CN101268151B - Colored composition and photosensitive transfer material - Google Patents

Colored composition and photosensitive transfer material Download PDF

Info

Publication number
CN101268151B
CN101268151B CN2006800341739A CN200680034173A CN101268151B CN 101268151 B CN101268151 B CN 101268151B CN 2006800341739 A CN2006800341739 A CN 2006800341739A CN 200680034173 A CN200680034173 A CN 200680034173A CN 101268151 B CN101268151 B CN 101268151B
Authority
CN
China
Prior art keywords
light shield
shield layer
display unit
silver
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2006800341739A
Other languages
Chinese (zh)
Other versions
CN101268151A (en
Inventor
畠山晶
后藤英范
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN101268151A publication Critical patent/CN101268151A/en
Application granted granted Critical
Publication of CN101268151B publication Critical patent/CN101268151B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

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 with light shield layer and method of manufacture thereof, filter, liquid crystal display device and band display unit substrate with light shield layer.
Background technology
The filter that in colour liquid crystal display device etc., uses forms colored pixels layer (R, G, B) on transparency carrier, then, for improve show contrast gradient etc. and in the gap of each colored pixels of R, G, B (red, green, blue) the formation display unit use light shield layer.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 mf is formed metallic membrane.On this mf, 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 mf that etching is exposed at last through 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 mf, can not ignore the problems such as burden to environment when existing cost to uprise.In addition, owing to be metallic membrane,, under strong outer light, show that contrast gradient is low so reflectivity is high.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 the for example method of sooty photosensitive polymer combination of opacifying property pigment.This method is for example on transparency carrier, to form 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 said metallic membrane, although the manufacturing cost step-down, in order to obtain sufficient opacifying property, the thickness thickening.As a result, between display unit is with light shield layer and R, G, B pixel, produce overlapping (staggered floor), the flatness variation of filter, the unit interval that liquid crystal display device takes place is uneven, causes that look unequal demonstration is bad.
In addition, contain the sooty photosensitive polymer combination and make display unit and use light shield layer if on substrate, use at first, to form rgb pixel then, then display unit is with the thickness thickening of light shield layer.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 through making the relief on the said transparency carrier, can obtain metallics that the shading of particle diameter 0.01～0.05 μ m uses within it portion's display unit of disperseing equably to form use light shield layer.As said 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 using light shield layer with low-cost production's display unit.
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 the shading performance is high, can with low-cost production, little to the influence of environment, can make coloured composition and the photosensitive transfer printing material of the display unit of black (Achromatic color of non-cohesive color and taste) with light shield layer.In addition, the present invention also provide use said coloured composition or photosensitive transfer printing material display unit with light shield layer and method of manufacture thereof, filter and the liquid crystal display device of said display unit with light shield layer is set.And then the present invention also provides and forms display unit as stated with the band display unit of the light shield layer substrate with light shield layer.
Said problem solves with light shield layer and method of manufacture, filter, liquid crystal display device and the band display unit substrate with light shield layer through 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 said (1) described coloured composition, it is characterized in that,
Volume fraction in the solids component of said metallics with silver-colored tin alloy portion is 0.05～0.7, and in the light shield layer that the colored coating compsn 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 said light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤0.01 relation.
(3) according to said (1) or (2) described coloured composition, it is characterized in that,
Said median size with metallics of silver-colored tin alloy portion is below the 500nm.
(4) according to any described coloured composition in said (1)～(3), it is characterized in that,
Said 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 said light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤0.01 relation.
(6) a kind of display unit is used light shield layer, and it is to use any described coloured composition in said (1)～(4) or said (5) described photosensitive transfer printing material and the display unit of making is used light shield layer.
(7) a kind of 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; Said pixel groups is made up of pigmented layer; Each pixel that constitutes this pixel groups is shown device each other to be separated with light shield layer, and it is that said (6) described display unit is used light shield layer that this display unit is used 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 filter that between this substrate, has, liquid crystal layer and liquid crystal drive mechanism, said filter is said (7) described 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 filter that between this substrate, has, liquid crystal layer and the liquid crystal drive mechanism of photopermeability; Said liquid crystal drive mechanism has active component, between each active component, is formed with said (6) described display unit and uses light shield layer.
(10) a kind of display unit wherein, has with the method for manufacture of light shield layer:
Form the operation of the layer of any described coloured composition in photopermeability substrate and said (1)～(4) on this substrate; And
Via display unit with light shield layer with photomask to said coloured composition the layer make public after, the operation of developing.
(11) a kind of display unit wherein, has with the method for manufacture of light shield layer:
In photopermeability substrate laminated said (5) described photosensitive transfer printing material that the photosensitivity light shield layer forms and the operation that it is contacted with said photosensitivity light shield layer are set on supporter at least;
Peel off the operation of supporter from the duplexer of said photosensitive transfer printing material and photopermeability substrate; And
After said photosensitivity light shield layer being made public with photomask with light shield layer via display unit, the operation of developing.
(12) a kind ofly it is characterized in that with the substrate of display unit with light shield layer,
Has the photopermeability substrate and the display unit on this substrate is used light shield layer; 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; It is more than 3.5 that the display unit of the per 1 μ m of corresponding dry film thickness is used 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 said 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 using light shield layer for film and the high and low cost of shading performance,, the outstanding display unit of black (Achromatic color of non-cohesive color and taste) tone 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 filter of light shield layer.And then it is uneven that the liquid crystal indicator of assembling this filter can the generating unit spacing between 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 applies said coloured composition formation; Illuminant-C sees through the XYZ color specification system tristimulus coordinates of light, and (x is y) with the tristimulus coordinates (x of said light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤0.01 relation.
