CN101373291A - Liquid crystal display element - Google Patents

Liquid crystal display element Download PDF

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Publication number
CN101373291A
CN101373291A CNA2008101475337A CN200810147533A CN101373291A CN 101373291 A CN101373291 A CN 101373291A CN A2008101475337 A CNA2008101475337 A CN A2008101475337A CN 200810147533 A CN200810147533 A CN 200810147533A CN 101373291 A CN101373291 A CN 101373291A
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China
Prior art keywords
organic pigment
solvent
pigment
nano particle
liquid crystal
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CNA2008101475337A
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Chinese (zh)
Inventor
吉野晴彦
松本圭右
鸭崎彻
柴田直也
伊藤英明
儿玉知启
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Fujifilm Corp
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Fujifilm Corp
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Publication of CN101373291A publication Critical patent/CN101373291A/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336—Illuminating devices
    • G02F1/133621—Illuminating devices providing coloured light

Abstract

The invention provides a liquid crystal display component with a wide color reappearance range and a high contrast via making particle diameter of purple organic pigment of C.I. pigment smaller, and combined with tri-wavelength backlight. The invention provides a liquid crystal display component having a color filter and tri-wavelength backlight; wherein the color filter comprises at least one organic pigment nano-particle with average particle diameter less than 50 nm; the peak value of green bright line spectrum of the tri-wavelength backlight is between 520 nm and 540 nm.

Description

Liquid crystal display cells
Technical field
The present invention relates to a kind of liquid crystal display cells, this liquid crystal display cells has excellent long-time demonstration adaptability for the color reproduction wide ranges of green and contrast excellence and its.
Background technology
In recent years, in LCD, in order to widen the color reproduction scope of green (G) direction, people are using the LED-backlit of three-wavelength type to replace traditional three-wavelength cold-cathode tube.
And, in order to improve the contrast of panel,, also require it finer for employed pigment in the color filter.
All the time, pigment has distinct high colouring power and the weatherability of color harmony, has obtained using widely in a lot of fields.As a rule, in these pigment, what have important value in actual applications is the pigment with minuteness particle mostly, carries out miniaturization by the aggegation that prevents this pigment and handles, and can obtain the distinct high colouring power of color harmony.But if adopt the physical method such as salt mill method that pigment is carried out more miniaturization processing, then this dispersing of pigments liquid often presents high viscosity.Therefore, when preparing this dispersible pigment dispersion, can produce many problems, for example be difficult to from dispersion machine to take out this dispersible pigment dispersion, maybe can not utilize pipeline to carry, and in storage process, gelation take place and can not continue to use with industrial scale, or the like.
Therefore, traditionally, for dispersible pigment dispersion or the coloring photosensitive combination that obtains flowability, excellent dispersion, known method has: organic pigment (is for example carried out surface treatment, with reference to patent documentation 1 and 2), or use various spreading agents (for example, with reference to patent documentation 3 and 4).In addition, also addressed such method of using in the patent documentation 5: the sample that will be dissolved in the good solvent is injected in stirring condition and the controlled poor solvent of temperature, thereby obtains the reprecipitation method of nano particle.
When using this coloring photosensitive combination to form rendered image, as a rule, the coating liquid of coloring photosensitive combination is coated on the substrate to form the layer that is made of this coloring photosensitive combination, expose then, develop.Developer solution as being adopted when this development in most cases uses the alkaline aqueous solution little to environmental impact, is with it can corresponding material but require this coloring photosensitive combination.On the other hand, the solvent that uses in the coating liquid as coloring photosensitive combination (dispersing of pigments medium), requiring it is to be easy to dry material after applying.
In addition, layer as being made of this coloring photosensitive combination usually requires as thin as a wafer, and requires also to demonstrate under the condition of thinner thickness high colour saturation, therefore, need with organic pigment with to heavens and the state of miniaturization equably be dispersed in (for example) organic solvent.
But, also do not develop at present and can satisfy these requirements, excellent performances such as described dispersing of pigments, flowability and can satisfy pigment dispersing thing, do not develop the pigment dispensing composition and the coloring photosensitive combination that contain this pigment dispersing thing yet as the requirement of the display characteristic of the color filter of liquid crystal indicator.
[patent documentation 1] Japanese kokai publication hei 11-269401 communique
[patent documentation 2] Japanese kokai publication hei 11-302553 communique
[patent documentation 3] Japanese kokai publication hei 8-48890 communique
[patent documentation 4] TOHKEMY 2000-239554 communique
[patent documentation 5] TOHKEMY 2004-123853 communique
Summary of the invention
Invent problem to be solved
The purpose of this invention is to provide a kind of liquid crystal display cells, this liquid crystal display cells has wide color reproduction scope and high contrast.Compare with the G peak of three-wavelength cold-cathode tube, the green of LED-backlit (G) peak position is in short wavelength regions and amplitude broad, therefore, when combining with traditional color filter, shortcoming can appear, particularly can appear at and sneak into green (G) in the blueness (B), to such an extent as to narrow down in the color reproduction scope of B direction.For fear of this shortcoming, be necessary to make the B peak of color filter close to shortwave, usually use violet pigment as C.I. pigment Violet 23 and so on for this reason, but have such shortcoming: the organic pigment particles particle diameter in traditional C.I. pigment violet is big, because the effect of light scattering, contrast is had very big harmful effect, and long-time continuous is when showing, permanance is also not enough.
The means of dealing with problems and being adopted
In order to address the above problem, the inventor furthers investigate, and found that, the particle diameter of organic pigment particles such as C.I. pigment violet is formed nanoscale, and by with the combination backlight of three-wavelength type, the liquid crystal display cells with wide color reproduction scope and high contrast can be provided.Finish the present invention based on above-mentioned discovery.
Address the above problem by following means.
(1) a kind of liquid crystal display cells, it is characterized in that, has color filter and the three-wavelength type is backlight, wherein, it is the following organic pigment nano particle of 50nm that described color filter contains at least a mean grain size, the bright-line spectrum peak value (Green Se Hui Line ピ-Network of the green that described three-wavelength type is backlight) between 520nm～540nm.
(2) above-mentioned (1) described liquid crystal display cells is characterized in that having color filter, and it is the following organic pigment nano particle of 30nm that this color filter contains at least a mean grain size.
(3) above-mentioned (1) or (2) described liquid crystal display cells, it is characterized in that, described mean grain size is that the following organic pigment nano particle of 50nm is preparation like this: organic pigment is dissolved in the good solvent, then gained solution is injected in the solvent as the poor solvent of above-mentioned organic pigment.
(4) any described liquid crystal display cells in above-mentioned (1)～(3) is characterized in that, described three-wavelength type is backlight to be made of red, green and blue light emitting diode (LED).
(5) any described liquid crystal display cells in above-mentioned (1)～(4), wherein said organic pigment nano particle is the C.I. pigment Violet 23.
(6) any described liquid crystal display cells in above-mentioned (1)～(5), it is characterized in that, described color filter is to form by such method, this method is: use interim stilt to be provided with thermoplastic resin, the photosensitive resin transfer material of middle layer and coloring phototonus resin bed, described coloring phototonus resin bed and substrate are heated so that they are combined closely, thereby described coloring phototonus resin bed is transferred on the described substrate, then described interim stilt is peeled off or described interim stilt and described thermoplastic resin are peeled off, and the described coloring phototonus resin bed that is transferred on the described substrate carried out pattern exposure, develop then, thereby on described substrate, form image.
The effect of invention
Its green color reproduction wide ranges of liquid crystal display cells of the present invention, and contrast excellence.In addition, liquid crystal display cells of the present invention also has excellent black density etc. and describes power.Liquid crystal display cells of the present invention also goes for the liquid crystal indicator of big pictures such as display that notebook computer uses and TV monitor etc.
Brief Description Of Drawings
Fig. 1 shows the sectional drawing of formation of a kind of embodiment of liquid crystal display cells of the present invention for summary.
The key diagram of a structure example of the ultrafiltration apparatus that Fig. 2 uses when being the organic pigment nano particle that uses in making the present invention.
Fig. 3 shows is the figure of the three-wavelength type that uses among embodiment luminescent spectrum backlight.
[explanation of label]
1 transparency carrier
2 color filters
3 transparency electrodes
4 array base paltes
5 ITO electrodes
6 liquid crystal layers
The transparency carrier of 7 array base palte sides
8 three-wavelength types are backlight
21 hold the container that disperses thing
22 circulation pumps
23 ultrafiltration modules
24 replenish pure water metering flowmeter
25 permeate water metering flowmeter
26 reverse flushing pumps
Preferred forms of the present invention
At first, liquid crystal display cells of the present invention is described.
Liquid crystal display cells of the present invention has color filter and the three-wavelength type is backlight, wherein, it is the following organic pigment nano particle of 50nm that described color filter contains at least a mean grain size, and the bright-line spectrum peak value of the green that described three-wavelength type is backlight is between 520nm～540nm.
Liquid crystal display cells of the present invention is by following color filter and the following three-wavelength type liquid crystal display cells that combines backlight, can by and the array base palte that is provided with in opposite directions of described color filter and liquid crystal layer of between described color filter and described array base palte, enclosing etc. constitute.
Liquid crystal display cells of the present invention can have the chromatic characteristic of NTSC specification by LED-backlit and color filter combination are formed, and its NTSC ratio also may be more than 100%; Wherein, the color reproduction wide ranges of described LED-backlit, and carry out color separated easily by color filter; Described color filter is for versicolor color separated effect excellence, and it sees through wavelength coverage and coincide with peak wavelength as the versicolor LED of LED-backlit.
Except backlight, color filter, the component parts of liquid crystal display cells of the present invention can comprise that also electrode base board, polarizing coating, phase retardation film, dottle pin, field angle ensure various parts such as film.Relevant these parts are for example at " ' 94 liquid crystal デ イ ス プ レ イ Zhou side material ヶ ミ カ Le ズ city Games " (Island Itou Kentaro (strain) シ-エ system シ-1994 year distribution) ", " 2003 Ye Jing Off Even Shi Games Now shape と look forward in the future " (last volume) (the good lucky キ メ ラ of (strain) Fuji Gross of table grinds distribution in 2003) " on the books.
Based on Fig. 1, a kind of preferred embodiment of liquid crystal display cells of the present invention is described.
Fig. 1 shows is the sectional drawing of formation summary of a kind of embodiment of liquid crystal display cells of the present invention.
A kind of embodiment of liquid crystal display cells of the present invention is such liquid crystal display cells: be disposed with color filter 2, transparency electrode 3 on transparency carrier 1, be provided with ITO electrode 5 with above-mentioned color filter 2 array base palte 4 in opposite directions, between above-mentioned transparency electrode 3 and above-mentioned ITO electrode 5, be provided with the liquid crystal layer of being enclosed 6, and it is backlight 8 also to be provided with the three-wavelength type in this liquid crystal display cells, and this transparency carrier 7 sides irradiation from above-mentioned array base palte 4 sides backlight is come.
In addition, color filter 2 suitably has black matrix 9, and liquid crystal layer 6 has liquid crystal 10.
Next, the color filter that uses among the present invention is described.
Used color filter among the present invention, it is corresponding to (this three-wavelength type employing backlight red (R) backlight of above-mentioned three-wavelength type, the LED of green (G) and blue (B)), described color filter preferably has the redness (R) with LED-backlit, the wavelength of green (G) and blue (B) is corresponding redness (R) pixel portion respectively, green (G) pixel portion, and blue (B) pixel portion, wherein, the peak wavelength of the redness of described LED-backlit (R) LED is more than 620nm, the peak wavelength of green (G) LED is at 520～540nm, the peak wavelength of blue (B) LED is below 470nm.
