality %, is preferably 10～30 quality % especially.
In addition, as solvent, can use known organic solvent.As particularly preferred organic solvent, can enumerate methyl alcohol, Virahol, MEK, vinyl acetic monomer, toluene etc.In addition, water is also preferably as solvent.These solvents also can mix use as required.
[photosensitive transfer printing material]
In the present invention, can use the described photosensitive coloured composition that has, make photosensitive transfer printing material, use it to make the display unit light shield layer.
Described photosensitive transfer printing material is that the material that has the photosensitivity light shield layer that photosensitive coloured composition forms by described at least is set on interim supporter.The thickness of photosensitivity light shield layer is preferably the scope of 0.2～2 μ m, the scope of preferred especially 0.2～1 μ m.
As interim supporter of the present invention, can use known supporters such as polyester, polystyrene.Wherein, as interim supporter, from the viewpoint of cost, thermotolerance, dimensional stability, the preferred polyethylene terephthalate of two-way stretch.The thickness of interim supporter is preferably about 15～200 μ m, more preferably about 30～150 μ m.In interim supporter, when carrying out stacked operation, there is the shortcoming because of the tabular wrinkle of heat generation galvanized iron in thickness during less than 15 μ m.On the contrary, surpass under the situation of 200 μ m at the thickness of interim supporter, unfavorable on the cost.
In addition, interim supporter also can be arranged on the spy as required and open the conductive layer of putting down in writing among the flat 11-149008.
(thermoplastic resin)
In addition, preferably between supporter and photosensitivity light shield layer or supporter and middle layer, thermoplastic resin is set.
Thermoplastic resin plays the effect as the fender of concavo-convex (also comprise and utilize the concavo-convex etc. of established image etc.) that can the absorption base basal surface.So preferably having can be to character that should deformation of unevenness.
As the resin that contains in thermoplastic resin, that preferably selects from saponified, the Vinyl toluene of saponified, the vinylbenzene of ethene and acrylate copolymer and (methyl) acrylate copolymer and saponified, poly-(methyl) acrylate of (methyl) acrylate copolymer and (methyl) acrylate copolymer of (methyl) butyl acrylate and vinyl acetate etc. etc. saponified etc. is at least a.And then, as the resin that contains in the thermoplastic resin, can use also that (Japanese plastics industry connects alliance in " plastics performance brief guide ", all Japan plastics forming industry Colaesce meeting is write, the census of manufacturing can be issued, October 25 nineteen sixty-eight distribution) organic polymer in alkali aqueous solution soluble resin.
In addition, in these thermoplastic resins, preferred softening temperature is the resin below 80 ℃.In addition, in this manual, " (methyl) vinylformic acid " is the general name of vinylformic acid and methacrylic acid, also comprises the situation of its derivative.
In these resins, select to use in can be 50,000～500,000 in the weight-average molecular weight scope of (Tg=0～140 ℃) and then preferably be 60,000～200,000 resin of scope of (Tg=30～110 ℃) in weight-average molecular weight.As the concrete example of these resins, can enumerate at the public clear 54-34327 of spy number, special public clear 55-38961 number, special public clear 58-12577 number, special public clear 54-25957 number, the spy opens clear 61-134756 number, special public clear 59-44615 number, the spy opens clear 54-92723 number, the spy opens clear 54-99418 number, the spy opens clear 54-137085 number, the spy opens clear 57-20732 number, the spy opens clear 58-93046 number, the spy opens clear 59-97135 number, the spy opens clear 60-159743 number, OLS3504254 number, the spy opens clear 60-247638 number, the spy opens clear 60-208748 number, the spy opens clear 60-214354 number, the spy opens clear 60-230135 number, the spy opens clear 60-258539 number, the spy opens clear 61-169829 number, the spy opens clear 61-213213 number, the spy opens clear 63-147159 number, the spy opens clear 63-213837 number, the spy opens clear 63-266448 number, the spy opens clear 64-55551 number, the spy opens clear 64-55550 number, Te Kaiping 2-191955 number, Te Kaiping 2-199403 number, Te Kaiping 2-199404 number, Te Kaiping 2-208602 number, special hope flat 4-39653 number, the soluble resin of putting down in writing in each communique specification sheets of Te Kaiping 5-241340 number in alkali aqueous solution.Open methacrylic acid/acrylic acid-2-ethyl polyhexamethylene/methacrylic acid benzyl ester/methylmethacrylate copolymer of putting down in writing in the clear 63-147159 specification sheets particularly preferably in the spy.
In addition, select to use in in described various resins, can be preferably be 3,000～30,000 scope of (Tg=30～170 ℃) and then preferably be 4,000～20,000 scope of (Tg=60～140 ℃) in weight-average molecular weight in weight-average molecular weight.Preferred concrete example can be selected from the concrete example of putting down in writing described patent specification, especially preferably enumerates the public clear 55-38961 of spy number, spy and opens the styrene/methacrylic acid multipolymer of putting down in writing in each communique of flat 5-241340 specification sheets.
In addition, in order to be adjusted in these organic polymer materials the bonding force with supporter, can add various softening agent, various polymkeric substance or overcooling material, adhesion promotor or tensio-active agent, releasing agent etc.As the concrete example of preferred plasticizer, can enumerate polypropylene glycol, polyoxyethylene glycol, dioctyl phthalate (DOP), diheptyl phthalate, dibutyl phthalate, tritolyl phosphate, phosphoric acid cresols diphenyl, phosphoric acid xenyl diphenyl, polyoxyethylene glycol one (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol one (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the addition reaction product of Resins, epoxy and polyoxyethylene glycol one (methyl) acrylate, the addition reaction product of organic diisocyanate and polyoxyethylene glycol one (methyl) acrylate, the addition reaction product of organic diisocyanate and polypropylene glycol one (methyl) acrylate, the condensation reaction products of dihydroxyphenyl propane and polyoxyethylene glycol one (methyl) acrylate etc.The amount of the softening agent in the thermoplastic resin is this thermoplastic resin relatively, is generally below the 200 quality %, is preferably 20～100 quality %.The thickness of thermoplastic resin is preferably more than the 1.0 μ m.If the thickness of thermoplastic resin is more than the 1.0 μ m, then can fully absorb the concavo-convex of substrate film.In addition,,, be generally below about 100 μ m, be preferably below about 50 μ m from development, manufacturing adaptability for the upper limit.