Said " volume fraction of particle is contained in the silver-colored tin alloy portion in the solids component " is meant applying the silver-colored tin alloy portion of containing in the light shield layer (said coloured composition has under the photosensitive situation, the layer after colored coating compsn and exposure are solidified) that dry said coloured composition obtains and contains the volume fraction of particle.In addition; The volume fraction that particle is contained in the silver-colored tin alloy portion that said volume fraction also refers to contain in light shield layer in display unit is (in coloured composition; Contain the particle except 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 is used g/m 2Expression, density is used g/cm 3Expression; Thickness (light shield layer or display unit are with the thickness of light shield layer) is represented with μ m; In said 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 through 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 is claimed, add exsiccant sample then, claim to calculate the quality (W2g) of sample, add sample in the gap of specific gravity hydrometer through essence; Can fully bury the liquid of known proportion (D1g) until sample integral body, use UW to carry out deaeration.After powdered sample fully precipitates, and then replenish said liquid, filling liq fully in specific gravity hydrometer with temperature regulation to 25 ℃, covers specific gravity hydrometer, the smart total quality (W3g) of claiming.Like this, can calculate the quality of said 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, through calculating primary stimuli value X, Y, Z the illuminant-C from this spectrum, tries to achieve tristimulus coordinates.The XYZ color specification system tristimulus coordinates (x of the illuminant-C that uses in the present invention in addition, 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 OSP-SP100 and the OSP-SP200 of OLYMPUS system etc.
In coloured composition of the present invention; If containing the median size and the volume fraction of particle, said 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 said light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤0.01 relation.
Said illuminant-C have with liquid crystal indicator in the proximate characteristic of backlight light source used, through satisfying said condition, then show can not receive the transmission display device with the influence of the light of light shield layer the tone variation of black part.Said 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 said 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 likewise 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 up of silver-colored tin alloy, metallics that is made up of silver-colored tin alloy part and other metal section and parts and the metallics that partly is made up 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) like 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 up of silver-colored tin alloy.This formation for example can use the HD-2300 of (strain) Hitachi system and the EDS (energy dispersion type x-ray analysis equipment) of Noran corporate system to confirm.Its condition determination is the spectrum in each the particle center 15nm zone under the acceleration voltage 200kV.
The black concentration that particle is contained in silver tin alloy portion is high, the luminescent properties that can do well with a small amount of or film, and have high thermal stability.Thereby, can not destroy black concentration and under high temperature (for example more than 200 ℃), heat-treat, 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 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 through making Ag especially in said scope, can obtain the black concentration of thermostability height high, that suppress the reflection of light rate under high-temperature area.
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 said scope.
The manufacturing that particle is contained in silver-colored tin alloy portion among the present invention can wait and forms through in crucible etc., utilizing usual methods such as heating, melting mixing formation to carry out alloying.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 through making Ag and/or Sn become complex salt, control the time of separating out.
As said 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 said 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 said reductive agent, can enumerate quinhydrones, catechol, PARA 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 or median size (size of particles), the particle shape etc. shown in following.
Silver-colored tin alloy portion among the present invention contains particle and is preferably the particle that in the mensuration of utilizing differential scanning calorimetry (DSC:Differential Scanning Calorimetry), has 240～400 ℃ fusing point.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 property (fusing point) of AgSn alloy with being described below, that is, the 20mgAgSn alloy is positioned over DSC (SSC/5200 as sample; Seiko instrument (セ イ コ one イ Application ス Star 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 said 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.
Said number average size of particles uses the photo that utilizes transmission electron microscope JEM-2010 (NEC's (strain) system) to obtain, and measures with being 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.
As the particle shape of " silver-colored tin alloy portion contain particle " among the present invention, not special restriction can not be random shapes such as cubic, high aspect ratio, middle aspect ratio, needle-like.
Contain in the particle in silver-colored tin alloy portion,, and then also can contain salt or organism, other elements (Ca, P, Na etc.) etc. except Ag and the Sn.Wherein, even in this case, also preferably have said 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 compsn 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 said scope, then can suppress the reflection of light rate, black concentration is high, 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 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 %, reflectivity is high, destroys sometimes to show contrast gradient.
(having photosensitive coloured composition)
Coloured composition among the present invention preferably has photosensitivity.In order to give photosensitivity, in said coloured composition, add photosensitive polymer combination.Photosensitive polymer combination contains binder polymer, has the monomer that under the irradiation of light, carries out addition polymerization of ethene property unsaturated double-bond, Photoepolymerizationinitiater initiater etc.
Photosensitive polymer combination comprises can carry out alkali aqueous solution compsn that develops and the compsn that can in organic solvent, develop.As photosensitive polymer combination,, preferably can carry out the compsn that alkali aqueous solution develops from the point of the cost of security and developing solution.
Photosensitive polymer combination can not accepted portion's solidified eurymeric for radioactive rays for accepting the part generation solidified minus of light, electron rays isoradial yet.
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 compsn 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.This photo-sensitive resin can utilize the spy to open " polymerizable compound B " " polymerization starter C " " tensio-active agent " " bonding auxiliary agent " or other compsns of putting 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 of afterwards stating etc.) and can contain monomer and Photoepolymerizationinitiater initiater at the ethene property unsaturated double-bond of addition polymerization under the rayed as staple.
As tackiness agent; Can enumerate the polymkeric substance that has the carboxylic acid group at side chain, the 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 special and opened the Sipacril 2739OF put down in writing in the clear 59-71048 communique, PEMULEN TR2, itaconic acid copolymer, Ba Dousuan multipolymer, maleic acid, partial esterification maleic acid etc.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 USP, or (methyl) vinylformic acid benzyl ester and (methyl) vinylformic acid and other monomeric multiple copolymers.
The tackiness agent that in photo-sensitive resin, uses 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 property etc. in order to improve various performances.As these polymkeric substance, can enumerate alcohol soluble nylon or epoxy resin.