Promptly, as the color filter that uses among the present invention, preferred such color filter, its redness (R) pixel portion, green (G) pixel portion and blueness (B) pixel portion see through wavelength coverage, corresponding with the peak wavelength of red (R), green (G) and blueness (B) LED respectively.
Below, each component part of the color filter that uses among the present invention is described.
The mean grain size of at least a organic pigment nano particle that is contained in the used color filter of the present invention is below the 50nm, and more preferably the mean grain size of at least a this organic pigment nano particle is below the 30nm.There is no particular limitation for the lower limit of this mean grain size, but be generally more than the 1nm.
1. green (G) pixel portion
The transmitance of the peak wavelength of green (G) pixel portion is preferably more than 75%, and more preferably 80～90%.By making peak wavelength in above-mentioned scope, can produce the color filter of high brightness.
In the present invention, there is no particular limitation for the kind of the organic pigment of above-mentioned green (G) pixel portion, as long as can be used for the pixel portion of color filter, but about the organic pigment nano particle that uses among the present invention, in the middle of following organic pigment, preferred viridine green or the yellow uitramarine of using, more preferably use the organic pigment nano particle of making by above-mentioned viridine green or yellow uitramarine, further preferably use by above-mentioned viridine green or yellow uitramarine manufacturing, particle diameter is the organic pigment nano particle below the 50nm.Thus, can suppress the transmitance of green (G) pixel portion to the wavelength coverage of red (R) and blue (B) LED.
Here, the spectrophotometric transmittance value measured for the spectrophotometer OSP-SP200 that adopts オ リ Application パ ス optics industry (strain) to make of the value of above-mentioned spectrophotometric transmittance.
2. blue (B) pixel portion
The transmitance of the peak wavelength of blue (B) pixel portion is preferably more than 72%, more preferably 75～85%.By making peak wavelength in above-mentioned scope, can produce the color filter of high brightness.
Also there is no particular limitation for above-mentioned blueness (B) pixel portion, as long as can be used for the pixel portion of color filter, but for the organic pigment nano particle that uses among the present invention, in the middle of following organic pigment, preferred blue pigment or the violet pigment of using, more preferably use the organic pigment nano particle of making by above-mentioned blue pigment or violet pigment, further preferably use by above-mentioned blue pigment or violet pigment manufacturing, particle diameter is the organic pigment nano particle below the 50nm.Thus, can suppress the transmitance of blue (B) pixel portion to the wavelength coverage of red (R) and green (G) LED.
3. red (R) pixel portion
The transmitance of the peak wavelength of red (R) pixel portion is preferably more than 85%, more preferably 90～100%.By making peak wavelength in above-mentioned scope, can produce the color filter of high brightness.
Also there is no particular limitation for above-mentioned redness (R) pixel portion, as long as can be used for the pixel portion of color filter, but for the organic pigment nano particle that uses among the present invention, in the middle of following organic pigment, preferred red pigment or the orange pigment of using, more preferably use the organic pigment nano particle of making by above-mentioned red pigment or orange pigment, further preferably use by above-mentioned red pigment or orange pigment manufacturing, particle diameter is the organic pigment nano particle below the 50nm.Thus, can suppress the transmitance of red (R) pixel portion to the wavelength coverage of blue (B) and green (G) LED.
About the color filter that uses among the present invention, especially for its structure etc. unqualified, except above-mentioned pixel portion, this color filter can also have black matrix, protective seam, transparency electrode, oriented layer etc.
In addition, also there is no particular limitation for the set-up mode of pixel portion, can formation be set according to strip or meander-like etc.
In addition, the thickness of the pixel portion of the color filter that uses among the present invention is preferably 0.1 μ m～4.0 μ m.Thickness by making pixel portion can reduce the possibility that orientation to liquid crystal etc. impacts, and can make resolution and the high color filter of brightness in above-mentioned scope.
Below, above-mentioned manufacturing method of color filter is described.
The color filter that uses among the present invention can adopt following method manufacturing: form the coloring phototonus resin bed on substrate, repeat to be equivalent to the exposure and the development of the number of times of number of color again.In addition, as required, also can form the structure of distinguishing its border with black matrix.
In above-mentioned manufacture method, as the method that on substrate, forms above-mentioned coloring phototonus resin bed, can enumerate (a) and adopt following photosensitive resin transfer material, carry out bonding method by laminating machine, and the method that (b) adopts coating unit commonly used to wait to apply each following photosensitive composition etc.
As above-mentioned manufacturing method of color filter, consider the method for preferably above-mentioned (a) from the flatness of color filter and the angle of cost.
As the method for above-mentioned (a) and (b), in the present invention, the method described in [0042]～[0056] section of also suitable use TOHKEMY 2006-276818 communique.Method as above-mentioned (a), specifically, the following method of preferred employing forms color filter: use interim stilt to be provided with thermoplastic resin, the photosensitive resin transfer material of middle layer and coloring phototonus resin bed, above-mentioned coloring phototonus resin bed and substrate are heated, they are combined closely, thereby the coloring phototonus resin bed is transferred on the substrate, then, above-mentioned interim stilt is peeled off or above-mentioned interim stilt and thermoplastic resin are peeled off, the above-mentioned coloring phototonus resin bed that is transferred on the aforesaid substrate is carried out pattern exposure, develop then, on aforesaid substrate, to form image.
Also have, when forming the coloring phototonus resin bed by following photosensitive resin transfer material, thickness is preferably 1.0～5.0 μ m, 1.0～4.0 μ m more preferably, preferred especially 1.0～3.0 μ m.
(substrate)
In the present invention,, for example transparency carrier can be used, known glass plates such as the soda-lime glass plate that has silicon oxide film on the surface, low-expansion glass, alkali-free glass, quartz glass plate can be enumerated as the substrate that is used to form color filter, or plastic foil etc.
In addition, by in advance aforesaid substrate being carried out coupling processing, itself and photosensitive composition or photosensitive resin transfer material are combined closely well.As this coupling processing, preferably use the method for putting down in writing in the TOHKEMY 2000-39033 communique.In addition, though there is no particular limitation for the thickness of substrate, be preferably 700～1200 μ m usually.
(oxygen barrier film)
For the color filter that uses among the present invention, forming under the situation of photo-sensitive resin, can the oxygen barrier film be set further on this photo-sensitive resin by applying photosensitive composition, can improve exposure sensitivity thus.As described oxygen barrier film, the oxygen barrier film that preferably demonstrates low oxygen permeability and can disperse or dissolve in water or alkaline aqueous solution can suitably be selected from known oxygen barrier film.Wherein, particularly preferably be the combination of polyvinyl alcohol (PVA) and polyvinylpyrrolidone.In addition, though there is no particular limitation for the thickness of oxygen barrier film, be preferably 0.5～3.0 μ m usually.
(pattern exposure and development)
Above the photo-sensitive resin that forms on the aforesaid substrate, predetermined mask is set, see through this mask, thermoplastic resin and middle layer then, top exposure from mask, then develop with developer solution, such operation of the number of times by repeating to be equivalent to number of color, the just color filter that can obtain using among the present invention.In addition, as required, can also carry out post-exposure and back oven dry.As the formation method of patterning of pattern exposure and development etc., the method described in [0040]～[0051] section of method described in [0059]～[0062] section of also suitable in the present invention use TOHKEMY 2006-276818 communique and TOHKEMY 2006-23696 communique.
The color filter that uses among the present invention is characterised in that to have excellent contrast.In the present invention, contrast is illustrated between two polaroids, the ratio of the light transmission capacity the when light transmission capacity when polarizing axis is parallel is vertical with polarizing axis (referring to " nineteen ninety the 7th the color reversion glory learn コ Application Off ァ レ Application ス; 512 colour specifications 10.4 " サ イ ズ TFT-LCD is with カ ラ-Off イ Le , plant wood, Xiao Guan, good fortune forever, in the mountain " etc.).
The contrast height of color filter means that the light and shade difference when itself and liquid crystal make up can become greatly, and in order to replace CRT with LCD, this is very important performance.
The color filter that uses among the present invention, preferably under the F10 light source, poor (the Δ E) of all the monochromatic colourities of red (R), green (G) and blue (B) and following table record value (below, be called " standard colorimetric " in the present invention) is in 5, more preferably in 3, in 2.
Figure A200810147533D00121
Colourity among the present invention is to utilize microscope spectrophotometer (オ リ Application パ ス optics society make, OSP100 or 200) to measure, and calculates as the results in the 2 degree visuals field under the F10 light source, represents with the xyY value of xyz coloring system.In addition, with the difference of standard colorimetric with La *b *The aberration of coloring system is represented.
Below, the photosensitive composition that uses in the manufacturing to above-mentioned color filter describes.
Above-mentioned photosensitive composition contains at least: (1) organic pigment nano particle, wherein in the presence of alkali solubility cementing agent (A) with acidic-group, the organic pigment solution that will be dissolved in the good solvent and form and can mixing mutually with the miscible poor solvent of this good solvent is particle below the 50nm thereby make this organic pigment form mean grain size; (2) has the alkali solubility cementing agent (B) of acidic-group; (3) monomer or oligomer; And (4) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system.But, (a) can be identical with (b), also can be different.
Contain organic pigment nano particle in the above-mentioned photosensitive composition, although this organic pigment nano particle has had the such nominal particle size of nano-scale, these organic pigment nano particles still can be concentrated and disperse and obtain the particle size of target.Therefore, when being used for color filter, the excellent in uniformity on its optical concentration height, color filter surface, the contrast height of color filter, and image noise is reduced.
In addition, with the organic pigment nano particle that contains in the above-mentioned photosensitive composition, with to heavens and also the state of miniaturization equably disperse, therefore can be under the thin condition of film thickness performance high colour saturation, thereby can make attenuation such as color filter.
And contain the organic pigment that shows the high colouring power of distinct color harmony in the above-mentioned photosensitive composition, therefore, this photosensitive composition can be with acting on the Image forming material of making color filter.
In addition, at used alkaline-based developer in when forming rendered image, exposing, develop, in above-mentioned photosensitive composition, used the material that dissolves in the alkaline aqueous solution as cementing agent (binder), so also satisfy the requirement on the environment.
And, can adopt organic solvent with appropriate drying property as the solvent that uses in the above-mentioned photosensitive composition (spreading agent of organic pigment), also can meet the demands aspect the drying property after coating.
Below, the neccessary composition of above-mentioned (1)～(4) in the above-mentioned photosensitive composition is described.
(1) organic pigment nano particle
Preparation method for organic pigment nano particle will be described in detail in the back.With respect to the whole solid contents in the photosensitive composition (in this manual, all solid content is meant the total of the composition component except that organic solvent), the content of organic pigment nano particle is preferably 3～60 quality %, more preferably 5～40 quality %.If should measure too much, then sometimes the viscosity of dispersion liquid rises, and can cause making the problem on the adaptability.If very few, colouring power deficiency sometimes then.