In the present invention,, get final product, be not particularly limited, can use so long as dissolving constitutes the solvent of the resin of this layer as the solvent of thermoplastic resin.As the example of this solvent, for example can enumerate ethyl methyl ketone, pimelinketone, propylene glycol monomethyl ether acetic ester, n-propyl alcohol, Virahol etc.
(middle layer)
Photosensitive transfer printing material of the present invention also can be provided with the middle layer between interim supporter and photosensitivity light shield layer.
Resin as constituting the middle layer is not particularly limited, and is preferably alkali-soluble.As the example of resin, can enumerate polyvinyl alcohol resin, polyvinylpyrrolidone and be resin, cellulose-based resin, acrylamide resin, oxyethane and be resin, gelatin, Vinyl Ether is resin, polyamide resin and their multipolymer.In addition, also can use polyester and so on will not be usually alkali-soluble resin with have the resin that carboxyl or sulfonic monomer copolymerizable form.
Wherein, be preferably polyvinyl alcohol.As polyvinyl alcohol, saponification deg is preferably more than 80%, more preferably from 83～98%.
It is two or more that the resin in formation middle layer preferably mixes use, and preferred especially the mixing used polyvinyl alcohol and polyvinylpyrrolidone.The weight ratio of the two is polyvinylpyrrolidone/polyvinyl alcohol=1/99～75/25, more preferably 10/90～50/50 scope.If should be than below 1/99, then produce the middle layer planar deterioration, with problems such as the adhesion that is coated with photo-sensitive resin provided thereon is bad.On the contrary, if the weight ratio of the two surpasses 75/25, the then resistance oxygen reduction in middle layer, sensitivity reduces.
Also can in the middle layer, add additives such as tensio-active agent as required.
The thickness in middle layer is 0.1～5 μ m, the more preferably scope of 0.5～3 μ m.Under the situation of thickness less than 0.1 μ m, sensitivity reduces owing to hinder the reduction of oxygen sometimes, surpasses under the situation of 5 μ m, and the problem of the increase of time is removed in the middle layer when taking place to develop sometimes.
As the coating solvent in middle layer, as long as described resin dissolves then is not particularly limited preferably water.The also preferred mixed solvent that in water, mixes described water Combination organic solvent.As the preferred concrete example of the coating solvent in middle layer, as described below.Water, water/methyl alcohol=90/10, water/methyl alcohol=70/30, water/methyl alcohol=55/45, water/ethanol=70/30, water/1-propyl alcohol=70/30, water/acetone=90/10, water/ethyl methyl ketone=95/5 (mass ratio).
When making photosensitive transfer printing material of the present invention, can be by on supporter, use turner (rotation mode, crack formula and rotary (slit and spin)), coating machine (ホ ヮ ィ ラ one), coating roller, curtain formula varnishing machine, knife coater, wire bar coating machine, forcing machine (the FAS mode etc.) coating machine of etc.ing, apply the solution that drying has a photosensitive coloured composition of the present invention and form.Under the situation of the layer that thermoplastic resin is set, similarly form.
Photosensitive transfer printing material of the present invention is owing to be provided with the photosensitivity light shield layer that is formed by coloured composition as mentioned above, so, can make the display unit light shield layer that possesses for the high light shield layer of film and optical density(OD).
[display unit light shield layer and preparation method thereof]
Display unit of the present invention uses described coloured composition or photosensitive transfer printing material to make with light shield layer.Its thickness is about 0.1～2.0 μ m, is preferably 0.1～0.9 μ m.The optical density(OD) of the per 1 μ m of corresponding light shield layer thickness is more than 3.5.Described display unit light shield layer is and then disperses silver-colored tin alloy portion to contain the layer of particle with 0.05～0.7 volume fraction, and the illuminant-C of light shield layer sees through the XYZ color specification system chromaticity coordinates of light, and (x is y) with the tristimulus coordinates (x of described light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤ 0.01 relation, as mentioned above, even because for film also has sufficient optical density(OD) and has the tone of outstanding black and then the tonal variation that causes of heating is little or do not have, so preferred.In addition, owing to be film, so under the situation that forms colour filter, be difficult to take place overlapping with pixel such as RGB, the flatness raising of colour filter.
Use has photosensitive coloured composition making display unit and uses the method for light shield layer to be the photosensitive coloured composition of coating on the photopermeability substrate, form the layer (method of coating method during with the described photosensitive transfer printing material of making is identical) of coloured composition, utilize ordinary method, expose with photomask with light shield layer via display unit, develop then, form the method for light shield layer thus.
In addition, do not have under the photosensitive situation at coloured composition, can contain silver-colored tin alloy of the present invention portion by coating on the photopermeability substrate contains the coloured composition of particle and forms after the layer of coloured composition, on this layer, form the layer that constitutes by the photosensitive polymer combination that can develop, utilize ordinary method, expose with photomask with light shield layer via display unit, then, develop, etching, form light shield layer thus.
