CN102789020B - The manufacture method of colored filter, liquid crystal display cells and colored filter - Google Patents
The manufacture method of colored filter, liquid crystal display cells and colored filter Download PDFInfo
- Publication number
- CN102789020B CN102789020B CN201210154317.1A CN201210154317A CN102789020B CN 102789020 B CN102789020 B CN 102789020B CN 201210154317 A CN201210154317 A CN 201210154317A CN 102789020 B CN102789020 B CN 102789020B
- Authority
- CN
- China
- Prior art keywords
- compound
- colored
- film
- colored filter
- radiation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3008—Polarising elements comprising dielectric particles, e.g. birefringent crystals embedded in a matrix
-
- 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
-
- 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
- G02F1/133502—Antiglare, refractive index matching layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Liquid Crystal (AREA)
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
The present invention provides colored filter and the manufacture method thereof of the high reliability of a kind of hardening at subcritical temerature, and uses this colored filter to provide liquid crystal display cells.Colored pattern, protecting film and distance piece is used to manufacture colored filter (10); it is any number of that described colored pattern contains in diketopyrrolopyrroles pigment, zinc halide phthalocyanine pigment, triarylmethane class dyestuff and azo dyes, and described protecting film is formed by the radiation-sensitive resin composition containing alkali soluble resins and the compound of following formula (1) or following formula (2).This colored filter (10) is used to constitute liquid crystal display cells (1).
Description
Technical field
The present invention relates to the manufacture method of a kind of colored filter, liquid crystal display cells and colored filter.
Background technology
Liquid crystal display cells comprises the liquid crystal panel being such as clamped with liquid crystal in a pair substrate such as glass substrate and constitute.On the surface of the substrate of clamping liquid crystal, LCD alignment alignment film can be set.And, previously, between a pair substrate, being configured the spherical or bar-shaped distance piece formed by glass, aluminium oxide or resin by distribution etc., the thickness of liquid crystal remains the setting of 1 μm～about 10 μm.The liquid crystal display cells light to radiating from the light source such as backlight or outer light plays the function as fine optical gate (shutter).And, liquid crystal display cells be make light partially through or shading and display.Liquid crystal display cells has the excellent features such as slim, light weight.
Liquid crystal display cells is at the display element being used as the computer centered by character shows etc. or clock originally of exploitation.It is additionally, since and becomes to carry out the lattice display in big picture, in display element that therefore purposes is extended to notebook computer etc..
Thereafter, liquid crystal display cells overcomes the problems such as high-precision refinement, colorization and visual angle expansion, purposes is expanded to further in the display applications of PC (PC).In recently, it is achieved that the high-speed response of wider array of visual angle or liquid crystal or the raising etc. of display quality, thus being used as large-scale slim TV display element.
One of the technology of development realizing this kind of liquid crystal display cells can be described above realizing the colorization technology of colored display.
Liquid crystal display cells is generally not capable of with himself colour developing, thus being difficult to colored display.Therefore, develop the technology utilizing colored filter, become to realize colored display.
It addition, use the colorization technology of colored filter also to may be used in the colored display of organic EL (Electroluminescence, electroluminescent) element or Electronic Paper etc. of white light-emitting layer.Additionally, if utilizing colored filter, then become to carry out CCD (ChargeCoupledDevice, charge coupled cell) colour phhotograpy of the solid-state imager such as imageing sensor, CMOS (ComplementaryMetalOxideSemiconductor, CMOS complementary metal-oxide-semiconductor) imageing sensor.
Colored filter comprises the slight pigmentation pattern of the transparency carriers such as glass and red, green and blue etc..Colored pattern adopts the regular shapes such as clathrate to be arranged on transparency carrier.