(2) alkali solubility cementing agent
For decentralizedly again having no particular limits of when decentralized again, using, as long as have acidic-group with the alkali solubility cementing agent.Disperse to use cementing agent again as this, preferably make the material that describes in detail in postpose " (alkali solubility cementing agent) " item, it is the compound that has analog structure when forming organic pigment nano particle with the alkali solubility cementing agent that is used to form nano particle that is added that preferred this disperses with cementing agent again, and most preferably both structures are identical.With respect to the whole solid contents in the photosensitive composition, the decentralized again content with the alkali solubility cementing agent is (residual when alkali solubility cementing agent used when forming organic pigment nano particle is arranged, can be their total content) be generally 15～50 quality %, be preferably 20～45 quality %.If should measure too much, then sometimes the viscosity of composition is too high, can cause the problem of making on the adaptability.If very few, then sometimes can have problems aspect the formation coat film.
(3) monomer or oligomer
As monomer contained in the above-mentioned photosensitive composition or oligomer, be preferably the ethylenical unsaturated double bonds that has more than 2, and can carry out the monomer or the oligomer of addition polymerization by illumination.As this monomer or oligomer, monomer or the oligomer described in [0027] section of also suitable in the present invention use TOHKEMY 2006-276818 communique.
Wherein, preferred trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate.
These monomers or oligomer are (as monomer or oligomer, preferred molecular weight is 200～1000) can use separately, also can mix use more than two kinds, this monomer or oligomer are generally 5～50 quality % with respect to the content of whole solid contents of photosensitive composition, are preferably 10～40 quality %.If should measure too much, then sometimes the viscosity of composition is too high, can cause the problem of making on the adaptability.If very few, the curing power deficiency when then sometimes exposing.
(4) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system
As the Photoepolymerizationinitiater initiater that in above-mentioned photosensitive composition, contains or Photoepolymerizationinitiater initiater system (Photoepolymerizationinitiater initiater system be meant combine realize that photopolymerization causes the potpourri of function by multiple compound), also be fit to use Photoepolymerizationinitiater initiater or the Photoepolymerizationinitiater initiater system described in [0028] section of TOHKEMY 2006-276818 communique in the present invention.Preferred especially trihalomethyl-s-triazine, San halogen Jia oxadiazole and triarylimidazoles dipolymer.
These Photoepolymerizationinitiater initiaters or Photoepolymerizationinitiater initiater system can be used separately, also can mix use more than two kinds, especially preferably use more than two kinds.If use at least two kinds of Photoepolymerizationinitiater initiaters, then can reduce the demonstration non-uniform phenomenon in the display performance especially.
With respect to whole solid contents of photosensitive composition, the content of Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system is generally 0.5～20 quality %, is preferably 1～15 quality %.If should measure too much, then sometimes susceptibility is too high, is difficult to control.If very few, then sometimes exposure sensitivity is low excessively.
(other adjuvant)
In above-mentioned photosensitive composition, except above-mentioned composition, can also be with an organic solvent, other adjuvant such as surfactant, thermal polymerization inhibitor, the auxiliary dyestuff that uses, pigment, ultraviolet light absorber.
As above-mentioned other adjuvant, also be fit to use other the adjuvant described in [0035] to [0040] section of TOHKEMY 2006-276818 communique in the present invention.
(coat film of photosensitive composition)
The coat film of above-mentioned photosensitive composition contains at least: (1) organic pigment nano particle, wherein in the presence of alkali solubility cementing agent (A) with acidic-group, the organic pigment solution that will be dissolved in the good solvent and form and can mixing mutually with the miscible poor solvent of this good solvent is particle below the 50nm thereby make this organic pigment form mean grain size; (2) has the alkali solubility cementing agent (B) of acidic-group; (3) monomer or oligomer; And (4) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system.
In the coat film of above-mentioned photosensitive composition,, identical with the composition of putting down in writing in the above-mentioned photosensitive composition about the neccessary composition of above-mentioned (1)～(4) and other composition.In addition, the thickness of the coat film of above-mentioned photosensitive composition can be suitably definite according to its purposes, but be preferably 0.5～5.0 μ m, more preferably 1.0～3.0 μ m.
Below, the photosensitive resin transfer material that uses in the manufacturing to above-mentioned color filter describes.
Above-mentioned photosensitive resin transfer material preferably adopts the photosensitive resin transfer material of putting down in writing in the Japanese kokai publication hei 5-72724 communique, and promptly the film with monolithic devices forms.The example that constitutes of the film of this monolithic devices as an illustration; can enumerate and carry out laminated in this order interim stilt/thermoplastic resin/middle layer/photo-sensitive resin/diaphragm and structure that obtain; as the photosensitive resin transfer material that uses among the present invention, be to form by using above-mentioned photosensitive composition to be arranged to the coloring phototonus resin bed.
(interim stilt)
In the photosensitive resin transfer material of Shi Yonging,, has flexible also can not produce remarkable distortion, contraction or elongation under pressurization or heating and pressurizing material in the present invention even must be as interim stilt.As the example of this interim stilt, can enumerate polyethylene terephthalate film, tri cellulose acetate membrane, polystyrene film, polycarbonate membrane etc., wherein preferred especially biaxial stretch-formed polyethylene terephthalate film.
(thermoplastic resin)
As the composition that uses in the thermoplastic resin, the organic polymer material of putting down in writing in the preferred Japanese kokai publication hei 5-72724 communique, be to select in about organic polymer material below 80 ℃ especially preferably from the softening point that records by Wei Ka-Vicat method (specifically, being the method for measuring the polymkeric substance softening point according to U.S. material test method(s) ASTMD1235).Specifically, can enumerate tygon, polyolefin such as polypropylene, the ethylene copolymer that ethene and vinyl acetate or its are saponified etc., ethene and acrylate or its are saponified, Polyvinylchloride, vinyl chloride and vinyl acetate and saponified etc. vinyl chloride copolymer thereof, Vingon, polyvinylidene chloride copolymer, polystyrene, the styrol copolymer that styrene and (methyl) acrylate or its are saponified etc., polyvinyl toluene, the vinyl toluene copolymer that vinyltoluene and (methyl) acrylate or its are saponified etc., poly-(methyl) acrylate, (methyl) acrylate copolymer that (methyl) butyl acrylate and vinyl acetate etc. form, vinyl acetate copolymerization nylon, copolymer nylon, N-alkoxy methyl nylon, the organic polymers such as polyamide of N-dimethylamino nylon and so on.
(middle layer)
For the photosensitive resin transfer material that uses among the present invention, when applying a plurality of coat, reach when after coating, preserving, in order to prevent the mixing of composition, the middle layer is set preferably.As this middle layer, the preferred oxygen barrier film of putting down in writing as " separating layer " in the Japanese kokai publication hei 5-72724 communique that uses with the function that intercepts oxygen, in this case, the susceptibility during exposure rises, reduce the time load of exposure machine, improved throughput rate.
(diaphragm)
The pollution when preferably on described coloring phototonus resin bed, being provided for protecting it to avoid storing and the thin diaphragm of damage.Diaphragm can be to be made of or materials similar identical with interim stilt, but must separate with photo-sensitive resin easily.As the material of diaphragm, for example organosilicon paper, polyolefin or polytetrafluoroethylsheet sheet suit.
(method for making of photosensitive resin transfer material)
The photosensitive resin transfer material that uses among the present invention can be made in the following manner, that is: on interim stilt, apply the adjuvant dissolving that makes thermoplastic resin and the coating liquid (thermoplastic resin coating liquid) that forms, dry then, thermoplastic resin is set thus; On thermoplastic resin, apply the intermediate layer material solution that constitutes by the solvent of heat of solution plastic resin layer not then, and carry out drying; Adopt the solvent that does not dissolve the middle layer to apply and drying photo-sensitive resin then, thereby photosensitive resin transfer material is set.
In addition, also can make in the following manner, that is: the above-mentioned interim stilt of preparation is provided with the sheet material in thermoplastic resin and middle layer, and diaphragm is provided with the sheet material of described coloring phototonus resin bed, carries out bonding mutually according to the mode that the middle layer is contacted with described coloring phototonus resin bed; Also have, prepares the sheet material that above-mentioned interim stilt is provided with thermoplastic resin, and diaphragm is provided with the sheet material in described coloring phototonus resin bed and middle layer, carry out bonding mutually according to the mode that makes thermoplastic resin and middle layer joint.
There is no particular limitation for other the preferred thickness of each layer, but the thickness of preferred interim stilt is that 15～100 μ m, thermoplastic resin are that 2～30 μ m, middle layer are that 0.5～3.0 μ m, diaphragm are 4～40 μ m usually.
Below, the organic pigment nano particle that uses among the present invention is described.
At least contain employed organic pigment nano particle among a kind of the present invention in the above-mentioned color filter.
The organic pigment nano particle that uses among the present invention preferably obtains by reprecipitation method, and wherein said reprecipitation method is injected into preferably under stirring condition and in the controlled poor solvent of temperature for the organic pigment that will be dissolved in the good solvent.
Next, the organic pigment that is used as organic pigment nano particle among the present invention is described.
Can not be subjected to the restriction of tone as the organic pigment of organic pigment nano particle of the present invention.Specifically, can be listed as and lift perylene, perylene ketone, quinoline a word used for translation ketone, quinoline a word used for translation ketone quinone, anthraquinone, three benzopyrene diketone, benzimidazolone, disazo condensation thing, bisdiazo, azo, indanthrone, phthalocyanine, triaryl carbonium, dioxazine, amino anthraquinones, diketopyrrolopyrrolecocrystals, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone class pigment, or their potpourri etc.
More particularly, can enumerate for example colorant described in the pigment described in the pigment described in TOHKEMY 2005-17716 communique [0038]～[0054], TOHKEMY 2004-361447 communique [0068]～[0072], TOHKEMY 2005-17521 communique [0080]～[0088].
In liquid crystal display cells of the present invention, as blue pigment or violet pigment as organic pigment nano particle, be preferably C.I. pigment Violet 23 (C.I. numbering 51319), C.I. pigment blue 15: 6 or C.I. pigment blue 60, more preferably C.I. pigment blue 15: 6 with the combination of pigment Violet 23.
As viridine green or yellow uitramarine as organic pigment nano particle, be preferably C.I. pigment Green 7, C.I. pigment green 36, C.I. pigment yellow 150, C.I. pigment yellow 13 9 or C.I. pigment yellow 13 8, more preferably the combination of C.I. pigment green 36 and C.I. pigment yellow 150 or C.I. pigment yellow 13 8 or C.I. pigment yellow 13 9.
Red pigment or orange pigment as organic pigment nano particle are preferably C.I. paratonere 254, C.I. paratonere 177 or C.I. pigment orange 66, and more preferably the C.I. paratonere 254.
Also can use the organic pigment more than 2 kinds or be used in combination the solid solution of organic pigment.
As organic pigment, for example can enumerate azo class pigment, cyanine class pigment, merocyanine class pigment, Coumarins pigment etc.As macromolecular compound, for example can enumerate polydiacetylene, polyimide etc.
Below, the preferred good solvent that adopts during organic pigment nano particle that preparation is used among the present invention describes.
There is no particular limitation for good solvent, as long as it can dissolve employed organic pigment, and can with used getting final product miscible or even mixing of poor solvent when the preparation organic pigment particles.About the dissolubility of organic pigment in good solvent, the solubleness of preferred organic pigment is more than the 0.2 quality %, more preferably more than the 0.5 quality %.There is no particular limitation for the upper limit of the solubleness of organic pigment in good solvent, but consider that employed organic pigment, the upper limit of this solubleness are generally below the 50 quality %.This solubleness also can be the solubleness when dissolving under acidity or alkali condition.In addition, for the compatibility or the even Combination of good solvent and poor solvent, the preferred solubleness of good solvent in poor solvent is more than the 30 quality %, more preferably more than the 50 quality %.There is no particular limitation to the upper limit of the meltage of good solvent in poor solvent, and they can mix with ratio arbitrarily.