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 the San Lu that puts down in writing in No. 4212976 specification sheets of trihalomethyl group-s-triaizine compounds, USP of putting down in writing in the benzothiazole compound put down in writing in the combination put down in writing in No. 2722512 specification sheets of accidental cause ether compound, USP of putting down in writing in disclosed vicinal polyketals (Polyketaldonyl) compound in No. 2367660 specification sheets of USP, No. 2448828 specification sheets of USP, the special public clear 51-48516 communique and trihalomethyl group-s-triaizine compounds, No. 4239850 specification sheets of USP for Jia oxadiazole compound etc. with triarylimidazoles dimer of putting down in writing in No. 3549367 specification sheets of polynucleation quinone compound, USP of putting down in writing in the substituted aromatic series accidental cause of α-hydrocarbon compound, No. 3046127 specification sheets of USP and No. 2951758 specification sheets of USP and p-keto-amine.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 property unsaturated double-bond monomer (being designated hereinafter simply as " monomer "), can enumerate boiling point is the compound more than 100 ℃ under normal pressure.For example can enumerate simple function (methyl) propenoate such as polyoxyethylene glycol one (methyl) propenoate, W 166 one (methyl) propenoate and (methyl) vinylformic acid phenoxy ethyl ester; Polyoxyethylene glycol two (methyl) propenoate, W 166 two (methyl) propenoate, trimethylolethane trimethacrylate propenoate, Viscoat 295, trimethylolpropane diacrylate, NSC 6366 two (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, tetramethylolmethane three (methyl) propenoate, Dipentaerythritol six (methyl) propenoate, Dipentaerythritol five (methyl) propenoate, pinakon two (methyl) propenoate, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) chlorinated isocyanurates, three (acryloxy ethyl) cyanurate, glycerine three (methyl) propenoate, on polyfunctional alcohols such as TriMethylolPropane(TMP) or glycerine after addition of ethylene oxide or the propylene oxide, multifunctional (methyl) propenoate 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 epoxy resin with (methyl) acrylic acid reaction product.Wherein, preferred trimethylolpropane tris (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, Dipentaerythritol six (methyl) propenoate, Dipentaerythritol five (methyl) propenoate.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 said 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, β-Nai Fen, 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, skimmer, fire retardant, brightening agent, solvent etc.
As tackifier, for example can enumerate petroleum resin, silane coupling agent of alkylphenol/formaldehyde phenolic resin varnish, Vilaterm ethyl ether, PVI polyvinyl isobutyl ether, polyvinyl butyral acetal, polyisobutene, styrene-butadiene copolymer rubber, butyl 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 said photosensitive polymer combination, the compsn of essential water system.As such photosensitive polymer combination, except the spy opens the compsn 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 compsn.
(not having photosensitive coloured composition)
Do not have photosensitive coloured composition in the present invention and contain the particle, contain tackiness agent, dispersion agent, solvent etc. as required except aforesaid silver-colored tin alloy portion.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 property.The soluble polymer resin tackiness agent for example can be enumerated gelatin, Z 150PH, methylcellulose gum, hydroxypropylcellulose, gather 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) academy issued 2000 towards the storehouse) ".
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, and the census of manufacturing can be issued, distribution on October 25 nineteen sixty-eight) 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, PS, resol, Vilaterm; Polycarbonate, silicone resin, urethane, polyacid acid anhydride, polysulfones, gather imines, polysulfide, polyacrylonitrile, nylon, PVA, polyvinyl ether, ROHM 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 with 48 years), put down in writing.
As said 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 (tree elastomer), 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 said polymer emulsion.As can and the polymer emulsion of usefulness; The for example preferred SBR material different with the nitro amount of 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 material of material and the cationic of anionic property.
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 said 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 special preferred organic, 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 said photosensitive coloured composition that has, make photosensitive transfer printing material, use it to make display unit and use light shield layer.
Said photosensitive transfer printing material is that the material that has the photosensitivity light shield layer that photosensitive coloured composition forms by said 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, PS.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 range upon range of operation, there is the shortcoming because of the tabular wrinkle of heat generation zinced 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 in thermoplastic resin, contains, that preferably from saponified, (methyl) Yodo Sol GH 28 of gathering (methyl) propenoate and (methyl) Bing Xisuandingzhi and vinyl acetate etc. of saponified, the Vinyl toluene of saponified, the vinylbenzene of ethene and Yodo Sol GH 28 and (methyl) Yodo Sol GH 28 and (methyl) Yodo Sol GH 28 etc. saponified etc., selects 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, and the census of manufacturing can be issued, distribution on October 25 nineteen sixty-eight) 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 methylacrylic acid, also comprises the situation of its verivate.
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 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, spy open clear 61-134756 number, special public clear 59-44615 number, spy open clear 54-92723 number, spy open clear 54-99418 number, spy open clear 54-137085 number, spy open clear 57-20732 number, spy open clear 58-93046 number, spy open clear 59-97135 number, spy open clear 60-159743 number, OLS3504254 number, spy open clear 60-247638 number, spy open clear 60-208748 number, spy open clear 60-214354 number, spy open clear 60-230135 number, spy open clear 60-258539 number, spy open clear 61-169829 number, spy open clear 61-213213 number, spy open clear 63-147159 number, spy open clear 63-213837 number, spy open clear 63-266448 number, spy open clear 64-55551 number, spy open clear 64-55550 number, spy open flat 2-191955 number, spy open flat 2-199403 number, spy open flat 2-199404 number, spy open flat 2-208602 number, specially be willing to that flat 4-39653 number, spy open the soluble resin of putting down in writing in each communique specification sheets of flat 5-241340 number in alkali aqueous solution.Open methylacrylic acid/acrylic acid-2-ethyl polyhexamethylene/methylacrylic acid benzyl ester/methylmethacrylate copolymer of putting down in writing in the clear 63-147159 specification sheets particularly preferably in the spy.
In addition, in described various resins, can be preferably be 3,000～30,000 scope of (Tg=30～170 ℃) and then preferably, weight-average molecular weight selects to use in being 4 do～2 ten thousand scope of (Tg=60～140 ℃) in weight-average molecular weight.Preferred concrete example can be selected from the concrete example of said patent specification, putting down in writing, and 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 the condensation reaction products etc. of addition reaction product, dihydroxyphenyl propane and polyoxyethylene glycol one (methyl) propenoate of addition reaction product, organic diisocyanate and W 166 one (methyl) propenoate of addition reaction product, organic diisocyanate and polyoxyethylene glycol one (methyl) propenoate of W 166, polyoxyethylene glycol, DOP, diheptyl phthalate, Witcizer 300, tritolyl phosphate, phosphoric acid cresols diphenyl, phosphoric acid xenyl diphenyl, polyoxyethylene glycol one (methyl) propenoate, polyoxyethylene glycol two (methyl) propenoate, W 166 one (methyl) propenoate, W 166 two (methyl) propenoate, epoxy resin and polyoxyethylene glycol one (methyl) propenoate.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 property, manufacturing flexibility for the upper limit.