The display unit of using described photosensitive transfer printing material is configuration, a stacked described photosensitive transfer printing material on the photopermeability substrate with the making method of light shield layer, and it is contacted with the photosensitivity light shield layer of photosensitive transfer printing material, then, peel off supporter from the duplexer of photosensitive transfer printing material and photopermeability substrate, then,, develop then with the light shield layer described layer of photomask exposure via display unit, form the method for display unit with light shield layer.
Display unit of the present invention does not need loaded down with trivial details operation with the manufacture method of light shield layer, so be low-cost.
[colour filter]
Colour filter of the present invention has structure as described below, promptly, on the photopermeability substrate, have 2 the above pixel groups that present the color that differs from one another that constitute by pigmented layer, and the structure that each pixel of described pixel groups is separated with light shield layer by display unit each other, this display unit uses described coloured composition of the present invention or photosensitive transfer printing material to make with light shield layer.Pixel groups can for 2, more than 3 or 4.For example be under 3 the situation, can use red (R), green (G) and blue (B) 3 tones.Under the situation of 3 kinds of pixel groups of configuration red, green, blue, configurations such as preferred mosaic, trilateral type under the situation of the pixel groups of configuration more than 4 kinds, can be disposed for any one.
As described photopermeability substrate, can use known sheet glass such as the soda-lime glass plate that has the silicon oxide tunicle on the surface, low expansion glass plate, non-alkali glass plate, quartz glass plate or plastics film etc.
When making colour filter, on the photopermeability substrate, utilize ordinary method, form after 2 above pixel groups, can form the display unit light shield layer as described above, perhaps also can form the pixel groups more than 2 then at the initial display unit light shield layer that forms.
Colour filter of the present invention possesses the display unit light shield layer as mentioned above, thus show the contrast gradient height, and also flatness is outstanding.And then, because display unit is little with the thickness of light shield layer, so when making the colour filter pixel, the number of bubbles that is involved in is also less or do not have.
[liquid crystal display device]
One of liquid crystal display device of the present invention is to possess at least: at least one has 1 pair of substrate of photopermeability; And the liquid crystal display device of the colour filter between this substrate, liquid crystal layer and liquid crystal drive mechanism (comprising simple matrix type of drive and driven with active matrix mode), as described colour filter, use to have a plurality of pixel groups as mentioned above, each pixel that constitutes described pixel groups is each other by the colour filter of display unit of the present invention with the light shield layer separation.Because the flatness height of described colour filter, so the liquid crystal display device that possesses this colour filter generating unit spacing inequality not between colour filter and substrate, it is bad that look unequal demonstration can not take place.
In addition, another mode of liquid crystal display device of the present invention is for to possess at least: at least one has 1 pair of substrate of photopermeability; And the colour filter between this substrate, liquid crystal layer and liquid crystal drive mechanism, described liquid crystal drive mechanism has active component (for example TFT), and is formed with the display unit light shield layer that uses coloured composition of the present invention or photosensitive transfer printing material to make between each active component.
[the band display unit substrate of light shield layer]
Band display unit of the present invention is that the substrate of described display unit with light shield layer is set on the photopermeability substrate with the substrate of light shield layer, it is characterized in that, to the optical density(OD) of the per 1 μ m of thickness that should layer is more than 3.5, disperse to contain silver-colored tin alloy portion with volume fraction 0.05～0.7 and contain particle, and illuminant-C sees through the XYZ color specification system tristimulus coordinates of light, and (x is y) with the tristimulus coordinates (x of described light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤ 0.01 relation.
Band display unit of the present invention can be used to make colour filter with the substrate of light shield layer.So, even owing to also can realize sufficient optical density(OD) for film, so can reduce the thickness of display unit with light shield layer, when making the colour filter pixel on the substrate of light shield layer, the number of bubbles that is involved in is also lacked in the band display unit.
Embodiment
Below utilize embodiment further to specify the present invention, but the present invention is not limited by these embodiment.In addition, in the following, " part " and " % " represents " mass parts " and " quality % " respectively.
(embodiment 1～5)
＜have a preparation of dispersion liquid (dispersion liquid A1) of the metallics of silver-colored tin alloy portion 〉
In pure water 1000ml, dissolving Silver monoacetate (I) 23.1g, tin acetate (II) 65.1g, glyconic acid 54g, trisodium phosphate 45g, polyoxyethylene glycol (molecular weight 3,000) 2g and E735 (ISPJapan (strain) system; V-Pyrol RC/vinyl acetate copolymer) 5g obtains solution 1.
In addition, dissolving pyruvic alcohol 36.1g obtains solution 2 in pure water 500ml.
Stir tempestuously when the described solution that obtains 1 is remained on 25 ℃, and wherein add described solution 2 with 2 fens clockwise simultaneously, continue lentamente to stir 6 hours.Like this, mixed solution becomes black, obtains to have the metallics (silver-colored tin alloy portion contain particle) of silver-colored tin alloy portion.Then, this liquid of centrifugation makes silver-colored tin alloy portion contain particle precipitation.Centrifugation is the aliquot liquid measure that is divided into 150ml, utilizes desk-top separating centrifuge H-103n ((strain) KOKUSAN system), and with rotation number 2,000r.p.m. carried out 30 minutes.Then, supernatant discarded makes full liquid measure become 150ml, to wherein adding pure water 1350ml, stirs 15 minutes, makes silver-colored tin alloy portion contain particle once more and disperses.Carry out 2 these operations repeatedly, remove the soluble substance of water.
Then, this liquid further carries out centrifugation relatively, makes silver-colored tin alloy portion contain particle precipitation once more.Centrifugation with described identical condition under carry out.After carrying out centrifugation,, so that being 150ml, total liquid measure to wherein adding pure water 850ml and acetone 500ml, and then stirred 15 minutes with described supernatant discarded similarly, and make silver-colored tin alloy portion contain particle once more and disperse.