As good solvent, for example (for example can enumerate the water kind solvent, water, or hydrochloric acid, sodium hydrate aqueous solution), alcohols solvent, amide solvent, ketones solvent, ether solvent, the aromatic series kind solvent, carbon disulphide, the aliphatic category solvent, nitrile solvents, the sulfoxide kind solvent, halogen-containing kind solvent, esters solvent, ionic liquid, perhaps their mixed solvent etc., the preferred water kind solvent, alcohols solvent, esters solvent, sulfoxide kind solvent or amide solvent, more preferably water kind solvent, sulfoxide kind solvent or amide solvent, preferred especially sulfoxide kind solvent or amide solvent.
As alcohols solvent, for example can enumerate methyl alcohol, ethanol, isopropyl alcohol, n-propanol, 1-methoxyl-2-propyl alcohol etc.As amide solvent, for example can enumerate N, dinethylformamide, 1-Methyl-2-Pyrrolidone, 2-Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 2-Pyrrolidone, epsilon-caprolactams, formamide, N-NMF, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl propanamide, HMPA etc.As ketones solvent, for example can enumerate acetone, MEK, methyl isobutyl ketone, cyclohexanone.As ether solvent, for example can enumerate dimethyl ether, Anaesthetie Ether, tetrahydrofuran etc.As the aromatic series kind solvent, for example can enumerate benzene, toluene etc.As the aliphatic category solvent, for example can enumerate hexane etc.As nitrile solvents, for example can enumerate acetonitrile etc.As the sulfoxide kind solvent, for example can enumerate dimethyl sulfoxide (DMSO), diethyl sulfoxide, hexamethylene sulfone, sulfolane etc.As halogen-containing kind solvent, for example can enumerate methylene chloride, triclene etc.As esters solvent, for example can enumerate ethyl acetate, ethyl lactate, 2-(1-methoxyl) propyl-acetic acid ester etc.As ionic liquid, for example can enumerate 1-butyl-3-methylimidazole and PF 6 -Salt etc.
In addition, as the concentration that organic pigment is dissolved in the organic pigment solution that forms in the good solvent, preferably its scope be under the condition in when dissolving the saturation concentration of organic pigment in good solvent to about 1/100 of this saturation concentration.
In the preparation condition of organic pigment solution, be not particularly limited for the preparation condition of organic pigment solution, can select from normal pressure to scope subcritical, super critical condition.When dissolving under normal pressure, temperature is preferably-10 ℃～150 ℃, more preferably-5 ℃～130 ℃, be preferably 0 ℃～100 ℃ especially.
The organic pigment that contains in the used organic pigment solution must be dissolved in the good solvent equably, but also preferably dissolves under acidity or alkali condition.Usually, use alkali condition when in adopting molecule, having the pigment of the group that can under alkali condition, dissociate, and do not exist in use acid condition when having a plurality of nitrogen-atoms that is easy to the addition proton in the group of disassociation alkali condition under and the molecule in the molecule.For example, quinoline a word used for translation ketone pigment, diketopyrrolopyrroles pigment, disazo condensation thing class pigment dissolve under alkali condition, and phthalocyanine pigment dissolves under acid condition.
The alkali that uses when dissolving under alkali condition is inorganic bases such as lithium hydroxide, NaOH, potassium hydroxide, calcium hydroxide or baryta hydrate, or organic bases such as trialkylamine, diazabicyclo hendecene (DBU), metal alkoxide, but preferred inorganic base.
There is no particular limitation for the amount of employed alkali, so long as the amount of organic pigment uniform dissolution is got final product, but under the situation of using inorganic base, be 1.0 molar equivalents～30 molar equivalents preferably with respect to organic pigment, more preferably 1.0 molar equivalents～25 molar equivalents, more preferably 1.0 molar equivalents～20 molar equivalents.Using under the situation of organic base, be 1.0 molar equivalents～100 molar equivalents preferably with respect to organic pigment, more preferably 5.0 molar equivalents～100 molar equivalents, more preferably 20 molar equivalents～100 molar equivalents.
The acid of using when dissolving under acid condition is mineral acids such as sulfuric acid, hydrochloric acid or phosphoric acid, perhaps organic acids such as acetate, trifluoroacetic acid, oxalic acid, methane-sulforic acid or trifluoromethanesulfonic acid, but preferred mineral acid.Special preferably sulfuric acid.
There is no particular limitation for the amount of employed acid, so long as the amount of organic pigment uniform dissolution is got final product, but compare often excessive use with alkali.No matter be to use mineral acid or organic acid, be 3 molar equivalents～500 molar equivalents preferably with respect to organic pigment, more preferably 10 molar equivalents～500 molar equivalents, more preferably 30 molar equivalents～200 molar equivalents.
Below, the preferred poor solvent that adopts during organic pigment nano particle that preparation is used among the present invention describes.
There is no particular limitation to poor solvent, as long as this poor solvent do not dissolve employed organic pigment, and can be when making organic pigment particles employed good solvent miscible or get final product even the mixing.The solubleness of organic pigment in poor solvent is preferably below the 0.02 quality %, more preferably below the 0.01 quality %.There is no particular limitation for the lower limit of the solubleness of organic pigment in poor solvent, but consider that employed organic pigment, the lower limit of this solubleness are generally more than the 0.000001 quality %.The compatibility of poor solvent and good solvent or even blended preferable range are as previously mentioned.
As poor solvent, for example (for example can enumerate the water kind solvent, water or hydrochloric acid, sodium hydrate aqueous solution), alcohols solvent, ketones solvent, ether solvent, aromatic series kind solvent, carbon disulphide, aliphatic category solvent, nitrile solvents, halogen-containing kind solvent, esters solvent, ionic liquid, perhaps their mixed solvent etc., preferred water kind solvent, alcohols solvent or esters solvent.
As alcohols solvent, for example can enumerate methyl alcohol, ethanol, isopropyl alcohol, n-propanol, 1-methoxyl-2-propyl alcohol etc.As ketones solvent, for example can enumerate acetone, MEK, methyl isobutyl ketone, cyclohexanone.As ether solvent, for example can enumerate dimethyl ether, Anaesthetie Ether, tetrahydrofuran etc.As the aromatic series kind solvent, for example can enumerate benzene, toluene etc.As the aliphatic category solvent, for example can enumerate hexane etc.As nitrile solvents, for example can enumerate acetonitrile etc.As halogen-containing kind solvent, for example can enumerate methylene chloride, triclene etc.As esters solvent, for example can enumerate ethyl acetate, ethyl lactate, acetate 2-(1-methoxyl) propyl ester etc.As ionic liquid, for example can enumerate 1-butyl-3-methylimidazole and PF 6 -Salt etc.
Certain solvent is good solvent or poor solvent, depends on the kind as the organic pigment of object.In the present invention, for certain organic pigment, good solvent and poor solvent must not be with a kind of compound.
(alkali solubility cementing agent)
Preferably when forming organic pigment nano particle, add alkali solubility cementing agent with acidic-group.Alkali solubility cementing agent with acidic-group can be added in organic pigment solution and the poor solvent (in this poor solvent, adding organic pigment solution) to generate organic pigment nano particle both or one in.Perhaps, also preferably when forming organic pigment nano particle, adopt other system to add alkali solubility binder solution with acidic-group.As the alkali solubility cementing agent with acidic-group (below, abbreviate " cementing agent " as), preferably on side chain, has the polymkeric substance of carboxylic acid group or carboxylic acid ester groups isopolarity group.As its example, can be set forth in maleic acid of the methacrylic acid copolymer put down in writing in Japanese kokai publication sho 59-44615 communique, Japanese Patent Publication 54-34327 communique, Japanese Patent Publication 58-12577 communique, Japanese Patent Publication 54-25957 communique, Japanese kokai publication sho 59-53836 communique and the Japanese kokai publication sho 59-71048 communique, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification etc.In addition, can also be set forth in the cellulose derivative that has the carboxylic acid group on the side chain, in addition, can also preferably use have the material that forms behind the addition cyclic acid anhydride on the polymkeric substance of hydroxyl.And, as more preferred example, can be set forth in United States Patent (USP) the 4th, 139, (methyl) benzyl acrylate of putting down in writing in No. 391 the instructions and (methyl) acrylic acid multipolymer, and the multiple copolymer of (methyl) benzyl acrylate, (methyl) acrylic acid and the formation of other monomer.These have the binder polymer of polar group, can use separately, and the state that also can form composition also to use with the film forming polymkeric substance of routine uses.With respect to the organic pigment of 100 mass parts, its addition is generally 10～200 mass parts, preferred 25～100 mass parts.
When the alkali solubility cementing agent with acidic-group is macromolecular compound, quantity for the acidic-group in this macromolecular compound has no particular limits, but, when the quantity of the repetitive that contains in a part is 100, the quantity that contains the repetitive of acidic-group is preferably 5～100, and more preferably 10～100.In addition, for (1) by the repetitive of compound deriving and (2) with carboxyl for the polymerization ratio of the repetitive of compound deriving with carboxylic acid ester groups, the mole % of repetitive (1) is preferably 5～40, the mole % of repetitive (2) is preferably 40～90, and the mole % of other repetitive except repetitive (1) or (2) is preferably below 25.And, be preferably 3000～1000000 as the molecular weight of the macromolecular compound of alkali solubility cementing agent with acidic-group, more preferably 4000～200000, be preferably 5000～80000 especially.
(spreading agent when forming organic pigment nano particle)
Spreading agent can be added in organic pigment solution and the poor solvent (in this poor solvent, adding organic pigment solution) to generate organic pigment nano particle both or one in.Perhaps, also preferably when forming organic pigment nano particle, adopt other system to add dispersant solution.Spreading agent has following effect: (1) is adsorbed on the surface of pigments of separating out quickly, forms fine organic pigment particles, and (2) prevent that these particles from aggegation taking place again.
As spreading agent, for example can use the low molecule or the macromolecule dispersing agent of anionic, cationic, amphoteric ion type, nonionic or color type.Also have, the molecular weight of macromolecule dispersing agent is had no particular limits, as long as this macromolecule dispersing agent is dissolved in the solution equably, but preferred molecular weight is 1,000～2,000,000, more preferably 5,000～1,000,000, more preferably 10,000～500,000, be preferably 10,000～100 especially, 000 (in the present invention, if do not illustrate especially that molecular weight is meant weight-average molecular weight.Macromolecular compound is a polydisperse system, not necessarily has identical molecular weight or grain amount.Therefore, the value quovis modo of measured molecular weight all is the mean molecular weight after average.Mean molecular weight mainly contains following 3 kinds of forms.That is Z mean molecular weight Mz weight-average molecular weight Mw, 3,1) number-average molecular weight Mn, 2)), they have such Mn＜Mw＜Mz) of concerning.As macromolecule dispersing agent, specifically can enumerate polyvinylpyrrolidone, polyvinyl alcohol (PVA), polyvinyl methyl ether, polyethylene oxide, polyglycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, the part formalizing thing of polyvinyl alcohol (PVA), the part butyralization thing of polyvinyl alcohol (PVA), vinylpyrrolidone/vinyl acetate copolymer, the polyethylene oxide/propylene oxide segmented copolymer, polyacrylate, polyvinyl sulfate, poly-(4-vinylpridine) salt, polyamide, PAH salt, the condensation naphthalene sulfonate, cellulose derivative, starch derivative etc.In addition, can also use natural polymer compounds such as alginate, gelatin, albumin, casein, Arabic gum, bassora gum, lignosulfonate.Wherein, preferably polyethylene base pyrrolidone.These macromolecules can a kind of independent use, also can be used in combination.These spreading agents can use separately or share.About the spreading agent that uses in the organic pigment dispersion, write up is in the 29th～46 page of " pigment dispersing stabilization と surface treatment skill Intraoperative Evaluation value " (chemical corps intelligence association, distribution in Dec calendar year 2001).