In the present invention, as the solvent of thermoplastic resin, get final product so long as dissolving constitutes the solvent of the resin of this layer, not special restriction can be used.As the example of this solvent, for example can enumerate ethyl methyl ketone, pimelinketone, Ucar 35 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.
As the resin that constitutes the middle layer, not special restriction is preferably alkali-soluble.As the example of resin, can enumerate polyvinyl alcohol resin, Vinylpyrrolidone polymer 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 Z 150PH.As Z 150PH, 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 Z 150PH and Vinylpyrrolidone polymer.The weight ratio of the two is Vinylpyrrolidone polymer/Z 150PH=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 property 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 property 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, if said resin dissolves, then not special restriction, preferably water.The also preferred mixed solvent that in water, mixes said water Combination organic solvent.Preferred concrete example as the coating solvent in middle layer is 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 through on supporter; Use turner (rotation mode, crack formula and rotary (slit and spin)), coating machine (ホ ワ イ 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, the solution that the coating drying has photosensitive coloured composition of the present invention forms.Under the situation of the layer that thermoplastic resin is set, likewise 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 stated, so, can make the display unit that possesses for the high light shield layer of film and optical density(OD) and use light shield layer.
[display unit is with light shield layer and preparation method thereof]
Display unit of the present invention uses said 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.Said display unit with 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 said light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤0.01 relation, as stated, even since for film also have sufficient optical density(OD) and have tone and then the tonal variation that causes of heating of outstanding black little or do not have, so preferred.In addition, owing to be film, so under the situation that forms filter, be difficult to take place overlapping with pixel such as RGB, the flatness raising of 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 said photosensitive transfer printing material of making is identical) of coloured composition; Utilize ordinary method; Make public 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, can contain silver-colored tin alloy of the present invention portion and contain the coloured composition of particle and form after the layer of coloured composition through on the photopermeability substrate, applying at coloured composition; On this layer, form the layer that constitutes by the photosensitive polymer combination that can develop, utilize ordinary method; Make public with photomask with light shield layer via display unit; Then, develop, etching, form light shield layer thus.
The display unit of using said photosensitive transfer printing material is configuration, a range upon range of said 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; Via display unit with light shield layer with the said layer of photomask exposure, develop then, 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 method for manufacture of light shield layer, so be low-cost.
[filter]
Filter of the present invention has the structure that is 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 said pixel groups is separated with light shield layer by display unit each other, this display unit uses said 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 said 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.
During color filter manufacturing, on the photopermeability substrate, utilize ordinary method; Form after 2 above pixel groups; Can form display unit as described above and use light shield layer, perhaps also can use light shield layer, form the pixel groups more than 2 then in the initial display unit that forms.
Filter of the present invention possesses display unit as stated and uses light shield layer, thus show that contrast gradient is high, and also flatness is outstanding.And then, because display unit is little with the thickness of light shield layer, so when the color filter manufacturing pixel, the number of bubbles that is involved in is also few perhaps not to be had.
[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 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 said filter; Use to have a plurality of pixel groups as stated, each pixel that constitutes said pixel groups is each other by the filter of display unit of the present invention with the light shield layer separation.Because the flatness of said filter is high, the generating unit spacing is uneven between filter and substrate so possess the liquid crystal display device of this filter, and 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 filter between this substrate, liquid crystal layer and liquid crystal drive mechanism; Said liquid crystal drive mechanism has active component (for example TFT), and between each active component, is formed with the display unit of using coloured composition of the present invention or photosensitive transfer printing material to make and uses light shield layer.
[the band display unit is with the 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; The optical density(OD) of the per 1 μ m of thickness to 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 said 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 for color filter manufacturing 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, be with display unit with the substrate of light shield layer on during the color filter manufacturing pixel, the number of bubbles that is involved in is also less.
Embodiment
Below utilize embodiment further to specify the present invention, but the present invention is not limited by these embodiment.In addition, in following, " part " and " % " is represented " mass parts " and " quality % " respectively.
(embodiment 1～5)
< the preparation of dispersion liquid (dispersion liquid A1)>with 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 said solution that obtains 1 is remained on 25 ℃, and wherein add said 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 spinning makes silver-colored tin alloy portion contain particle precipitation.Spinning is the aliquot liquid measure that is divided into 150ml, utilizes desk-top separating centrifuge H-103n ((strain) KOKUSAN system), and several 2 to rotate, 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 spinning relatively, makes silver-colored tin alloy portion contain particle precipitation once more.Spinning with said identical condition under carry out.After carrying out spinning,, so that being 150ml, total liquid measure to wherein adding pure water 850ml and acetone 500ml, and then stirred 15 minutes with said supernatant discarded likewise, and make silver-colored tin alloy portion contain particle once more and disperse.
Likewise carry out with said once more; Carry out spinning, making after silver-colored tin alloy portion contains particle precipitation, with said supernatant discarded likewise; 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 spinning once more.The condition of the spinning of this moment is except being extended down to the time 90 minutes, with said identical.Then, supernatant discarded makes total liquid measure become 70ml, to wherein adding acetone 30ml.Use Eiger kibbler (Eiger kibbler 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 up 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's (strain) system) to obtain, and utilizes said method to carry out.
< sensitive layer applies the preparation of liquid >
Contain among the dispersion of particles liquid A1 in the silver-colored tin alloy portion of said making and to add following compositions, be formulated in the sensitive layer that uses among embodiment 1～embodiment 5 and apply liquid.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 said silver-colored tin alloy portion ... 50.00 part