Similarly carry out with described once more, carry out centrifugation, make after silver-colored tin alloy portion contains particle precipitation, with described supernatant discarded similarly, make liquid measure become 150ml, to wherein adding pure water 150ml and acetone 1200ml, further stirred 15 minutes, make silver-colored tin alloy portion contain particle once more and disperse.Then, carry out centrifugation once more.The condition of the centrifugation of this moment will be except will being extended down to 90 minutes, with described identical the time.Then, supernatant discarded makes total liquid measure become 70ml, to wherein adding acetone 30ml.Use Eiger pulverizer (Eiger pulverizer M-50, medium: the zirconium oxide bead 130g of diameter 0.65mm, EigerJapan (strain) system), disperseed 6 hours, obtain silver-colored tin alloy portion and contain dispersion of particles liquid (dispersion liquid A1).
Utilizing the X ray scattering to confirm should silver tin alloy portion to contain particle is the complex body that is made of AgSn alloy (2 θ=39.5 °) and Sn metal (2 θ=30.5 °).At this, the numeral in the bracket is the scattering angle of (III) face separately.With this particle dispersion liquid of transmission electron microscope observation, it is 40nm with the number average size of particles that the result disperses median size.
In addition, the mensuration of number average size of particles is used the photo that utilizes transmission electron microscope JEM-2010 (NEC (strain) system) to obtain, and utilizes described method to carry out.
The preparation of＜sensitive layer coating liquid 〉
Contain among the dispersion of particles liquid A1 in the silver-colored tin alloy portion of described making and to add following compositions, be formulated in the sensitive layer coating liquid that uses among embodiment 1～embodiment 5.In addition, the addition of the dipentaerythritol acrylate silver-colored tin alloy portion that is adjusted to embodiment 1～embodiment 5 volume fraction that contains particle becomes the value of record in the table 1.
Dispersion of particles liquid (dispersion liquid A1) is contained in described silver-colored tin alloy portion ... 50.00 part
Propylene glycol monomethyl ether acetic ester ... 28.6 part
Ethyl methyl ketone ... 37.6 part
Fluorine is a tensio-active agent ... 0.2 part
(F-780-F, big Japanese ink chemical industry (strain) system)
The quinhydrones monomethyl ether ... 0.001 part
Styrene/acrylic acid co-polymer ... 9.6 part
(mol ratio=56/44, weight-average molecular weight 30,000)
Dipentaerythritol acrylate ... (be added into silver-colored tin alloy portion and contain the value that the volume fraction of particle becomes table 1)
(KAYARAD DPHA, Japanese chemical drug corporate system)
Two [4-[N-[4-(4, the two trichloromethyls of 6--s-triazine-2-yl) phenyl] formamyl] phenyl] sebate ... 0.5 part
The preparation of＜protective layer coating liquid 〉
Polyvinyl alcohol ((strain) CLEA makes PVA205) ... 3.0 part
Polyvinylpyrrolidone (ISPJapan (strain) makes PVP-K30) ... 1.3 part
Distilled water ... 50.7 part
Methyl alcohol ... 45.0 part
The making of＜sensitive materials 〉
After UV washing unit cleaning alkali-free glass substrate, use clean-out system to scrub, and then carry out ultrasonic cleaning with ultrapure water.120 ℃ of these substrates of following thermal treatment 3 minutes make the condition of surface stabilization.
Cool off this substrate, temperature transfers to after 23 ℃, with the coating machine (coater) (flat field machine worker (strain) system) of the glass substrate with slot-shaped nozzle, applies the sensitive layer coating liquid of each embodiment respectively.Then, with VCD (Minton dryer; Chemical industry (strain) system is answered in Tokyo), in 30 seconds an of part of dry solvent, the flowability of overlay is disappeared.Then,, use spin coater thereon, coating protective layer coating liquid makes dry film thickness become 1.5 μ m, and drying is 5 minutes under 100 ℃, obtains photo-sensitive resin K1.
＜display unit the making of light shield layer 〉
With the close induction type exposure machine with ultrahigh pressure mercury lamp (Hitachi's high-tech electronic engineering (strain) system), with substrate and the vertical state that erects of mask (quartzy exposed mask) with picture pattern, with the distance setting between exposed mask face and this photo-sensitive resin is 200 μ m, with exposure 70mJ/cm 2Carry out pattern exposure.
Then, with the spray spout pure water of spraying, make the surface of this photo-sensitive resin K1 moistening equably after, with 23 ℃, 80 seconds, flat burner pressure 0.04MPa, to KOH is that developing solution (contains KOH, nonionogenic tenside, trade(brand)name: CDK-1, Fujiphoto electronics synthesis material) spray development, obtain the patterning image.Then, use the ultra-high voltage washing nozzle, under the pressure of 9.8MPa, spray ultrapure water, remove resistates, and then utilize spray spout, from two sides spray ultrapure water, remove the developing solution or the described photo-sensitive resin solute of attachment removal, utilize the squeegee liquid that breaks, obtain on glass substrate, to form display unit with the band display unit of the embodiment 1～embodiment 5 of light shield layer substrate with light shield layer.
(sensitive layer determining film thickness)
Measure the thickness of sensitive layer in the following method.Be produced on the sensitization tunic that applies with each sensitive layer coating liquid phase coating amount together with described (making of sensitive materials) middle coating on the glass substrate, the use ultrahigh pressure mercury lamp from the applicator surface side, carries out 70mJ/cm to it 2Exposure, with this sensitization tunic as working sample.Use contact pin type surfaceness meter P-1 (TENKOR corporate system) to measure the thickness of this laminated samples.
The thickness of this working sample is as shown in table 1.