As anionic dispersing agent (anionic surface active agent), can enumerate N-acyl-N-alkyltaurate, soap, alkyl sulfate salt, alkyl benzene sulfonate, alkylnaphthalene sulfonate, dialkyl sulfosuccinates, alkyl phosphate salt, naphthalene sulfonic acid-formaldehyde condensation product, polyxyethylated sulfuric acid etc.Wherein, preferred N-acyl-N-alkyltaurate.As the N-acyl-N-alkyltaurate, preferably be recorded in those compounds in the Japanese kokai publication hei 3-273067 instructions.These anionic dispersing agents can use separately, also can be used in combination.
Cationic dispersing agent (cationic surfactant), diamines of comprise quaternary ammonium salt, alkoxylate polyamines, fatty amine polyglycol ether, fatty amine, deriving by fatty amine and aliphatic alcohol and polyamines, by the imidazoline of fatty acid derived and the salt of these cationic materials.These cationic dispersing agents can use separately, also can be used in combination.
The amphoteric ion type spreading agent is to have the cation radical spreading agent partly that contains in the anion base part that contains in the above-mentioned anionic dispersing agent molecule and the cationic dispersing agent molecule in the molecule simultaneously.
As non-ionic dispersing agent (non-ionics), can enumerate polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl amine, fatty acid glyceride etc.Wherein, preferred polyoxyethylene alkylaryl ether.These non-ionic dispersing agents can use separately, also can be used in combination.
So-called color type spreading agent, be defined as by derive as the organic pigment of parent material, by this precursor structure being carried out the color type spreading agent that chemical modification prepares.For example can enumerate and contain sugared color type spreading agent, contain the color type spreading agent that piperidyl color type spreading agent Nai Huo perylene is derived, has the color type spreading agent that is connected the structural functional group of pigment matrix by methylene, have the pigment matrix structure and the sulfonic color type spreading agent that have carried out chemical modification with polymkeric substance, pigment spreading agent with sulfoamido, color type spreading agent with ether, or has a color type spreading agent of carboxylic acid group or carboxylic acid ester groups or carboxamide groups.
####
In addition, also preferably use put down in writing in the TOHKEMY 2000-239554 communique by the represented compound of general formula (I).
In order further to improve the uniformly dispersed and bin stability of pigment, with respect to the organic pigment of 100 mass parts, the content of spreading agent is preferably 0.1～1000 mass parts, more preferably 1～500 mass parts, more preferably 10～250 mass parts.If content is too small, then can't see the raising of organic pigment nano particle dispersion stabilization sometimes.
(condition when forming organic pigment nano particle)
Condition when making organic pigment be generated as organic pigment nano particle has no particular limits, and can select from normal pressure to subcritical, super critical condition.Temperature under the normal pressure is preferably-30～100 ℃, more preferably-10～60 ℃, is preferably 0～30 ℃ especially.
Have no particular limits for the method that organic pigment solution is mixed with poor solvent, preferably, the limit stirs wherein one, the limit will other addings wherein, particularly preferably be, organic pigment solution is joined in the poor solvent that is stirred.Can use equipment such as also can not using pump during interpolation.In addition, can in liquid, submergence add, also can outside liquid, add, but more preferably submergence interpolation in liquid.When employing submergence in liquid is added, add that mouthful can be one also can be a plurality of.The diameter that adds mouth is preferably below the 20mm, more preferably below the 10mm.
Stirring wherein 1 o'clock stirring rate is preferably 100～10000rpm, and more preferably 150～8000rpm is preferably 200～6000rpm especially.
The ratio of organic pigment solution and poor solvent (good solvent/poor solvent) is preferably 1/50～2/3 by volume, and more preferably 1/40～1/2, be preferably 1/20～3/8 especially.
There is no particular limitation for the concentration of the dispersion liquid of preparation behind the organic pigment nano particle, as long as organic pigment nano particle is disperseed, but with respect to the 1000ml dispersion solvent, organic pigment nano particle is preferably 10～40000mg, more preferably 20～30000mg is preferably 50～25000mg especially.
(mean grain size of organic pigment nano particle, monodispersity)
Mean grain size about organic pigment nano particle, thereby have by the quantize method of expression group average-size of determination method, particle diameter as frequent use, performance distribute peaked particle diameter the most frequently, the meta particle diameter that is equivalent to the integral distribution curve central value, various mean grain size (number average, length is average, area is average, weight average, volume averaging etc.) etc. are arranged, in the present invention, if do not particularly point out, then mean grain size is meant number average bead diameter.The mean grain size of organic pigment nano particle (primary particle) is preferably 50nm following (for example, being big or small like this crystal or aggregate), more preferably 10～45nm, more preferably 15～40nm.
In addition, as the index of expression particle monodispersity, short of in the present invention specifying, the ratio (Mv/Mn) of use volume average particle size (Mv) and number average bead diameter (Mn).The monodispersity of the particle (primary particle) that contains in the organic pigment nano particle dispersion liquid of when the organic pigment dispersive composition that preparation is used among the present invention, being prepared, be that Mv/Mn is preferably 1.0～2.0, more preferably 1.0～1.8, be preferably 1.0～1.5 especially.
(concentrating of organic pigment nano particle dispersion liquid)
By the organic pigment nano particle dispersion liquid is carried out desalination and concentration, can be suitable for being used as the organic pigment nano particle dispersion liquid of color filter coating liquid with industrial-scale production.
Below, the method for concentration of dispersion liquid is described.
Method for concentration is had no particular limits, as long as can concentrate the organic pigment nano particle dispersion liquid, for example preferably in the organic pigment nano particle dispersion liquid, add and extract solvent and mixing, with the organic pigment nano particle concentration extraction to this extract solvent mutually in, and form the method for concentrated nano particle liquid with this concentrated extracting solution of filtration such as filtrator; The method of utilizing centrifuging to make the organic pigment nano particle sedimentation and concentrating; Utilize ultrafiltration to carry out the method for desalination and concentration; The method that solvent distillation is concentrated by vacuum freeze drying; Make method that solvent seasoning concentrates etc. by heating or decompression.Or very preferably use the combination of these methods.
The concentration of the organic pigment nano particle after concentrating is preferably 1～100 quality %, and more preferably 5～100 quality % are preferably 10～100 quality % especially.
Below, the concentration extraction method is described.The extraction solvent that uses in this concentration extraction is had no particular limits, but in fact with the dispersion solvent of organic pigment nano particle dispersion liquid (for example, aqueous solvent) do not mix (in the present invention, do not take place in fact to mix and be meant that mutual solubility is low, meltage is preferably below the 50 quality %, and more preferably 30 quality % are following) and the solvent that forms the interface when after mixing, leaving standstill be preferred.In addition, preferred this extraction solvent is organic pigment nano particle is scattered in again also produce the weak aggegation solvent of (also can disperse again even do not apply high shear force by grind or high-speed stirred etc.) in the extraction solvent.If reach this state, then can not form the strong aggegation that particle size is changed, available extraction wet with solvent purpose organic pigment nano particle can easily remove the diffusing solvent of the five equilibrium that anhydrates by filtering to wait on the other hand, from these aspects, described solvent is preferred.As extracting solvent, preferred esters solvent, alcohols solvent, aromatic series kind solvent, aliphatic category solvent, more preferably esters solvent, aromatic series kind solvent or aliphatic category solvent, especially preferably esters solvent.
As esters solvent, for example can enumerate acetate 2-(1-methoxyl) propyl ester, ethyl acetate, ethyl lactate etc.As alcohols solvent, for example can enumerate normal butyl alcohol, isobutyl alcohol etc.As the aromatic series kind solvent, for example can enumerate benzene,toluene,xylene etc.As the aliphatic category solvent, for example can enumerate normal hexane, cyclohexane etc.In addition, the extraction solvent can be the simple solvent in the above-mentioned preferred solvent, also can be the mixed solvent that is formed by multiple solvent.
The amount of extracting solvent is not particularly limited, as long as can extract organic pigment nano particle, considers concentration extraction, preferably its amount ratio organic pigment nano particle dispersion liquid still less.If represent with volume ratio, then the organic pigment nano particle dispersion liquid was made as 100 o'clock, the extraction solvent that is added is preferably 1～100, and more preferably 10～90, be preferably 20～80 especially.If too much, then sometimes concentrating needs a large amount of time, if very few, then sometimes extract insufficient, residual nano particle in the dispersion solvent.
After adding the extraction solvent,, preferably mix in order fully to contact with dispersion liquid.Mix and to use usual way.Have no particular limits adding the temperature of extracting solvent and mixing when, but be preferably 1～100 ℃, more preferably 5～60 ℃.For interpolation, the mixing of extracting solvent, just can use any device as long as can implement each operation satisfactorily, for example can use separating funnel type device to carry out.
Under the situation that adopts ultrafiltration, for example can use the desalination/concentrated method that is used for silver emulsion.Open (Research Disclosure) No.10 208 (1972), No.13 122 (1975) and No.16 351 (1977) are studied in known having.For pressure differential and flow as the important operation condition, can publish (1978) with reference to the big spring man of virtue and ability of arrow work " film utilizes technology Ha Application De Block Star Network " good fortune study, the family curve of putting down in writing among the p275 is selected, but disperse the object space face at the processing target organic pigment nano particle, in order to suppress the aggegation of particle, also need to find out optimum condition.In addition,, the constant volume formula of continuous interpolation solvent and the batch-type that gradation is intermittently added are arranged, but the preferred desalting processing time is relatively than the constant volume formula of weak point with regard to replenishing because of film sees through for the method for the solvent that lose.Solvent for replenishing thus can use the pure water that obtains by ion-exchange or distillation, but also can sneak into the poor solvent of spreading agent, spreading agent in pure water, also can directly add organic pigment nano particle to and disperse in the thing.
Fig. 2 has shown that one of the device that is used to carry out ultrafiltration constitutes example.As shown in Figure 2, this device possesses the jar 21 that holds fatty acid silver and disperse thing, makes dispersion thing in this jar 21 carry out the round-robin circulation with pump 22 and the ultrafiltration module 23 that will remove as permeate water with the by-product inorganic salts in the dispersion thing of pump 22 importings by circulation.The dispersion thing of isolated permeate water is turned back in the jar 21 once more, carries out same operation repeatedly, until reaching the predetermined purpose of removing by-product inorganic salts.In addition, also be provided with additional pure water metering in this device, be used for measuring, and be provided with the permeate water metering flowmeter 25 that is used for determining the pure water magnitude of recruitment replenish used a certain amount of water because of the solvent that runs off by permeate water with flowmeter 24.In addition, also can be provided for importing the reverse flushing pump 26 of the dilution water of permeate water.