Ucar 35 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
< resist applies the preparation of liquid >
Z 150PH ((strain) CLEA makes PVA205) ... 3.0 part
Vinylpyrrolidone polymer (ISPJapan (strain) makes PVP-K30) ... 1.3 part
Zero(ppm) water ... 50.7 part
Methyl alcohol ... 45.0 part
< 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 ℃, and with coating machine (coater) (flat field machine worker (strain) system), the sensitive layer that applies each embodiment respectively applies liquid with the glass substrate with slot-shaped nozzle.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 above that, apply resist and apply liquid, make dry film thickness become 1.5 μ m, drying is 5 minutes under 100 ℃, obtains photo-sensitive resin K1.
< display unit is with the making of light shield layer >
With close induction type exposure machine (Hitachi's high-tech electronic engineering (strain) system) with ultrahigh pressure mercury lamp; 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 utilizing spray spout, the spray ultrapure water removes the developing solution or the said photo-sensitive resin solute of attachment removal from the two sides; 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 with following method.Be produced on the glass substrate and apply the sensitization tunic that liquid phase coating amount together applies with each sensitive layer with said (making of sensitive materials) middle coating, 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 said 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 said 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 said 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)
On the substrate of said band display unit with light shield layer, use is opened use R (R1), G (G1), B (B1) pixel put down in writing in the paragraph 0030～0036 of 2002-341127 communique the spy and is formed the method with photosensitive transfer printing material, forms pixel of all kinds.
Since in display unit with the pixel of all kinds of formation on light shield layer concavo-convex, so between glass substrate and each pixel, get into 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.
(because of the display unit of heating with the tonal variation of light shield layer)
Under 220 ℃, said 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 filter in the bubble evaluation from the rear, the poor contrast when visual observation shows black and white, classification with being 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 with being described below is contained in the silver-colored tin alloy portion that will in embodiment 1, use; And sensitive layer is applied liquid be altered to following prescription; In addition; Likewise carry out with embodiment 1, make display unit and use light shield layer.The result is as shown in table 1.
< preparation of the dispersion liquid of silver-colored particulate (A2) >
(preparation of A liquid)
In decalcification gelatin 50g, add zero(ppm) water 1950g, the mixture heating up that obtains to about 40 ℃, is dissolved 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 zero(ppm) water 1350g, the mixture heating up that obtains to about 40 ℃, is dissolved gelatin.Use the 5%NaOH aqueous solution, it is adjusted to pH9.2.Stirring is also dissolved calcium acetate 16.0g and is dissolved in the Silver Nitrate 160g in the 320cc zero(ppm) water, adds zero(ppm) water, and final volume is adjusted to 2000cc, is incubated down at 40 ℃.
(preparation of C liquid)
Dissolving 110g S-WAT (anhydrous) in zero(ppm) water 700cc is dissolved in the product that 70cc methyl alcohol and 80cc water form to wherein mixing with quinhydrones 80g, and then adds zero(ppm) water, and final volume is adjusted to 2000cc, is incubated down at 40 ℃.
Stir said 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 deposition, cooling with concentrated hydrochloric acid 70cc and zero(ppm) water 8000cc dissolving SODIUM SULPHATE ANHYDROUS 99PCT 1600g gained.Remove after the supernatant, even, till can not precipitating, use zero(ppm) 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.
Use the solution that S-WAT (anhydrous) 20g, NaOH0.6g are dissolved in zero(ppm) water 2000cc gained that it is cleaned, and then use the solution that Glacial acetic acid min. 99.5 20g is dissolved in gained among the zero(ppm) water 2000cc to clean.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 with 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)
In the silver-colored dispersed slurry 5000g that obtains as stated, 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 spinning 5 minutes, make silver-colored particulate sedimentation.Supernatant discarded is cleaned with zero(ppm) 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 (ア PVC シ ア) (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.
< sensitive layer applies the preparation of liquid >
In the silver-colored particle dispersion liquid A2 of said making, add following compositions, be formulated in the sensitive layer that uses in comparative example 1 and the comparative example 2 and apply liquid.In addition, with embodiment 1 likewise, 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
Ucar 35 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); Replace being dispersed with silver-colored tin alloy portion and contain the silver-colored tin alloy portion of particle and contain particle dispersion A1, use the carbon particulate dispersion liquid of the carbon particulate that is dispersed with median size 30nm, in addition; Likewise carry out with embodiment 3, make display unit and use 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]
Table 1
Figure DEST_PATH_IMAGE002
[0245]As shown in table 1; Even it is that the following film of 1 μ m also can have high optical density(OD) that the display unit of embodiment is used light shield layer; Black tone is outstanding, and this tone can be because of heating change in addition, even and then when color filter manufacturing, 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 in embodiment 3, uses 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; Likewise carry out with embodiment 3, form display unit and use 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]
Table 2
[0253](embodiment 11～20)
In embodiment 1～10, except not being provided with on the sensitive layer the resist, likewise carry out with embodiment 1～10 respectively, make display unit and use light shield layer.These samples can not be at the 70mJ/cm that uses ultrahigh pressure mercury lamp 2Exposure form down display unit and use light shield layer, but can be at 500mJ/cm 2Exposure under obtain good display unit and use 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 resist, likewise carry out with comparative example 1～3 respectively, make display unit and use light shield layer.These samples can not be at the 70mJ/cm that uses ultrahigh pressure mercury lamp 2Exposure form down display unit and use light shield layer, but can be at 500mJ/cm 2Exposure under obtain display unit and use 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, likewise measure.It is not likewise to be realistic scale with comparative example 1～3 that the display unit that comparative example 4～6 is made is used light shield layer.The result is as shown in table 3.
[table 3]
Table 3
Figure DEST_PATH_IMAGE006
[0260](embodiment 21～30)
In these each embodiment, use photosensitive transfer printing material to make display unit and use 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 applying liquid, 100 ℃ dry 5 minutes down.Then, on this film, apply the middle layer and apply liquid so that dry film thickness becomes 1.5 μ m, and 100 ℃ dry 5 minutes down, and then apply sensitive layer and apply liquid, 100 ℃ dry 5 minutes down.
Sensitive layer among the embodiment 21～30 applies the sensitive layer coating liquid that liquid uses respectively the same composition corresponding with embodiment 1～10.In addition, the middle layer applies liquid formula and uses the coating liquid of forming together with the resist coating liquid phase of embodiment 1.Show that below thermoplastic resin applies the composition of liquid.
(thermoplastic resin coating liquid)
TEB 3K/acrylic acid-2-ethyl polyhexamethylene/methylacrylic acid benzyl ester/Sipacril 2739OF (copolymerization ratio of components (mol ratio)=55/11.7/4.5/28.8; Molecular weight=90,000,70 ℃ of Tg