The manufacture method of colored filter is such as known method as described below.On transparency carrier or be formed with on the transparency carrier of light shield layer of desired pattern, it is coated with the colored composition of suitable sensed illuminated line.The painted radiation-sensitive composition of pigment-dispersing type of the pigment that colored composition is usable in coloring agent comprising red, green, blue etc..Secondly, after making dried coating film, it is situated between, every mask, dry coating is irradiated lonizing radiation (hereinafter referred to as " exposure "), implement development treatment.Then, carry out the hardening of the high temperature more than 200 DEG C such as such as 230 DEG C, obtain fixing colored pattern (referring for example to patent documentation 1 or patent documentation 2) by those operations.
In recent years, the higher image quality of display element and the requirement of high brightness are uprised day by day, colored filter is also strongly required to can aid in this kind of performance and improves.The high-precision refinement of high-contrast or solid-state imager in order to realize display element, effectively uses dyestuff as coloring agent (with reference to patent documentation 3～patent documentation 5).In colored filter, dyestuff is used to be also affected by paying close attention to as the technology of coloring agent.In the previous colored composition comprising dyestuff, mainly adopt method for curing polyfunctional acrylic ester, alkoxy methyl melmac etc. and polymerization initiator combined.
But, there is following problem in the colored pattern that formed using the colored composition comprising dyestuff: with use the colored pattern of the colored composition comprising pigment Comparatively speaking, reliability, particularly poor heat resistance.Therefore, in order to be formed in the cure step of colored pattern, it is desirable to the heating under more low temperature.
And, in the manufacture of colored filter, after forming colored pattern, before film forming becomes the ITO (IndiumTinOxide: doped with the Indium sesquioxide. of stannum) of electrode, it is possible to form protecting film on colored pattern.This protecting film is in order to colored pattern is protected, and realizes the ITO of excellent characteristic on the other hand and is formed.Herein, in order to form protecting film, typically required cure step.Colored composition that the use that heating in cure step becomes to cause being in protecting film lower floor comprises dyestuff and the deterioration of colored pattern that formed.It is therefore desirable to the low temperature of the cure step in order to form protecting film.
It addition, in colored filter, nearest exploitation prevailing arranges the technology (referring for example to patent documentation 6) of column spacer.On colored filter, the upright column spacer arranged can use the such as photoresist that the interval between a pair substrate of clamping liquid crystal can remain setting etc. to be formed.The distance piece of column can realize the control of the thickness of liquid crystal clamped between substrate accurately.Therefore, the technology replacing the spherical or bar-shaped distance piece configured between aforesaid substrate in prior art is become.
When on colored filter, column spacer is set, this distance piece be formed at colored filter as on the ITO of transparency electrode.That is, substrate is formed after colored pattern, forms ito film thereon, utilize such as photoetching technique etc. to form column spacer on ITO.Now, in order to form distance piece, typically required cure step.Heating in the cure step of this distance piece causes the colored pattern deterioration being in the colored filter of its lower floor.Particularly when being formed colored pattern by the colored composition containing dyestuff, this deterioration becomes big problem.Therefore, for the cure step of column spacer, it is strongly required low temperature.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2-144502 publication
[patent documentation 2] Japanese Patent Laid-Open 3-53201 publication
[patent documentation 3] Japanese Patent Laid-Open 2005-99584 publication
[patent documentation 4] Japanese Patent Laid-Open 2007-219466 publication
[patent documentation 5] Japanese Patent Laid-Open 2007-316179 publication
[patent documentation 6] Japanese Patent Laid-Open 11-344700 publication
As it has been described above, in the problem using the previous colored composition comprising dyestuff and there is poor heat resistance in the colored filter that formed.
Therefore it is required that manufactured the colored filter comprising colored pattern, protecting film and column spacer by the cure step of low temperature.In this case, previous colored filter exists following phenomenon: sufficient performance cannot be realized in the reliability such as voltage retention in resistance to developability or when being applied in liquid crystal display cells, thus becoming problem.The reason of this kind of problem can be enumerated: the sclerous reaction of the colored composition of hardening at subcritical temerature or protecting film or distance piece is insufficient.The colored composition of dyestuff can be comprised, the colored filter that the reliability that can be formed is high by hardening at subcritical temerature it is therefore desirable to develop to use.