As ultra filtration membrane, ultra filtration membrane such as plate, the screw type of packing into, cylinder type, macaroni yarn type, hollow fiber type as module, there are society of Asahi Chemical Industry's (strain), ダ イ セ Le chemistry (strain) society, (strain) DongレShe, (strain) day Dong Diangongshe etc. to sell, but from the angle of total membrane area and cleaning, preferred screw type or macaroni yarn type ultra filtration membrane.In addition,, must determine, be preferably more than 5,000 below 50,000, more preferably more than 5,000 below 15,000 according to the molecular weight of employed spreading agent as the molecular cut off of the threshold value index of membrane-permeable composition.
For the dispersion solvent with the organic pigment nano particle dispersion liquid separates with concentrated extracting solution, preferably carry out filtrator and filter.As the filtration unit that filtrator uses, for example can use the device of pressure filtration and so on.As preferred filtrator, can enumerate nanofilter, ultrafilter etc.Preferably filter, remove residual dispersion solvent, the organic pigment nano particle in the concentrated extracting solution is concentrated and forms concentrated nano particle liquid by filtrator.
Freeze-drying method is had no particular limits any method that to use those skilled in the art to adopt.For example, can enumerate refrigerant direct expansion method, repeated freezing method, heating agent round-robin method, triple heat-exchanging method, indirect heating freezing, but preferably use refrigerant direct expansion method, indirect heating freezing, more preferably use the indirect heating freezing.All preferably after carrying out precooling, carry out freeze drying in any method.The precooling condition is had no particular limits, and to carry out cryodesiccated sample freezing equably but must make.
Device as the indirect heating freezing, can enumerate small frozen dryer, FTS freeze drier, LYOVAC freeze drier, experiment freeze drier, research freeze drier, triple heat interchange vacuum freeze drier, single-cooling type freeze drier, HULL freeze drier, but preferably small frozen dryer, experiment with freeze drier, research with freeze drier, single-cooling type freeze drier, preferred small frozen dryer, single-cooling type freeze drier.
Cryodesiccated temperature is had no particular limits, for example be-190～-4 ℃ approximately, preferred-120～-20 ℃ approximately, more preferably from about-80～-60 ℃.Cryodesiccated pressure is also had no particular limits, and those skilled in the art can suitably select, for example can be at about 0.1～35Pa, and preferred about 1～15Pa more preferably from about carries out under 5～10Pa.Sublimation drying is for example about 2～48 hours, preferred about 6～36 hours, and more preferably from about 16～26 hours.Certainly, these conditions can suitably be selected by those skilled in the art.About freeze-drying, can reference example such as pharmaceutical machine technology Ha Application De Block Star Network: pharmaceutical machine technical research meeting be compiled, book shop, people from ground, p.120～129 (in September, 2000); Vacuum Ha Application De Block Star Network: ULVAC Corp compiles, オ-system society, p.328～331 (1992); Freezing and drying study Hui Hui Chi: she controls him at the rattan filial piety, No.15, p.82 (nineteen sixty-five) etc.
Below centrifuging is described.As concentrating the centrifugal separator that uses in the organic pigment nano particle by centrifuging, as long as can make the organic pigment nano particle sedimentation in the organic pigment nano particle dispersion liquid (or organic pigment nano particle concentrated extracting solution), can use any device.As centrifugal separator, for example, except fexible unit, the centrifugal separator etc. that can enumerate the hydro-extractor of the skin function of taking (suction supernatant layer in rotation, and be discharged into system outer function with it) and discharge solid content continuously.
As the condition of centrifuging, centrifugal force (be expressed as need times over the value of the centrifugal acceleration of acceleration of gravity) is preferably 50～10000, and more preferably 100～8000, be preferably 150～6000 especially.Temperature during centrifuging depends on the solvent species of dispersion liquid, but is preferably-10～80 ℃, more preferably-5～70 ℃, is preferably 0～60 ℃ especially.
Below drying is described.The device that uses when concentrating organic pigment nano particle by drying under reduced pressure has no particular limits, as long as can make the solvent evaporation of organic pigment nano particle dispersion liquid (or organic pigment nano particle concentrated extracting solution).Thereby for example can enumerate general vacuum dryer and rotary pump and on one side agitated liquid heat on one side drying under reduced pressure device, can make the pipe of liquid by the heating decompression carry out the device etc. of continuous drying.
Heating drying under reduced pressure temperature is preferably 30～230 ℃, more preferably 35～200 ℃, is preferably 40～180 ℃ especially.Pressure during decompression is preferably 100～100000Pa, and more preferably 300～90000Pa is preferably 500～80000Pa especially.
According to above-mentioned method for concentration, can from the organic pigment nano particle dispersion liquid, concentrate out organic pigment nano particle effectively.About cycles of concentration, if for example will be made as 1 as the nano particle concentration in the organic pigment nano particle dispersion liquid of raw material, then can be concentrated into the concentration that concentrates in the organic pigment nano particle paste and be preferably about 100～about 3000 times, more preferably about 500～about 2000 times.
(dispersion again of organic pigment nano particle dispersion liquid)
In the present invention, can with the organic pigment nano particle after concentrating in the organic solvent that contains alkali solubility cementing agent with acidic-group fine once more decentralized (below, be also referred to as " decentralized again ") (in the present invention, fine decentralized be to instigate the agglutination particle in the dispersion liquid to scatter, to improve dispersion degree).
Purposes being used for color filter etc. can join the organic pigment nano particle after concentrating and make its dispersion in the carrier.Above-mentioned carrier is meant the medium part that organic pigment is disperseed, and comprises aqueous combine part (cementing agent) that also set films with above-mentioned organic pigment and it being carried out the composition (organic solvent) of dissolved dilution.In addition, in the present invention, the cementing agent that the cementing agent that is adopted when forming nano particle is adopted when decentralized again can be identical, also can difference; Sometimes also divide into the cementing agent that uses when forming nano particle respectively and the cementing agent of use when disperseing again.
Organic pigment concentration after decentralized again determines suitably that according to purpose with respect to the total amount of dispersive composition, organic pigment concentration is preferably 2～30 quality %, and more preferably 4～20 quality % are preferably 5～15 quality % especially.For aforesaid situation of in carrier, disperseing, cementing agent and dissolved dilution carry out suitably determining according to the kind of organic pigment etc. with the amount of composition, total amount with respect to the organic pigment dispersive composition, the amount of cementing agent is preferably 1～30 quality %, more preferably 3～20 quality % are preferably 5～15 quality % especially.Dissolved dilution is preferably 5～80 quality % with the amount of composition, more preferably 10～70 quality %.
In the organic pigment nano particle liquid after above-mentioned concentration extraction, become under the possible state in filtrator filtration fast, aggegation takes place owing to concentrating in organic pigment nano particle usually.In addition, aggegation also takes place owing to concentrating in organic pigment nano particle easily that adopt centrifugal separation or seasoning to concentrate.
As the method that this aggegation nano particle (among the present invention, the aggegation nano particle is meant the nano particle of assembling by the effect of secondary force, as agglutination body etc.) is disperseed, for example can adopt ultrasonic scattering method and apply the method for physical energy.
The ultrasonic irradiation device preferably has the device that can apply the above hyperacoustic function of 10kHz, for example can enumerate ultrasonic homogenizer, supersonic wave cleaning machine etc.If the temperature of solution rises during ultrasonic irradiation, then can cause the thermal thermocoagulation of nano particle, so the preferred solution temperature is 1～100 ℃, more preferably 5～60 ℃.As temperature-controlled process, can be by control dispersion liquid temperature, the adjustment layer of control dispersion liquid temperature is carried out temperature control and implement.
To being not particularly limited, for example can enumerate known dispersion machines such as kneader, roll crusher, second reduction machine, high-speed grinder, dissolving machine, homo-mixer, sand mill as applying the dispersion machine that uses when physical energy disperses organic pigment nano particle after concentrating.
As when disperseing again when forming organic pigment nano particle employed spreading agent, preferably reuse at those compounds shown in (spreading agent when forming organic pigment nano particle).
Can make the organic pigment nano particle (primary particle) after disperseing again become fine decentralized particle, its mean grain size is preferably below the 50nm, and more preferably 10～45nm is preferably 15～40nm especially.In addition, the Mv/Mn of the particle after disperseing again is preferably 1.0～2.0, and more preferably 1.0～1.8, excellent especially is 1.0～1.5.
Below, to backlight the describing of three-wavelength type of using among the present invention.
The three-wavelength type that uses among the present invention is backlight, preferably is made of green (G) LED, redness (R) LED and blueness (B) LED.More preferably, the peak wavelength of above-mentioned green (G) LED is in the scope of 520～540nm, and the peak wavelength of above-mentioned redness (R) LED is more than 620nm, and the peak wavelength of above-mentioned blueness (B) LED is below 470nm.
In liquid crystal display cells of the present invention, the peak wavelength by making each color can make green reproduction regions broaden in above-mentioned scope, can utilize color filter that each color is carried out color separated in addition easily.
Below, the LED of each color is described.
1. green (G) LED
There is no particular limitation for kind of the green among the present invention (G) LED etc., so long as peak wavelength gets final product at green (G) LED of 520～540nm.The peak wavelength of the green (G) of NTSC specification (dotted line) is near 530nm.
In liquid crystal display cells of the present invention, the peak wavelength by making green (G) LED in the three-wavelength type LED-backlit can make green reproduction regions broaden, and can improve the NTSC ratio at 520～540nm.
Here, NTSC is than the color reproduction scope of the actual measurement that the is meant liquid crystal display cells ratio with respect to the color reproduction scope of NTSC specification.
In the present invention, the peak wavelength of above-mentioned green (G) LED is in the scope of 520～540nm, and is wherein preferred in the scope of 530～540nm.
Specifically, as the kind of green (G) LED of its peak wavelength in above-mentioned scope, can enumerate for example DG1112H (ス Application レ-electric (strain) manufacturing), UG1112H (ス Application レ-electric (strain) manufacturing), E1L51-3G (Toyota's synthetic (strain) makes), E1L49-3G (Toyota's synthetic (strain) makes), NSPG500S (day inferior chemical industry (strain) is made) etc.
2. red (R) LED
There is no particular limitation for the kind of the redness among the present invention (R) LED, so long as the LED of peak wavelength more than 620nm gets final product.The peak wavelength of the redness of NTSC specification (R) is near 610nm.
In liquid crystal display cells of the present invention, the peak wavelength of redness (R) LED by making three-wavelength type LED-backlit can reproduce the chroma point of red NTSC specification, and can improve the NTSC ratio more than 620nm.
In addition, the peak wavelength of red (R) LED is opened its color separated with above-mentioned green (G) LED easily by color filter, so can be improved the colour purity of liquid crystal display cells in above-mentioned scope.
In the present invention, the peak wavelength of red (R) LED is more than 620nm, and is wherein preferred in the scope of 625nm～635nm.
Specifically, as redness (R) LED of peak wavelength in above-mentioned scope, the kind of operable LED can be enumerated for example FR1112H (ス Application レ-electric (strain) manufacturing), FR5366X (ス Application レ-electric (strain) manufacturing), NSTM515AS (R) (day inferior chemical industry (strain) is made), GL3ZR2D1COS (シ ャ-プ (strain) manufacturing), GM1JJ35200AE (シ ヤ-プ (strain) manufacturing) etc.