(mensuration of optical density(OD))
Each working sample that use is used in described determining film thickness is measured the optical density(OD) of film.Use Mike and measure the optical density(OD) (OD) of this each working sample than thinking (Macbeth) densitometer (Mike is than thinking corporate system TD-904).In addition, measure the optical density(OD) (OD of another glass substrate with identical method 0).To deduct OD from OD 0The value of gained is as the optical density(OD) of film.The optical density(OD) of each working sample is as shown in table 1.
(mensuration of volume fraction)
At first, the mensuration that the amount of being coated with of particle is contained in silver-colored tin alloy portion is used employed each working sample in described determining film thickness, uses fluorescent X-ray device 3370E ((strain) system of science) to measure the amount of being coated with in this each working sample.
The thickness that uses this value and measure in the above utilizes following formula volume calculated branch rate.The volume fraction of each working sample is as shown in table 1.
The volume fraction of particle=(silver-colored tin alloy portion contains the amount of being coated with of particle/silver-colored tin alloy portion and contains Particle Density)/thickness is contained in silver tin alloy portion
In addition, utilize described method to calculate silver-colored tin alloy portion and contain Particle Density.
(XYZ shows chroma color coordinate (x, mensuration y))
(x, mensuration y) is used spectrophotometer OSP-SP200 (OLYMPUS (strain) system) to XYZ table chroma color coordinate, carries out as described above.
(evaluation of the formation of blue, red, green pixel and the bubble of pixel)
, use the spy and open use R (R1), the G (G1) that puts down in writing in the paragraph 0030～0036 of 2002-341127 communique, the method that photosensitive transfer printing material is used in the formation of B (B1) pixel with on the substrate of light shield layer in described band display unit, form pixel of all kinds.
Since in display unit with forming pixel of all kinds on light shield layer concavo-convex, so between glass substrate and each pixel, enter bubble sometimes.Measure this bubble generation degree with following method.
To each 100 of 3 color pixels of this glass substrate, totally 300 pixels, use opticmicroscope, the number of visual calculating bubble.The result is as shown in table 1.
(using the tonal variation of light shield layer because of the display unit of heating)
Under 220 ℃, described band display unit is carried out 2 hours thermal treatment with the substrate of light shield layer, the display unit before and after this thermal treatment of visual valuation is with the variation of the tone of light shield layer.
Do not find to change A fully
There is metalluster B slightly
Have little metal gloss, but practical going up allows C
Deposit and become the metalluster of obstruction degree D in actual use
There is metalluster E completely
That wherein, allow in the practicality is A～C.The result is as shown in table 1.
(evaluation of tone)
To liquid crystal indicator, be inserted in employed colour filter in the bubble evaluation from the rear, the poor contrast when visual observation shows black and white, classification as described below.
The higher-grade A that contrast gradient is very high
The higher-grade B that contrast gradient is very high
The middle grade C that contrast gradient is low
The low-down low-grade D of contrast gradient
The result is as shown in table 1.
(comparative example 1 and 2)
The dispersion liquid (A2) that dispersion of particles liquid (dispersion liquid A1) is altered to the silver-colored particulate that obtains is as described below contained in the silver-colored tin alloy portion that will use in embodiment 1, and sensitive layer is applied liquid be altered to following prescription, in addition, carry out similarly to Example 1, make the display unit light shield layer.The result is as shown in table 1.
The preparation of the dispersion liquid of＜silver-colored particulate (A2) 〉
(preparation of A liquid)
In decalcification gelatin 50g, add distilled water 1950g, with the mixture heating up that obtains to about 40 ℃, the dissolving gelatin.Use the 5%NaOH aqueous solution, it is adjusted to pH9.2,40 ℃ of insulations down.
(preparation of B liquid)
In decalcification gelatin 150g, add distilled water 1350g, with the mixture heating up that obtains to about 40 ℃, the dissolving gelatin.Use the 5%NaOH aqueous solution, it is adjusted to pH9.2.Stir and dissolving calcium acetate 16.0g and the Silver Nitrate 160g that is dissolved in the 320cc distilled water, add distilled water, final volume is adjusted to 2000cc, 40 ℃ of insulations down.
(preparation of C liquid)
Dissolving 110g S-WAT (anhydrous) in distilled water 700cc is dissolved in the product that 70cc methyl alcohol and 80cc water form to wherein mixing with quinhydrones 80g, and then adds distilled water, and final volume is adjusted to 2000cc, 40 ℃ of insulations down.
Stir described A liquid on one side apace, on one side with adding B liquid and C liquid 10 seconds simultaneously.After 10 minutes, add solution, after stirring 80 minutes, make its precipitation, cooling with concentrated hydrochloric acid 70cc and distilled water 8000cc dissolving anhydrous sodium sulphate 1600g gained.Remove after the supernatant, even, till can not precipitating, use distilled water drip washing immediately until adding the Br salts solution.After cutting off the water supply, dissolving again under 40 ℃ then is cooled to product near the gelling temperature then, then, makes it pass through little hole, and is added in the chilled water, forms very trickle noodles (noodle) thus.
With the solution that S-WAT (anhydrous) 20g, NaOH0.6g is dissolved in distilled water 2000cc gained it is cleaned, and then use the solution cleaning that Glacial acetic acid 20g is dissolved in gained among the distilled water 2000cc.Make the black slurry grain that obtains, in nylon net bag (nylon mesh bag), pass through tap water,, clean, wash out all salt so that rinse water was passed through bag about 30 minutes via slurry.For the black that has cleaned in being scattered in gel slurry silver, the aqueous vapor of removing product in the mode of the black silver dispersions of the silver that obtains to have under the fused state 1.5% concentration.