Figure 2006800341739_0
) 58 parts
The multipolymer of styrene/acrylic=70/30 (copolymerization ratio of components (mol ratio)=63/37; Molecular weight=10,000,100 ℃ of Tg
Figure 2006800341739_1
) 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
[display unit is with the making of light shield layer]
Utilize spray, spray adjusted in 20 second is 25 ℃ a glass washing composition liquid on alkali-free glass substrate, cleans with the rotating brush with nylon hair simultaneously; 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 said photosensitive transfer printing material contain layer (that is, sensitive layer) contact so that particle is contained in said 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 close induction type exposure machine (Hitachi's high-tech electronic engineering (strain) system) with ultrahigh pressure mercury lamp; 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 skimmer; Trade(brand)name: T-PD1, Fujiphoto (strain) are made, and are 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 hydrogencarbonate of 0.06 mol, with the yellow soda ash of concentration, 1% sodium dibutyl naphthalene sulfonate, AS, skimmer, 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 skimmer stablizer, trade(brand)name " T-SD1 " Fujiphoto (strain) is made, and is diluted to 10 times liquid with pure water); With 33 ℃, 20 seconds, pyramid type nozzle pressure 0.02MPa; Through 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 in the mensuration of mensuration of making determining film thickness, optical density(OD) and volume fraction, uses is 70mJ/cm too 2The result is as shown in table 4.
(comparative example 7～9)
In the making of display unit of embodiment 21 with light shield layer; The sensitive layer that replaces applying the embodiment 1 of liquid as sensitive layer applies liquid, uses the sensitive layer that in comparative example 1～3, uses to apply liquid respectively, in addition; Likewise carry out with embodiment 21, make display unit and use 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]
Table 4
Figure DEST_PATH_IMAGE008
[0287]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 of tonal variation is used light shield layer 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 the band display unit with the substrate of light shield layer on during the color filter manufacturing pixel, the number of bubbles that is involved in is also less.
Relative therewith; With carbon black when the black pigment, even it is identical that this median size and volume fraction and this part are invented, 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 of said making to use light shield layer, be utilized in the method for putting down in writing among 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 look uneven, 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 to make film and the high and low cost of shading performance,, black (Achromatic color of non-cohesive color and taste) tone outstanding display unit little to the influence of environment used light shield layer.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, so, can make flatness outstanding, when forming rgb pixel, can not sneak into the considerably less filter of bubble or bubble.And then this filter can be used to make 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,
The volume fraction that has in the solids component of metallics of silver-colored tin alloy portion is 0.21～0.7.
2. coloured composition according to claim 1 is characterized in that,
In the light shield layer that the colored coating compsn forms, illuminant-C sees through the XYZ color specification system tristimulus coordinates of light, and (x is y) with the tristimulus coordinates (x of said 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,
Said 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,
Said 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,
Said coloured composition has photosensitivity.
6. coloured composition according to claim 2 is characterized in that,
Said 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 0.21～0.7, 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 said light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤0.01 relation.
8. a display unit is used light shield layer, and its display unit that is to use the described coloured composition of claim 1 to make is used light shield layer.
9. a display unit is used light shield layer, and its display unit that is to use the described coloured composition of claim 2 to make is used light shield layer.
10. a display unit is used light shield layer, and its display unit that is to use the described coloured composition of claim 5 to make is used light shield layer.
11. a display unit is used light shield layer, its display unit that is to use the described coloured composition of claim 6 to make is used light shield layer.
12. a display unit is used light shield layer, its display unit that is to use the described photosensitive transfer printing material of claim 7 to make is used light shield layer.
13. a 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; Said pixel groups is made up of pigmented layer; Each pixel that constitutes said pixel groups is shown device each other to be separated with light shield layer, and said display unit uses light shield layer to use light shield layer as the described display unit 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 filter that between this substrate, has, liquid crystal layer and the liquid crystal drive mechanism of photopermeability, and said filter is the described 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 filter that between this substrate, has, liquid crystal layer and the liquid crystal drive mechanism of photopermeability; Said liquid crystal drive mechanism has active component, between each active component, is formed with the described display unit of claim 8 and uses light shield layer.
16. a display unit wherein, has with the method for manufacture of light shield layer:
On the photopermeability substrate, form the operation of the layer that constitutes by the described coloured composition of claim 1; And
After said layer being made public with photomask with light shield layer via display unit, the operation of developing.
17. a display unit wherein, has with the method for manufacture of light shield layer:
On the photopermeability substrate, form the operation of the layer that constitutes by the described coloured composition of claim 2; And
After said layer being made public with photomask with light shield layer via display unit, the operation of developing.
18. a display unit wherein, has with the method for manufacture of light shield layer:
In photopermeability substrate laminated the described photosensitive transfer printing material of claim 7 that the photosensitivity light shield layer forms is set on supporter at least, and the operation that this photosensitive transfer printing material is contacted with said photosensitivity light shield layer;
Peel off the operation of supporter from the duplexer of said photosensitive transfer printing material and photopermeability substrate; And
After said photosensitivity light shield layer being made public with photomask with light shield layer via display unit, the operation of developing.
19. one kind with the substrate of display unit with light shield layer, it is characterized in that,
The display unit that has the photopermeability substrate and on this substrate, be provided with is used light shield layer; Said display unit with light shield layer in; Metallics with silver-colored tin alloy portion disperses with volume fraction 0.21～0.7; It is more than 3.5 that corresponding per 1 μ m display unit is used the optical density(OD) of light shield layer, and display unit with the illuminant-C of light shield layer see through light XYZ color specification system tristimulus coordinates (x, y) and the tristimulus coordinates (x of said light source 0, y 0) have (an x-x 0) 2+ (y-y 0) 2≤0.01 relation.
CN2006800341739A 2005-09-16 2006-07-18 Colored composition and photosensitive transfer material Expired - Fee Related CN101268151B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP270977/2005 2005-09-16
JP2005270977 2005-09-16
PCT/JP2006/314170 WO2007032144A1 (en) 2005-09-16 2006-07-18 Colored composition and photosensitive transfer material