It addition, in the manufacture of colored filter previously, carried out colored pattern formation by the elevated temperature heating stage more than 200 DEG C, protecting film is formed, the formation of column spacer (being hereinafter, sometimes referred to simply as distance piece).The film forming of LCD alignment alignment film is also undertaken by the elevated temperature heating stage more than 200 DEG C.But, in recently, consider from energy-conservation viewpoint, pursue the low temperature of heating steps in this kind of manufacturing step gradually.That is, pursue gradually and realize energy-conservation by making to comprise the manufacturing step low temperature of cure step.
According to above situation; the colored filter that strong expectation is following: be there is the colored composition that can be formed colored pattern by hardening at subcritical temerature; the protecting film that can be formed by hardening at subcritical temerature and the distance piece that can be formed by hardening at subcritical temerature; and the excellence such as resistance to developability, thermostability, solvent resistance, voltage retention, it is possible to realize the higher image quality of liquid crystal display cells and the colored filter of high brightness.
Summary of the invention
The present invention forms in view of problem as above.That is; it is an object of the invention to provide colored filter and manufacture method thereof, described colored filter comprises: use colored pattern, the protecting film formed by hardening at subcritical temerature and the distance piece formed by hardening at subcritical temerature that can comprise the colored composition of dyestuff and formed by hardening at subcritical temerature.
And; other purposes of the present invention are in that to provide and use the liquid crystal display cells that constitutes of colored filter, and described colored filter comprises: use the colored composition that can comprise dyestuff and the colored pattern, the protecting film formed by hardening at subcritical temerature and the distance piece formed by hardening at subcritical temerature that are formed by hardening at subcritical temerature.
1st aspect of the present invention relates to a kind of colored filter, it is characterised in that comprise colored pattern, protecting film and distance piece,
Described colored pattern contains at least one coloring agent of the group selecting free diketopyrrolopyrroles pigment, zinc halide phthalocyanine pigment, triarylmethane class dyestuff and azo dyes to constitute；
Described protecting film is formed by the 1st radiation-sensitive resin composition containing, for example lower compound:
[A] have epoxy radicals compound,
[B] have ethylene unsaturated bond polymerizable compound,
[C] radioactivity-sensitive polymerization initiator and
At least one compound of the group that the compound represented by [D] the free following formula of choosing (1) and the compound represented by following formula (2) are constituted；
Described distance piece is formed by the 2nd radiation-sensitive resin composition containing, for example lower compound:
[E] alkali soluble resins,
[F] have ethylene unsaturated bond polymerizable compound,
[G] radioactivity-sensitive polymerization initiator and
At least one compound of the group that the compound represented by [H] the free following formula of choosing (1) and the compound represented by following formula (2) are constituted；
[changing 1]
[changing 2]
(in formula (1), R1～R6It is each independently hydrogen atom, electron-withdrawing group or amino；Wherein, R1～R6In at least 1 be electron-withdrawing group, and R1～R6In at least 1 be amino；And, all or part of of the hydrogen atom of above-mentioned amino can also be replaced by the alkyl that carbon number is 1～6；
In formula (2), R7～R16It is each independently hydrogen atom, electron-withdrawing group or amino；Wherein, R7～R16In at least 1 be amino；And, all or part of of the hydrogen atom of above-mentioned amino can also be replaced by the alkyl that carbon number is 1～6；A is singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number is the alkylene of 2～6；Wherein, all or part of of the hydrogen atom of above-mentioned methylene and alkylene can also be replaced by cyano group, halogen atom or fluoroalkyl).
In the 1st aspect of the present invention, it is preferable that colored pattern is formed by the colored composition containing, for example lower compound:
[I] alkali soluble resins,
[II] have ethylene unsaturated bond polymerizable compound,
[III] radioactivity-sensitive polymerization initiator and
[IV] described coloring agent.