(making of silver-colored particle dispersion liquid A2)
Disperse among the slurry 5000g at the silver that obtains as mentioned above, add dispersion agent (peppery skin foot sieve (ラ ピ ゾ one Le) B-90, Japanese grease (strain) system) 25g and papain 5% aqueous solution 1000g, preserved 24 hours down at 37 ℃.With 2000rpm this liquid was carried out centrifugation 5 minutes, make silver-colored particulate sedimentation.Supernatant discarded is cleaned with distilled water then, removes by zymolytic gelatin resolvent.Then, with washed with methanol silver particulate sediment, make its drying.Obtain the agglutinator of the silver-colored particulate of about 85g.In this agglutinator 73.5g, mix this Lu Si Paasche (ソ Le ス パ one ス) 20000 (A Bisiya (ァ PVC シ ァ) (strain) makes dispersion agent) 1.05g and ethyl methyl ketone 16.4g.Use pearl dispersion machine (zirconium oxide bead 0.3mm), obtaining median size from it is the silver-colored particle dispersion liquid A2 of 30nm.
The preparation of＜sensitive layer coating liquid 〉
In the silver-colored particle dispersion liquid A2 of described making, add following compositions, be formulated in the sensitive layer coating liquid that uses in comparative example 1 and the comparative example 2.In addition, similarly to Example 1, the addition of dipentaerythritol acrylate is adjusted to the value that volume fraction becomes record in the table 1.
Silver particle dispersion liquid A2 40.0g
Propylene glycol monomethyl ether acetic ester 40.0g
Ethyl methyl ketone 37.6g
F-780-F (big Japanese ink chemical industry (strain) system, 30% ethyl methyl ketone solution) 0.2g
Quinhydrones monomethyl ether 0.001g
Dipentaerythritol acrylate
The volume fraction that is added into silver-colored particulate becomes the value of record in the table 1
Two [4-[N-[4-(4, the two trichloromethyls of 6--s-triazine-2-yl) phenyl] formamyl] phenyl] sebate 0.1g
(comparative example 3)
In embodiment 3, it is constant that the volume fraction that particle is contained in silver-colored tin alloy portion remains on necessarily (0.39), replacing being dispersed with silver-colored tin alloy portion contains the silver-colored tin alloy portion of particle and contains particle dispersion A1, use is dispersed with the carbon particulate dispersion liquid of the carbon particulate of median size 30nm, in addition, carry out similarly to Example 3, make the display unit light shield layer.The result is as shown in table 1.
In using the sooty comparative example, the number of bubble increases, and is not realistic scale.
[table 1]
As shown in table 1, even the display unit of embodiment is that the following film of 1 μ m also can have high optical density(OD) with light shield layer, black tone is outstanding, this tone can not change because of heating in addition, even and then when making colour filter, do not have a generation of bubble or seldom, have outstanding characteristic on the whole, satisfy realistic scale.
On the other hand, replacing silver-colored tin alloy portion to contain particle and use silver-colored particulate, is that the number of bubble in 0.02 the comparative example 1 increases at volume fraction, and in volume fraction was 0.73 comparative example 2, the tone after the heating greatly changed, and the two all is not a realistic scale.In addition, in using sooty comparative example 3, the number of bubble increases, and is not realistic scale.
(embodiment 6～10)
The silver-colored tin alloy portion that uses in embodiment 3 contains silver-colored tin alloy portion among the particle dispersion A1 and contains the average particulate size of particle and be respectively 20nm, 60nm, 100nm, 250nm and 500nm, in addition, carry out similarly to Example 3, form the display unit light shield layer.The result is as shown in table 2.
Optical density(OD), thickness, black tone, the heating change of tone, bubble all satisfy realistic scale.
[table 2]
Figure A20068003417300331
(embodiment 11～20)
In embodiment 1～10, except not being provided with on the sensitive layer the protective layer, similarly carry out with embodiment 1～10 respectively, make the display unit light shield layer.These samples can not be at the 70mJ/cm that uses ultrahigh pressure mercury lamp 2Exposure form down the display unit light shield layer, but can be at 500mJ/cm 2Exposure under obtain good display unit light shield layer.So, during the sample that in the mensuration of mensuration of making determining film thickness, optical density(OD) and volume fraction, uses, with conditions of exposure from 70mJ/cm 2Be altered to 500mJ/cm 2The result is as shown in table 3.
(comparative example 4～6)
In comparative example 1～3, except not being provided with on the sensitive layer the protective layer, similarly carry out with comparative example 1～3 respectively, make the display unit light shield layer.These samples can not be at the 70mJ/cm that uses ultrahigh pressure mercury lamp 2Exposure form down the display unit light shield layer, but can be at 500mJ/cm 2Exposure under obtain the display unit light shield layer.So, in the mensuration of the mensuration of determining film thickness, optical density(OD) and volume fraction, with conditions of exposure from 70mJ/cm 2Be altered to 500mJ/cm 2, similarly measure.The display unit that comparative example 4～6 is made not is similarly to be realistic scale with comparative example 1～3 with light shield layer.The result is as shown in table 3.
[table 3]
(embodiment 21～30)
In these each embodiment, use photosensitive transfer printing material to make the display unit light shield layer.
[making of photosensitive transfer printing material]
Photosensitive transfer printing material is on the polyethylene terephthalate supporter of the thick 75 μ m of two-way stretch, uses the sliding type coating machine, and the mode that becomes 15 μ m with dry film thickness applies following thermoplastic resin with coating liquid, 100 ℃ dry 5 minutes down.Then, coating middle layer coating liquid on this film so that dry film thickness becomes 1.5 μ m, and 100 ℃ dry 5 minutes down, and then coating sensitive layer coating liquid, 100 ℃ dry 5 minutes down.