Publications (2)

Publication Number Publication Date
CN101268151A CN101268151A (en) 2008-09-17
CN101268151B true CN101268151B (en) 2012-03-28

Family

ID=37864744

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2006800341739A Expired - Fee Related CN101268151B (en) 2005-09-16 2006-07-18 Colored composition and photosensitive transfer material

Country Status (5)

Country Link
JP (1) JP5252919B2 (en)
KR (1) KR20080047545A (en)
CN (1) CN101268151B (en)
TW (1) TW200722485A (en)
WO (1) WO2007032144A1 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5076753B2 (en) * 2007-09-05 2012-11-21 三菱マテリアル株式会社 Method for producing high-concentration metal nanoparticle dispersion
CN102105245A (en) * 2008-07-23 2011-06-22 建筑研究和技术有限公司 Method for producing metal nanoparticles in polyols
JP4544370B2 (en) * 2008-10-28 2010-09-15 Ｊｓｒ株式会社 Radiation-sensitive resin composition, interlayer insulating film and microlens, and production method thereof
DE102009015470A1 (en) 2008-12-12 2010-06-17 Byk-Chemie Gmbh Process for the preparation of metal nanoparticles and metal nanoparticles obtained in this way and their use
JP5934463B2 (en) * 2009-07-07 2016-06-15 富士フイルム株式会社 Coloring composition for light shielding film, method for forming light shielding film and light shielding pattern, solid-state imaging device, and method for producing the same
US9017450B2 (en) 2010-12-09 2015-04-28 Carestream Health, Inc. Nanowire preparation methods, compositions, and articles
CN102799070B (en) * 2012-08-27 2014-03-05 珠海市能动科技光学产业有限公司 Double coating negative photoresist dry film
KR102130533B1 (en) * 2014-01-24 2020-07-06 동우 화인켐 주식회사 The a colored photosensitive resin composition for forming the frontal light shielding layer of a display device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1570683A (en) * 2003-04-18 2005-01-26 富士胶片株式会社 Shielding film for display device
CN1591050A (en) * 2003-04-18 2005-03-09 富士胶片株式会社 Light-shielding layer for display device
CN101027368A (en) * 2004-09-21 2007-08-29 住友大阪水泥股份有限公司 Black material, black particle dispersion liquid, black light-blocking film using same, and base with black light-blocking film