In the 1st aspect of the present invention, it is preferable that colored composition contains at least one compound of the group that [V] choosing freely compound represented by above-mentioned formula (1), the compound represented by above-mentioned formula (2), tertiary amine compound, amine salt, salt, amidine salt, amide compound, mercaptan compound, block isocyanate compound and the compound containing imidazole ring are constituted further.
In the 1st aspect of the present invention, it is preferable that [I] alkali soluble resins contained in colored composition is the copolymer comprising following construction unit: the construction unit that construction unit that (I-1) is formed by least one of the group selecting free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute, (I-2) are formed by the unsaturated compound containing epoxy radicals.
In the 1st aspect of the present invention, it is preferable that it is polymer that [A] contained in the 1st radiation-sensitive resin composition has the compound of epoxy radicals.
In the 1st aspect of the present invention, it is preferable that [A] contained in the 1st radiation-sensitive resin composition has the compound of epoxy radicals and have carboxyl further.
In the 1st aspect of the present invention, it is preferable that [E] alkali soluble resins contained in the 2nd radiation-sensitive resin composition is the copolymer comprising following construction unit: the construction unit that construction unit that (E-1) is formed by least one of the group selecting free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute, (E-2) are formed by the unsaturated compound containing epoxy radicals.
In the 1st aspect of the present invention, it is preferable that colored pattern is the colored pattern formed under the hardening temperature below 200 DEG C.
In the 1st aspect of the present invention, it is preferable that protecting film is the protecting film formed under the hardening temperature below 200 DEG C.
In the 1st aspect of the present invention, it is preferable that distance piece is the distance piece formed under the hardening temperature below 200 DEG C.
In the 1st aspect of the present invention, it is preferable that colored pattern is the colored pattern formed under than the less hardening temperature of the hardening temperature of protecting film.
In the 1st aspect of the present invention, it is preferable that colored pattern is the colored pattern formed under than the less hardening temperature of the hardening temperature of distance piece.
In the 1st aspect of the present invention, it is preferable that protecting film is the protecting film formed under than the less hardening temperature of the hardening temperature of distance piece.
In the 1st aspect of the present invention, preferably it comprises alignment film, and described alignment film is the alignment film using the crystal aligning agent comprising the radioactivity-sensitive polymer with light regiospecific base and any number of gained in the crystal aligning agent comprising the polyimides not having light regiospecific base.
In the 1st aspect of the present invention, it is preferable that alignment film is the alignment film using the crystal aligning agent gained comprising the radioactivity-sensitive polymer with light regiospecific base.
2nd aspect of the present invention relates to a kind of liquid crystal display cells, it is characterised in that comprise the colored filter of the 1st aspect of the present invention.