Sensitive layer among the embodiment 21～30 coating liquid uses respectively the sensitive layer coating liquid of the same composition corresponding with embodiment 1～10.In addition, coating liquid formula in middle layer uses the coating liquid of forming together with the protective layer coating liquid phase of embodiment 1.The composition that below shows thermoplastic resin coating liquid.
(thermoplastic resin coating liquid)
Methyl methacrylate/acrylic acid-2-ethyl polyhexamethylene/methacrylic acid benzyl ester/Sipacril 2739OF (copolymerization ratio of components (mol ratio)=55/11.7/4.5/28.8, molecular weight=90,000, Tg
Figure A20068003417300361
70 ℃) 58 parts
The multipolymer of styrene/acrylic=70/30 (copolymerization ratio of components (mol ratio)=63/37, molecular weight=10,000, Tg 100 ℃) 136 parts
2,90 parts in two [4-(methacryloyl polyethoxye) phenyl] propane of 2-(Xin Zhong village chemistry strain system, polyfunctional acrylic ester)
1 part of F-780-F (big Japanese ink chemical industry (strain) system, fluorine is a tensio-active agent)
541 parts of ethyl methyl ketones
63 parts of 1-methoxyl groups-2-propyl alcohol
111 parts of methyl alcohol
[the display unit making of light shield layer]
Utilize spray, spray adjusted in 20 second is 25 ℃ a glass washing composition liquid on alkali-free glass substrate, clean with rotating brush simultaneously with nylon hair, after the pure water spray Cleaning for High Capacity, utilize spray, spray 20 second silane coupling agent liquid (N-β (amino-ethyl) the gamma-amino propyl trimethoxy silicane 0.3 quality % aqueous solution, trade(brand)name: KBM603, SHIN-ETSU HANTOTAI's chemical industry (strain) system), use the pure water spray Cleaning for High Capacity.Prepare heating unit with substrate, heated this substrate 2 minutes down, deliver to next laminator at 100 ℃.
Overlapping glass substrate and described photosensitive transfer printing material contain layer (that is, sensitive layer) contact so that particle is contained in described glass substrate and silver-colored tin alloy portion, use laminator ((strain) INDASTRIES of Hitachi system (LamicII type)), fit the two.Lamination is to the substrate that is heated to 100 ℃, carries out with 130 ℃ of rubber rollers temperature, line pressure 100N/cm, transfer rate 2.2m/ part.Then, peel off the polyethylene terephthalate supporter.
With the interim supporter of the interface peel of thermoplastic resin after, with the close induction type exposure machine with ultrahigh pressure mercury lamp (Hitachi's high-tech electronic engineering (strain) system), with substrate and the vertical state that erects of mask (quartzy exposed mask) with picture pattern, with the distance setting between exposed mask face and this thermoplastic resin is 200 μ m, with exposure 70mJ/cm 2Carry out pattern exposure.
Then, with 30 ℃, 50 seconds, flat burner pressure 0.04MPa, to trolamine is that developing solution (will contain 2.5% trolamine, contains nonionic surfactant, contain polypropylene-based defoamer, trade(brand)name: T-PD1, Fujiphoto (strain) system, be diluted to 12 times liquid with pure water) spray development, remove thermoplastic resin and middle layer.
Then, use yellow soda ash be developing solution (will contain the sodium bicarbonate of 0.06 mol, with the yellow soda ash of concentration, 1% sodium dibutyl naphthalene sulfonate, anion surfactant, defoamer, stablizer, trade(brand)name: T-CD1, Fujiphoto (strain) system, liquid with 5 times of pure water dilutions), with 29 ℃, 30 seconds, pyramid type nozzle pressure 0.15MPa, spray development, photo-sensitive resin is developed, obtain pattern image.
Then, use clean-out system (will contain phosphate silicate nonionogenic tenside defoamer stablizer, trade(brand)name " T-SD1 " Fujiphoto (strain) system, be diluted to 10 times liquid with pure water), with 33 ℃, 20 seconds, pyramid type nozzle pressure 0.02MPa, by spray quinoline and rotating brush with nylon hair, remove resistates, deceived the image of (K).Then, and then this substrate from this resin layer one side, is used ultrahigh pressure mercury lamp, with 500mJ/cm relatively 2Light, carry out post-exposure, then with 220 ℃ of thermal treatments 15 minutes, form light shield layer.
Conditions of exposure during the sample that uses in the mensuration of mensuration of making determining film thickness, optical density(OD) and volume fraction is 70mJ/cm too 2The result is as shown in table 4.
(comparative example 7～9)
Use in the making of light shield layer in the display unit of embodiment 21, replace sensitive layer coating liquid, use the sensitive layer coating liquid that in comparative example 1～3, uses respectively, in addition as the embodiment 1 of sensitive layer coating liquid, carry out similarly to Example 21, make the display unit light shield layer.The result is as shown in table 4.
The display unit that obtains from comparative example 7～9 is identical with comparative example 1～3 with light shield layer, is not realistic scale.
[table 4]
Figure A20068003417300391
Shown in table 1～table 4, even can obtain extremely thin layer, even optical density(OD) is also high, black tone is also outstanding, the also little display unit light shield layer of tonal variation under the situation of accepting heating in addition from the coloured composition that satisfies important document of the present invention near 0.1 μ m.In addition because it is little with the thickness of light shield layer to be used to obtain the display unit of necessary optical density(OD), so in the band display unit when making the colour filter pixel on the substrate of light shield layer, the number of bubbles that is involved in is also few.
Relative therewith, when carbon black is used as black pigment, even make this median size and volume fraction identical with the invention of this part, can not realize that illuminant-C sees through the correlated condition of the XYZ color specification system tristimulus coordinates of light, the result, display unit in addition, is used to realize that the thickness of same optical density also becomes big with the tone variation of light shield layer.