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3692601B2 (en) * 1996-03-27 2005-09-07 東レ株式会社 Resin black matrix, black paste, and color filter
JP2005075965A (en) * 2003-09-02 2005-03-24 Toray Ind Inc Black coating film composition, resin black matrix, color filter, and liquid crystal display
JP4808383B2 (en) * 2004-03-17 2011-11-02 富士フイルム株式会社 COLORING COMPOSITION AND PHOTOSENSITIVE TRANSFER MATERIAL, LIGHT-EMITTING LAYER FOR DISPLAY DEVICE AND METHOD FOR PRODUCING THE SAME, COLOR FILTER, LIQUID CRYSTAL DISPLAY ELEMENT, AND SUBSTRATE WITH LIGHT-EMITTING LAYER FOR DISPLAY DEVICE
JP4237148B2 (en) * 2005-02-17 2009-03-11 住友大阪セメント株式会社 Black fine particle dispersion, black light shielding film using the same, and substrate with black light shielding film
KR101067206B1 (en) * 2004-09-21 2011-09-22 스미토모 오사카 세멘토 가부시키가이샤 Black material, black particle dispersion liquid, black light-blocking film using same, and base with black light-blocking film
JP4223487B2 (en) * 2005-02-17 2009-02-12 住友大阪セメント株式会社 Black fine particles, black fine particle dispersion, black light shielding film, and substrate with black light shielding film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1570683A (en) * 2003-04-18 2005-01-26 富士胶片株式会社 Shielding film for display device
CN1591050A (en) * 2003-04-18 2005-03-09 富士胶片株式会社 Light-shielding layer for display device
CN101027368A (en) * 2004-09-21 2007-08-29 住友大阪水泥股份有限公司 Black material, black particle dispersion liquid, black light-blocking film using same, and base with black light-blocking film

Also Published As

Publication number Publication date
KR20080047545A (en) 2008-05-29
TW200722485A (en) 2007-06-16
JP5252919B2 (en) 2013-07-31
WO2007032144A1 (en) 2007-03-22
JPWO2007032144A1 (en) 2009-03-19
CN101268151A (en) 2008-09-17

Similar Documents

Publication Publication Date Title
CN101268151B (en) Colored composition and photosensitive transfer material
CN101636452B (en) Black resin composition, resin black matrix, color filter and liquid crystal display
JP5526821B2 (en) Coloring composition, color filter and color liquid crystal display element
TWI446110B (en) Dye dispersion liquid, photosensitive resin composition for color filters, color filter, liquid crystal display device and organic light emitting display device
JP5446423B2 (en) Coloring composition, color filter and color liquid crystal display element
TW200836003A (en) Green photosensitive resin composition and color filter prepared therefrom
CN100545213C (en) Black combination, black by film composition, resin black matrix, liquid crystal indicator with colour filter and liquid crystal indicator
JP4592239B2 (en) Color filter composition and color filter
CN101291763B (en) Method for producing metal particle dispersion, metal particle dispersion, and colored composition, photosensitive transfer material, substrate with light-blocking image, color filter and liquid crystal display
TW201506091A (en) Black resin composition for touch panels
CN105093831A (en) Photosensitive resin composition and color filter using the same
CN101291989B (en) Fine particle-containing composition, ink for forming colored film for display, light-blocking film for display, light-blocking material, substrate with light-blocking film, color filter, liquid crystal element and device
CN101128544B (en) Resin composition for recording material
TW201022846A (en) Green photosensitive colored composition and color filter using the same
JPWO2012005203A1 (en) Triarylmethane colorant, coloring composition, color filter, and display element
CN101114034B (en) Black dispersion, pigmentation composition, photosensitive transprinting material containing metal particulate
TW202138477A (en) Black resin composition, near infrared ray-transmitting light-blocking membrane, decorative substrate, decorative film and colored partition wall for organic el display
JPH11323143A (en) Light-screening photosensitive resin composition and color filter prepared therefrom
TW201609990A (en) A red coloring agent composition for a color filter
JP2002162515A (en) Composition for color filter and the color filter
TWI534208B (en) A process for producing a pigment dispersion, a pigmented resin composition for a pigment dispersion and a color filter
JP4301716B2 (en) Color filter composition and color filter
TW201003143A (en) Green pixel, radiation-sensitive composition for producing green pixel, color filter and color liquid crystal display element
CN101071264A (en) Photosensitive combination and photosensitive transprinting material using same, display device shading film and manufacturing method, black matrix, substrate having shading film and display device
JPH11327128A (en) Light shielding photosensitive resin compound and color filter using same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120328

Termination date: 20210718