3. blue (B) LED
There is no particular limitation for the blueness of using among the present invention (B) LED, so long as the LED of peak wavelength below 470nm gets final product.The peak wavelength of the blueness of NTSC specification (B) is near 470nm.In liquid crystal display cells of the present invention, the peak wavelength of blueness (B) LED by making LED-backlit used in the liquid crystal display cells can reproduce the chroma point of blue NTSC specification, and can improve the NTSC ratio below 470nm.
In addition, the peak wavelength of blue (B) LED is opened its color separated with above-mentioned green (G) LED easily by color filter, so can be improved the colour purity of liquid crystal display cells in above-mentioned scope.
In the present invention, consider that the peak wavelength of blue (B) LED is below 470nm, and is wherein preferred in the scope of 450nm～465nm from the angle of carrying out color separated by color filter.
Specifically, as blueness (B) LED of peak wavelength in above-mentioned scope, the kind of operable LED can be enumerated for example DB1112H (ス Application レ-electric (strain) manufacturing), DB5306X (ス Application レ-electric (strain) manufacturing), E1L51-3B (Toyota's synthetic (strain) makes), E1L4E-SB1A (Toyota's synthetic (strain) makes), NSPB630S (day inferior chemical industry (strain) is made), NSPB310A (day inferior chemical industry (strain) is made) etc.
The three-wavelength type that uses among the present invention is backlight, combines by the LED with above-mentioned 3 kinds of colors, can widen the color reproduction scope, and easily each color is carried out color separated by color filter.
In addition, the brightness ratio of the LED by regulating above-mentioned 3 kinds of colors can be regulated white balance.That is, also can regulate chroma point as the illuminant-C of the white of NTSC specification.
The three-wavelength type that uses among the present invention is backlight, and is generally backlight as side-light type.Side-light type is backlight to be meant constitute so like this backlight: light source is configured in the side of back light unit, and is provided with the light guide plate of diffuse reflection parts etc. below, can access homogeneous light emitting area thus.Compare with direct-type backlight, adopt side-light type mode backlight can make the back light unit miniaturization, in addition, the number that constitutes required LED backlight is also less relatively, also is preferred from this point.
Here, the measured value of the spectrophotometric spectra among the present invention is that the beam split light measurer MCPD-2000 that adopts Otsuka Electronics Co., Ltd. to make measures.
Embodiment
Below, the present invention will be described in more detail based on embodiment, but the present invention is not limited to these examples.In addition, if not special explanation, " part " expression " mass parts " in following embodiment, " % " expression " quality % ", " molecular weight " is meant " weight-average molecular weight ".
(embodiment)
＜pigment dispensing composition A 〉
500ml methane-sulforic acid (the 1st solvent) (making with the pure medicine of light Co., Ltd.) is heated to 80 ℃, simultaneously to wherein adding 30.0g pigment C.I. pigment Violet 23 (manufacturing of Network ラ リ ア Application ト Co., Ltd., Hostaperm Violet RL-NF) and 30.0g polyvinylpyrrolidone (trade name K-30, make with the pure medicine of light Co., Ltd.), make pigment solution A (density: 1.0kg/m 2).
Use viscosity meter VM-10A-L (trade name, CBC マ テ リ ア Le ズ society makes) to measure the viscosity of this pigment solution A, the result shows that the viscosity of pigment solution A when the liquid temperature is 25.0 ℃ is 18.1mPas.Prepare 1500mL water in addition, wherein contain the 1mol/L sodium hydroxide solution (making) of 15mL, as poor solvent (the 2nd solvent) with the pure medicine of light Co., Ltd..
Here, temperature is controlled to be 25 ℃, to utilizing GK-0222-10 type ラ モ Application De ス -ラ-(trade name, Fujisawa Pharmaceutical Co., Ltd makes) in poor solvent-1500mL water of stirring with the rotating speed of 500rpm, inject 80 ℃ pigment solution A with NP-KX-500 type high capacity flexible hose pump (trade name, Japanese precision chemical society makes).Carry the fluid passage diameter and the supply port diameter of the pipeline of pigment solution A to be 0.8mm, supply port is put in the poor solvent, the flow velocity injection 400mL pigment solution A with 100mL/min forms organic pigment particles thus, makes dispersible pigment dispersion A.
The H-112 type filter centrifugal that uses コ Network サ Application (strain) society to make reaches and applies the P89C type filter cloth that island カ Application バ ズ (strain) society makes, the dispersible pigment dispersion A that adopts method for preparing is concentrated 90 minutes with the rotating speed of 5000rpm, from dispersible pigment dispersion A, remove solvent, reclaim and obtain the concentrated paste of pigment nano particle.The 8453 type spectrophotometric determinations made from ア ジ レ Application ト (Agilent) company concentrate the pigment containing ratio of sticking with paste, and the result is 17.1 quality %.
In 50.0mL ethyl lactate (the 3rd solvent), add 0.13g according to synthetic pigment dispersing agent A, the 2.50g ソ Le ス パ-ス 39000 that obtains of the method in the TOHKEMY 2000-239554 communique (PVC Star Network ケ ミ-society makes), be mixed with solution, add this solution to 15.4g above-mentioned pigment nano particle and concentrate in the paste.Stirred 60 minutes with the rotating speed of dissolving machine, add 25.0mL ethyl acetate again, stirred 10 minutes, obtain dispersion liquid with the rotating speed of dissolving machine with 500rpm with 1500rpm.
This dispersion liquid is filtered (the 2nd concentrated operation of removing) with the FP-010 type filter that the Off ァ イ of Sumitomo Electric Industries Application Port リ マ society makes, thereby obtain the concentrated pigment liquid A (nano dye concentration is 30.6 quality %) of pasty state.
Figure A200810147533D00341
(pigment dispersing agent A)
Use the concentrated pigment liquid A of above-mentioned pasty state, preparation has the pigment dispensing composition A of following composition.
The concentrated pigment liquid A 21.0g of above-mentioned pasty state
MFGAC 43.3g
Use ultrasonic homogenizer that the pigment dispensing composition of above-mentioned composition was disperseed 3 hours, obtain pigment dispensing composition A.By the pigment nano particle in the resulting pigment dispensing composition of sem observation, recording its mean grain size is 20nm.
＜pigment dispensing composition B 〉
According to following composition pigment preparation dispersive composition B.
Pigment (pigment Violet 23) 9.60g
Sodium chloride 100.0g
Pigment dispersing agent A 0.90g
ソ Le ス パ-ス 39000 (PVC Star Network ヶ ミ-society makes) 9.60g
To 1, the powder, the ソ Le ス パ-ス 39000 that add sodium chloride, pigment (pigment Violet 23 (manufacturing of Network ラ リ ア Application ト society, Hostaperm Violet RL-NF)) in the 3-butylene glycol diacetate esters liquid, and it is joined in the twin-screw kneader, 80 ℃ mixed 6 hours down.After mixed, said mixture is taken out and joins in 80 ℃ 1% aqueous hydrochloric acid solution of 700 mass parts, stir after 1 hour, filter, use hot wash, drying, pulverizing, add 1 of 2.4g according to the 1g crushed material then, the ratio of 3-butylene glycol diacetate esters is added the 1,3 butylene glycol diacetate esters and is mixed.Then, utilize electronic mill M-50 (ア イ ガ-ジ ヤ パ Application society makes) and use the zirconia microballon of diameter, under the condition of peripheral speed 9m/s, above-mentioned color compositions was disperseed 1 hour, obtained pigment dispersing thing B as 0.65mm.By the pigment particles in the resulting pigment dispensing composition of sem observation, recording its mean grain size is 85nm.
＜B pigment dispersing thing 1 〉
Prepare B pigment dispersing thing 1 according to the method identical with preparing pigment dispensing composition B, difference is, イ Application キ makes the Rionol BlueES that (strain) makes with PB15:6 (East ocean) replace employed PV-23 when the above-mentioned pigment dispensing composition B of preparation.By the pigment particles in the resulting B pigment dispersing of the sem observation thing 1, recording its mean grain size is 55nm.
Then, become phase-splitting to mix with other the B pigment dispersing thing that obtains 1, make to have the composition shown in the tabulation 1 down, thereby make color filter with photosensitive composition B1 and B2.
Table 1
Photosensitive composition B1 B2
B pigment dispersing thing 1 (C.I.P.B.15:6) 8.0 8.0
Pigment dispensing composition A (C.I.P.V.23) 1.1 0
Pigment dispensing composition B (C.I.P.V.23) 0 1.1
MFGAC 28 28
MEK 26 26
Cementing agent 1 19 19
DPHA liquid 4.2 4.2
2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole 0.17 0.17
Phenothiazine 0.020 0.020
Surfactant 1 0.060 0.060
(unit: mass parts)
＜cementing agent 1 〉
Polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid/methyl methacrylate=36/22/42 mol ratio, molecular weight 30,000) 27 mass parts
MFGAC 73 mass parts
＜DPHA liquid 〉
(contain polymerization inhibitor MEHQ 500ppm, Japanese chemical drug (strain) society makes dipentaerythritol acrylate, trade name: 76 mass parts KAYARAD DPHA)
MFGAC 24 mass parts
＜surfactant 1 〉
Following works 1 30 mass parts
MEK 70 mass parts
Works 1
Figure A200810147533D00361
(n＝6，x＝55，y＝5，Mw＝33940，Mw/Mn＝2.55，
PO: epoxypropane, EO: oxirane)
Then, prepare following photosensitive composition K1, R103, G103 according to prescription and the method described in the embodiment 1 and 13 of TOHKEMY 2006-276818 communique.
Table 2
Photosensitive composition K1
K pigment dispersing thing 1 (carbon black) 25
Propylene glycol monomethyl ether 8.0
MEK 53
Cementing agent 2 9.1
Hydroquinone monomethylether 0.002
DPHA liquid 4.2
2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methyl)-3 '-bromophenyl]-the s-triazine 0.16
Surfactant 1 0.044
(unit: mass parts)
＜K pigment dispersing thing 1 〉
Carbon black 13.1 mass parts
Spreading agent (following compound 1) 0.65 mass parts
Polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight 3.7 ten thousand) 6.72 mass parts
MFGAC 79.53 mass parts
＜cementing agent 2 〉
Polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=78/22 mol ratio, molecular weight 3.8 ten thousand) 27 mass parts
MFGAC 73 mass parts
Figure A200810147533D00371
Compound 1
Table 3
Photosensitive composition R103
R pigment dispersing thing 1 (C.I.P.R.254) 44.0
R pigment dispersing thing 2 (C.I.P.R.177) 5.0
Propylene glycol monomethyl ether 7.6
MEK 37
Cementing agent 3 0.8
DPHA liquid 4.4
2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole 0.14
2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methyl)-3 '-bromophenyl]-the s-triazine 0.06
Phenothiazine 0.010
Adjuvant 1 0.52
Surfactant 1 0.06
(unit: mass parts)
Table 4
Photosensitive composition G103
G pigment dispersing thing 1 (C.I.P.G.36) 23.7
Y pigment dispersing thing 1 (C.I.P.Y.150) 12.5
Propylene glycol monomethyl ether 29.1
MEK 26
Cyclohexanone 1.3
Cementing agent 2 3.0
DPHA liquid 4.3
2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole 0.15
2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methyl)-3 '-bromophenyl]-the s-triazine 0.06
Phenothiazine 0.005
Surfactant 1 0.07
(unit: mass parts)
＜R pigment dispersing thing 1 〉
C.I.P.R.254 8 mass parts
Spreading agent (above-claimed cpd 1) 0.8 mass parts
Polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight 30,000) 8 mass parts
MFGAC 83 mass parts
＜R pigment dispersing thing 2 〉
C.I.P.R.177 18 mass parts
Polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight 30,000) 12 mass parts
MFGAC 70 mass parts
＜cementing agent 3 〉
Polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid/methyl methacrylate=38/25/37 mol ratio, molecular weight 40,000) 27 mass parts
MFGAC 73 mass parts
＜G pigment dispersing thing 1 〉
C.I.P.G.36 18 mass parts
Polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight 3.8 ten thousand) 12 mass parts
Cyclohexanone 35 mass parts
MFGAC 35 mass parts
＜Y pigment dispersing thing 1 〉
Drive CF イ エ ロ-EX3393 (trade name) that state's pigment (strain) society makes
Use is according to photosensitive composition K1, B1, R103, the G103 of above-mentioned composition preparation, method (as described below) according to identical with the embodiment 11 of TOHKEMY 2006-276818 communique makes corresponding photosensitive resin transfer material K1, B1, R103, G103 respectively.