Use the display unit light shield layer of described making, utilize the method for record in the embodiment 1 of WO2006-38731, form rgb pixel, then, make liquid crystal indicator.
Use the display unit of making in an embodiment to compare with the liquid crystal indicator of light shield layer with the display unit of in comparative example, making, also do not have the look inequality, for height shows grade with the liquid crystal indicator of light shield layer.
Utilizability on the industry
Coloured composition of the present invention can be used for make film and the high and low cost of shading performance, to ring The impact in border is little, the outstanding display unit light shield layer of black (netrual colour of non-cohesive color and taste) tone. In addition, utilize tone variations that display unit that the present invention obtains do not cause because of heating with light shield layer or Considerably less, so, can make flatness outstanding, when forming rgb pixel, can not sneak into bubble The perhaps considerably less colour filter of bubble. And then this colour filter can be used for making liquid crystal indicator.

Claims (19)

1. a coloured composition is characterized in that,
Contain the metallics with silver-colored tin alloy portion, the optical density(OD) after the film of corresponding per 1 μ m dry film thickness forms is more than 3.5.
2. coloured composition according to claim 1 is characterized in that,
Volume fraction in the solids component of described metallics with silver-colored tin alloy portion is 0.05～0.7, and in the light shield layer that the colored coating composition forms, and illuminant-C sees through the XYZ color specification system tristimulus coordinates of light, and (x is y) with the tristimulus coordinates (x of described light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤ 0.01 relation.
3. coloured composition according to claim 1 is characterized in that,
Described median size with metallics of silver-colored tin alloy portion is below the 500nm.
4. coloured composition according to claim 2 is characterized in that,
Described median size with metallics of silver-colored tin alloy portion is below the 500nm.
5. coloured composition according to claim 1 is characterized in that,
Described coloured composition has photosensitivity.
6. coloured composition according to claim 2 is characterized in that,
Described coloured composition has photosensitivity.
7. a photosensitive transfer printing material is characterized in that,
The photosensitivity light shield layer that has supporter and on this supporter, be provided with at least, this photosensitivity light shield layer contains the metallics with silver-colored tin alloy portion, the optical density(OD) of the photosensitivity light shield layer of corresponding per 1 μ m dry film thickness is more than 3.5, the volume fraction of the metallics with silver-colored tin alloy portion in the photosensitivity light shield layer is 0.05～0.7, and the illuminant-C of light shield layer sees through the XYZ color specification system tristimulus coordinates of light, and (x is y) with the tristimulus coordinates (x of described light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤ 0.01 relation.
8. display unit light shield layer, the display unit light shield layer that it is to use the described coloured composition of claim 1 to make.
9. display unit light shield layer, the display unit light shield layer that it is to use the described coloured composition of claim 2 to make.
10. display unit light shield layer, the display unit light shield layer that it is to use the described coloured composition of claim 5 to make.
11. a display unit light shield layer, the display unit light shield layer that it is to use the described coloured composition of claim 6 to make.
12. a display unit light shield layer, the display unit light shield layer that it is to use the described photosensitive transfer printing material of claim 7 to make.
13. a colour filter is characterized in that,
Have the photopermeability substrate and be arranged on the pixel groups more than 2 that presents different colors from one another on this substrate, described pixel groups is made of pigmented layer, each pixel that constitutes described pixel groups is shown device each other to be separated with light shield layer, and described display unit light shield layer is the described display unit light shield layer of claim 8.
14. a liquid crystal display device is characterized in that,
At least possess: at least one has the 1 pair of substrate and the colour filter that has, liquid crystal layer and the liquid crystal drive mechanism of photopermeability between this substrate, described colour filter is the described colour filter of claim 13.
15. a liquid crystal display device is characterized in that,
At least possess: at least one has the 1 pair of substrate and the colour filter that has, liquid crystal layer and the liquid crystal drive mechanism of photopermeability between this substrate, described liquid crystal drive mechanism has active component, is formed with the described display unit light shield layer of claim 8 between each active component.
16. the display unit manufacture method of light shield layer wherein, has:
On the photopermeability substrate, form the operation of the layer that constitutes by the described coloured composition of claim 1; And
After described layer being exposed with photomask with light shield layer via display unit, the operation of developing.
17. the display unit manufacture method of light shield layer wherein, has:
On the photopermeability substrate, form the operation of the layer that constitutes by the described coloured composition of claim 2; And
After described layer being exposed with photomask with light shield layer via display unit, the operation of developing.
18. the display unit manufacture method of light shield layer wherein, has:
On the photopermeability substrate, be laminated to less the described photosensitive transfer printing material of claim 7 that the photosensitivity light shield layer forms is set on supporter, and the operation that this photosensitive transfer printing material is contacted with described photosensitivity light shield layer;
Peel off the operation of supporter from the duplexer of described photosensitive transfer printing material and photopermeability substrate; And
After described photosensitivity light shield layer being exposed with photomask with light shield layer via display unit, the operation of developing.
19. the substrate with display unit usefulness light shield layer is characterized in that,
The display unit light shield layer that has the photopermeability substrate and on this substrate, be provided with, use in the light shield layer in described display unit, metallics with silver-colored tin alloy portion disperses with volume fraction 0.05～0.7, corresponding per 1 μ m display unit is more than 3.5 with the optical density(OD) of light shield layer, and display unit sees through the XYZ color specification system tristimulus coordinates of light with the illuminant-C of light shield layer, and (x is y) with the tristimulus coordinates (x of described light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤ 0.01 relation.
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Cited By (4)

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WO2007032144A1 (en) 2007-03-22
TW200722485A (en) 2007-06-16

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