3rd aspect of the present invention is the manufacture method of a kind of colored filter, it is characterised in that comprise the steps:
[1] forming the step of the film of colored composition on substrate, described colored composition contains at least one coloring agent of the group selecting free diketopyrrolopyrroles pigment, zinc halide phthalocyanine pigment, triarylmethane class dyestuff and azo dyes to constitute；
[2] on colored composition film, form the step of colored pattern；
[3] step below 200 DEG C, the film being formed with colored pattern hardened；
[4] on substrate formed the 1st radiation-sensitive resin composition film step, described 1st radiation-sensitive resin composition containing, for example under compound:
[A] have epoxy radicals compound,
[B] have ethylene unsaturated bond polymerizable compound,
[C] radioactivity-sensitive polymerization initiator and
At least one compound of the group that the compound represented by [D] the free following formula of choosing (1) and the compound represented by following formula (2) are constituted；
[5] at least some of step irradiating lonizing radiation to the 1st radiation-sensitive resin composition film；
[6] irradiated, in step [5], the step that the film of lonizing radiation develops；
[7] below 200 DEG C, make the step of the film hardening developed in step [6]；
[8] forming the step of the 2nd radiation-sensitive resin composition film on the substrate of the film of the hardening with step [7], described 2nd radiation-sensitive resin composition is containing, for example lower compound:
[E] alkali soluble resins,
[F] have ethylene unsaturated bond polymerizable compound,
[G] radioactivity-sensitive polymerization initiator and
At least one compound of the group that the compound represented by [H] the free following formula of choosing (1) and the compound represented by following formula (2) are constituted；
[9] at least some of step irradiating lonizing radiation to the 2nd radiation-sensitive resin composition film；
[10] irradiated, in step [9], the step that the film of lonizing radiation develops；And
[11] film developed in step [10] hardening is made to form the step of distance piece below 200 DEG C；
[changing 3]
[changing 4]
(in formula (1), R1～R6It is each independently hydrogen atom, electron-withdrawing group or amino；Wherein, R1～R6In at least 1 be electron-withdrawing group, and R1～R6In at least 1 be amino；And, all or part of of the hydrogen atom of above-mentioned amino can also be replaced by the alkyl that carbon number is 1～6；
In formula (2), R7～R16It is each independently hydrogen atom, electron-withdrawing group or amino；Wherein, R7～R16In at least 1 be amino；And, all or part of of the hydrogen atom of above-mentioned amino can also be replaced by the alkyl that carbon number is 1～6；A is singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number is the alkylene of 2～6；Wherein, all or part of of the hydrogen atom of above-mentioned methylene and alkylene can also be replaced by cyano group, halogen atom or fluoroalkyl).
In the 3rd aspect of the present invention, it is preferable that colored composition contains [I] alkali soluble resins further, [II] has the polymerizable compound of ethylene unsaturated bond, [III] radioactivity-sensitive polymerization initiator.
In the 3rd aspect of the present invention, it is preferable that the hardening temperature of step [3] is the hardening temperature lower temperature than step [7].
In the 3rd aspect of the present invention, it is preferable that the hardening temperature of step [3] is the hardening temperature lower temperature than step [11].
In the 3rd aspect of the present invention, it is preferable that the hardening temperature of step [7] is the hardening temperature lower temperature than step [11].
In the 3rd aspect of the present invention, it is preferable that comprise [12] step at 200 DEG C of alignment films formed below after step [11].
In the 3rd aspect of the present invention, it is preferable that step [12] be use comprise the radioactivity-sensitive polymer with light regiospecific base crystal aligning agent and comprise the polyimides not having light regiospecific base crystal aligning agent in any number of and form described alignment film.
[effect of invention]
A kind of colored filter and manufacture method thereof manufactured by hardening at subcritical temerature and have high reliability is provided according to the present invention.
And, provide a kind of colored filter comprising and can being manufactured and have high reliability by hardening at subcritical temerature according to the present invention, the liquid crystal display cells that display characteristic is excellent.
Accompanying drawing explanation
Fig. 1 is the mode sectional drawing of the colored filter of this embodiment.
Fig. 2 is the mode sectional drawing of the color liquid crystal display device of the colored filter comprising this embodiment.
The explanation of symbol:
1: liquid crystal display cells
2,5: substrate
3: pixel electrode
4:ITO electrode
6: colored pattern
7: black matrix"
8: protecting film
9: distance piece
10: colored filter
12: alignment film
13: liquid crystal
14: Polarizer
16: encapsulant
17: backlight light
Detailed description of the invention
Hereinafter the embodiment of the present invention is illustrated.
It addition, in the present invention, " lonizing radiation " that irradiate when exposure are the concepts including luminous ray, ultraviolet, far ultraviolet rays, X ray, charged particle beam etc..
<liquid crystal display cells>
The liquid crystal display cells of this embodiment is the color liquid crystal display device of the colored filter comprising this embodiment.
Hereinafter, the structure of the color liquid crystal display device of this embodiment is illustrated.