The making of-photosensitive resin transfer material-
At thickness is on the interim stilt of polyethylene terephthalate film of 75 μ m, applies the thermoplastic resin coating liquid that is made of following prescription H1 with the slit-shaped nozzle, and carries out drying.Then, apply the middle layer coating liquid that constitutes by following prescription P1, and carry out drying.Apply above-mentioned photosensitive composition K1 again; and carry out drying; thereby the thermoplastic resin that dry film thickness is 14.6 μ m is set on this interim stilt, middle layer, the dry film thickness that dry film thickness is 1.6 μ m is the photo-sensitive resin of 2.4 μ m, and pressing diaphragm (thickness is the polypropylene screen of 12 μ m).
Make the photosensitive resin transfer material that forms one by the photo-sensitive resin of interim stilt, thermoplastic resin, middle layer (oxygen barrier film) and black (K) thus, the sample name is decided to be photosensitive resin transfer material K1.
Thermoplastic resin coating liquid: prescription H1
Methyl alcohol 11.1 mass parts
MFGAC 6.36 mass parts
MEK 52.4 mass parts
Methyl methacrylate/2-EHA/methacrylic acid benzyl ester/methacrylic acid copolymer (copolymerization ratio of components (mol ratio)=55/11.7/4.5/28.8, molecular weight=90,000,70 ℃ of Tg ≈) 5.83 mass parts
Styrene/acrylic acid co-polymer (copolymerization ratio of components (mol ratio)=63/37, molecular weight=10,000,100 ℃ of Tg ≈) 13.6 mass parts
Compound behind bisphenol-A and the pentanediol monomethacrylates 2 equivalent dehydrating condensations (make by Xin Zhong village chemical industry (strain), trade name: 2, two [4-(methacryloxy polyethoxy) phenyl] propane of 2-) 9.1 mass parts
Above-mentioned surfactant 1 0.54 mass parts
Middle layer coating liquid: prescription P1
PVA205 (polyvinyl alcohol (PVA), (strain) Network ラ レ society makes, saponification rate=88%, the degree of polymerization 550) 32.2 mass parts
(ア イ エ ス ピ-ジ ヤ パ Application Co., Ltd. makes polyvinyl pyrrolidone, K-30)
14.9 mass parts
Distilled water 524 mass parts
Methyl alcohol 429 mass parts
Then, adopt the method identical to prepare photosensitive resin transfer material R103, G103 and B1 with said method, difference is, the photosensitive composition K1 that will be adopted when the above-mentioned photosensitive resin transfer material K1 of preparation changes to above-mentioned photosensitive composition R103, G103 and B1 respectively.
Below, use above-mentioned photosensitive resin transfer material K1, B1, R103, G103, adopt the method identical with the embodiment 11 of TOHKEMY 2006-276818 communique, prepare by laminating have black matrix, the color filter of R pixel, G pixel, B pixel.
Then, the R of the filter substrate that obtains by said method pixel, G pixel, and B pixel and black matrix on, further form ITO (Indium Tin Oxide) transparency electrode by sputtering method.Then, according to the method for the embodiment 1 of TOHKEMY 2006-64921 communique, the position that is equivalent to black matrix top on the formed ITO film by said method forms dottle pin.
In addition, prepare glass substrate, applying the pattern that is used for the PVA pattern respectively on the transparency electrode of filter substrate and on relative substrate, and the alignment films that is made of polyimide further is being set thereon as relative substrate.
Then, the position that is equivalent to housing on the black matrix around being arranged in the mode of surrounding the color filter pixel group, utilize and divide leakage device mode to apply the ultraviolet curable resin sealant, and instillation PVA pattern liquid crystal, with relative substrate sticking, the substrate of pasting with the UV irradiation is heat-treated then then, makes sealant cures.On the two sides of the liquid crystal cell that obtains by this way, paste the polaroid HLC2-2518 that (strain) サ Application リ Star society makes.
Then, use the DB1112H (the chip type LED of ス Application レ-(strain) manufacturing) of DG1112H (the chip type LED that レ-(strain) of ス Application made), blue (B) LED of conduct of FR1112H (the chip type LED that レ-(strain) of ス Application made), green (G) LED of conduct as redness (R) LED, the three-wavelength type of structure sidelight mode is backlight, with its rear side that is installed in the liquid crystal cell that is provided with above-mentioned polaroid, be prepared into liquid crystal display cells 1.
Fig. 3 is the figure of the three-wavelength type that illustrates in the above embodiments to be adopted luminescent spectrum backlight.Can find out clearly that from Fig. 3 the peak value of green bright-line spectrum is at the 535nm place, the peak value of red bright-line spectrum is at the 630nm place, and the peak value of blue bright-line spectrum is at the 460nm place.
(comparative example 1)
In the prepared liquid crystal display cells 1 of embodiment 1, replace with cold-cathode tube backlight that LED's is backlight, construct backlightly with this, and, be prepared into liquid crystal display cells backlight 2 with cold-cathode tube with its rear side that is installed in the liquid crystal cell that is provided with above-mentioned polaroid.
(comparative example 2)
In embodiment 1, replace photosensitive composition B1 to prepare color filter with photosensitive composition B2, adopt identical method to prepare liquid crystal display cells 3.
(comparative example 3)
In the prepared liquid crystal display cells 1 of embodiment 1, use respectively with photosensitive composition B2 replace photosensitive composition B1 and the color filter for preparing, construct with the backlight of the replacement LED backlight of cold-cathode tube backlight, and will this rear side that is installed in the liquid crystal cell that is provided with above-mentioned polaroid backlight, thereby make the liquid crystal display cells backlight 4 that possesses cold-cathode tube.
Liquid crystal display cells for by above method preparation carries out following evaluation.
1) color reproduction scope (NTSC ratio)
(オ リ Application パ ス optics society makes to adopt microspectrophotometer; OSP100 or 200) colourity of mensuration liquid crystal indicator is represented with respect to the ratio of the color reproduction scope of NTSC specification with each color reproduction scope that actual measurement obtains.
2) contrast
In the liquid crystal display cells that makes, when measuring display white respectively and the light transmission capacity when showing black, its ratio is spent as a comparison (referring to " nineteen ninety the 7th the color reversion glory learn コ Application Off ァ レ Application ス; 512 colour specifications 10.4 " サ イ ズ TFT-LCD is with カ ラ-Off イ Le , plant wood, Xiao Guan, good fortune forever, in the mountain " etc.).Use chroma-luminance meter (BM-5 that (strain) ト プ コ Application society makes) when measuring colourity.The position of chroma-luminance meter is set to: distance and liquid crystal display cells backlight back to the position of polaroid 600mm the chroma-luminance meter is set, adopt this chroma-luminance instrumentation fixation degree.The mensuration angle of chroma-luminance meter is set at 1 °.Set light quantity backlight, make under the state that sample is not set, the brightness when being provided with 2 polaroids in parallel Nicol is 1280cd/m 2
3) long-time display characteristic
With the preparation liquid crystal display cells with 1280cd/m 2Brightness continuously show 1000 hours, in the darkroom, at distance liquid crystal indicator picture 400mm place illuminometer UV-M10-S[(strain is set) オ-Network making manufacturing], to measure the angle and be set at 2 °, measure the illumination (illumination of the light when showing blueness) of blue light, relative value before and after the test of each embodiment, comparative example (illumination that the illumination/test after the test is preceding), and the data of above-mentioned color reproduction scope, contrast are shown in Table 5 in the lump.
Table 5
Figure A200810147533D00421
Can find out clearly that from table 5 use the liquid crystal display cells of the comparative example 1 of cold-cathode tube, its color reproduction scope is relatively poor.Do not contain the liquid crystal display cells of the comparative example 2 of the organic pigment nano particle of defined among the present invention, its contrast is relatively poor.
On the other hand, the liquid crystal display cells of embodiments of the invention 1, its color reproduction scope, contrast are all excellent.
In addition, can clearly find out from the result of comparative example 1,3, use cold-cathode tube as situation backlight under, even contain the organic pigment nano particle of defined among the present invention, long-time display characteristic is not had a significant impact yet; But, can find out clearly that from the result of embodiment 1, comparative example 2 under the situation of using LED, long-time display characteristic significantly improves.
The concrete reason that produces this effect does not still have final conclusion, yet, it is believed that its reason is, the organic pigment nano particle of defined and in the past particle are different for the photostability of the light of specific wavelength among the present invention, because the wavelength characteristic of light source changes, so the light intensity that the photostability of the organic pigment nano particle of defined among the present invention is produced dysgenic wavelength diminishes.
The result is, by using the backlight of LED, and uses the organic pigment nano particle of defined among the present invention simultaneously, can satisfy color reproduction, contrast, long-time these 3 kinds of performances of display characteristic simultaneously.

Claims (6)

1. liquid crystal display cells, it is characterized in that having color filter and the three-wavelength type is backlight, wherein, it is the following organic pigment nano particle of 50nm that described color filter contains at least a mean grain size, and the bright-line spectrum peak value of the green that described three-wavelength type is backlight is between 520nm～540nm.
2. the described liquid crystal display cells of claim 1 is characterized in that having color filter, and it is the following organic pigment nano particle of 30nm that this color filter contains at least a mean grain size.
3. claim 1 or 2 described liquid crystal display cells, it is characterized in that, described mean grain size is that the following organic pigment nano particle of 50nm is made by following method: after being dissolved in organic pigment in the good solvent, gained solution is injected in the solvent as the poor solvent of described organic pigment.
4. any described liquid crystal display cells in the claim 1～3 is characterized in that, described three-wavelength type is backlight to be made of red, green and blue light emitting diode.
5. any described liquid crystal display cells in the claim 1～4, wherein, described organic pigment nano particle is the C.I. pigment Violet 23.
6. any described liquid crystal display cells in the claim 1～5, it is characterized in that, described color filter is to adopt following method to form: use interim stilt to be provided with thermoplastic resin, the photosensitive resin transfer material of middle layer and coloring phototonus resin bed, described coloring phototonus resin bed and substrate are heated so that they are combined closely, thereby described coloring phototonus resin bed is transferred on the described substrate, then, described interim stilt is peeled off or described interim stilt and described thermoplastic resin are peeled off, and the described coloring phototonus resin bed that is transferred on the described substrate carried out pattern exposure, develop then, thereby on described substrate, form image.
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