Color liquid crystal display device can be such as make to be configured with thin film transistor (TFT) (ThinFilmTransistor；TFT) driving substrate and constitute other substrates of colored filter of this embodiment be situated between every liquid crystal layer to structure.Or, color liquid crystal display device can also is that the colored pattern making to form described later embodiment on the driving substrate being configured with thin film transistor (TFT) (TFT) or protecting film or distance piece and the substrate that constitutes and be formed with ITO (IndiumTinOxide；Indium sesquioxide. doped with stannum) electrode substrate be situated between every liquid crystal layer to structure.The structure of the latter has the advantage that and numerical aperture can be made to significantly improve, and obtains the liquid crystal display cells of bright fine.
Fig. 1 is the mode sectional drawing of the colored filter of this embodiment.
Colored filter 10 shown in Fig. 1 is an example of the colored filter of this embodiment.There is following structure: on transparent substrate 5, be configured with redness (R), green (G) and the blue colored pattern 6 of (B), black matrix" 7, the protecting film 8 being located on colored pattern 6, the ITO electrode 4 being located on protecting film 8, the upright distance piece 9 arranged in ITO electrode 4.It addition, the color of colored pattern 6 is not limited to above-mentioned RGB3 color, it is also possible to select other colors or add yellow (Y) further and make the colored pattern of 4 colors.
As described later, in the colored filter 10 of this embodiment, colored pattern 6 is constituted containing suitable coloring agent.Specifically, after the colored composition containing preferred coloring agent being coated substrate being patterned so that it is hardening and formed.Protecting film 8 is similarly after being coated with radiation-sensitive resin composition and be patterned so that it is hardens and is formed；Distance piece 9 is similarly after being coated with radiation-sensitive resin composition and be patterned so that it is hardens and is formed.Additionally; in the following description; for convenience's sake, the radiation-sensitive resin composition in order to form protecting film 8 is called the 1st radiation-sensitive resin composition, the radiation-sensitive resin composition in order to form distance piece 9 is called the 2nd radiation-sensitive resin composition.And, this colored composition, the 1st radiation-sensitive resin composition and the 2nd radiation-sensitive resin composition can like that all be set to use the radiation-sensitive resin composition of the similar material of homology as described later.Those constituents have the feature that can be formed colored pattern respectively by the hardening at subcritical temerature of less than 200 DEG C with protecting film 8 with distance piece 9.
Therefore, in the colored filter 10 of this embodiment, become can be formed colored pattern 6 and protecting film 8 and distance piece 9 respectively by the hardening at subcritical temerature of less than 200 DEG C.The colored filter 10 of this embodiment can be manufactured by hardening at subcritical temerature.
And, in colored filter 10, it is subsequently formed protecting film 8 in forming colored pattern 6.Protecting film 8 can be formed by the hardening at subcritical temerature of less than 200 DEG C, therefore becomes without being exposed to after its formation under the state forming the high-temperature heating of protecting film by colored pattern 6.Similarly, in colored filter 10, it is subsequently formed distance piece 9 in formation colored pattern 6, formation protecting film 8.Distance piece 9 can be formed by the hardening at subcritical temerature of less than 200 DEG C, therefore becomes without being exposed to after its formation under the state forming the high-temperature heating of distance piece 9 by colored pattern 6.Therefore, in colored filter 10, even if although using color characteristics in the formation of colored pattern 6 excellent but there is the dyestuff of problem in thermostability as coloring agent, step deterioration also can be reduced.That is, optional dyestuff, as the coloring agent of colored composition, can be formed, by the colored composition using dyestuff, the colored pattern 6 that color characteristics is excellent.
It addition, as it has been described above, colored composition, the 1st radiation-sensitive resin composition and the 2nd radiation-sensitive resin composition can all be set to use the radiation-sensitive resin composition of the similar material of homology.And, it is respectively used to manufacture colored filter 10.Therefore, in time manufacturing colored filter 10, it may be considered that form protecting film 8 on colored pattern 6 and adjust hardening temperature when forming colored pattern 6.That is, on the substrate 5, utilize and form colored pattern 6 with hardening temperature optimum when independently forming colored pattern 6 Comparatively speaking less hardening temperature.Thereafter, the heating to colored pattern 6 can be carried out by the protecting film 8 formed on colored pattern 6 being carried out hardening heating.Similarly, in time manufacturing colored filter 10, it may be considered that form distance piece 9 after forming colored pattern 6 and adjust hardening temperature when forming colored pattern 6.That is, on the substrate 5, utilize with only formed colored pattern 6 time optimum hardening temperature Comparatively speaking less hardening temperature and form colored pattern 6.And, after forming ITO electrode 4, it is also possible to the hardening of the distance piece 9 by being uprightly arranged in ITO electrode 4 is heated and colored pattern 6 is heated.
Such as, in the optimum hardening temperature respectively less than 200 DEG C of colored pattern 6 with protecting film 8, specifically 180 DEG C when, it is possible to form colored pattern 6 in advance on the substrate 5 by the hardening temperatures of such as 150 DEG C.Secondly, this colored pattern 6 is formed the film of the 1st radiation-sensitive resin composition, hardens at optimum 180 DEG C, form protecting film 8 therefrom.And, become the colored pattern 6 to being in its lower floor and be heated, the colored pattern 6 of desired state can be obtained.It addition, on the substrate 5, it is pre-formed colored pattern 6 with the hardening temperatures of such as 150 DEG C, is formed distance piece 9 with the hardening temperature of optimum 180 DEG C by the 2nd radiation-sensitive resin composition thereafter.Its result, becomes the colored pattern 6 of the lower floor being in distance piece 9 is heated, can obtain the colored pattern 6 of desired state.In the above circumstances, the optional dyestuff coloring agent as colored composition, the colored pattern 6 that utilization is formed, it is possible to provide the colored filter 10 that color characteristics is excellent are become by the colored composition of use dyestuff.
And, in time manufacturing colored filter 10, it is contemplated that the hardening temperature when forming colored pattern 6 and be subsequently formed distance piece 9 with protecting film 8 and adjusting hardening temperature when forming colored pattern 6 and form protecting film 8.That is, on the substrate 5, utilize with only formed colored pattern 6 time optimum hardening temperature Comparatively speaking less hardening temperature and form colored pattern 6.Secondly, utilize with optimum hardening temperature Comparatively speaking less hardening temperature when only forming protecting film 8 and form protecting film 8.And, after forming ITO electrode 4, it is also possible to the hardening of the distance piece 9 by being uprightly arranged in ITO electrode 4 is heated and colored pattern 6 and protecting film 8 are also carried out heating.
Such as, when colored pattern 6 is with the optimum hardening temperature respectively less than 200 DEG C, specifically 180 DEG C of protecting film 8 and distance piece 9, it is possible to form colored pattern 6 in advance on the substrate 5 by the hardening temperatures of such as 150 DEG C.Secondly, on this colored pattern 6, form the film of the 1st radiation-sensitive resin composition, can use the hardening temperature of such as 150 DEG C and be pre-formed.Secondly, formed on protecting film 8 after ITO electrode 4, in ITO electrode 4, form the film of the 2nd radiation-sensitive resin composition.Secondly, this film is patterned, hardens with optimum 180 DEG C, form distance piece 9 therefrom.Its result, becomes colored pattern 6 and protecting film 8 to being in lower floor and is heated, can obtain colored pattern 6 and the protecting film 8 of desired state.In such cases, becoming the optional dyestuff coloring agent as colored composition, the colored pattern 6 that utilization is formed, it is possible to provide the colored filter 10 that color characteristics is excellent by the colored composition of use dyestuff.
It addition, in the colored filter 10 of this embodiment, after forming distance piece 9, LCD alignment alignment film (at Fig. 1 not shown) can be set as described later.Alignment film can use the crystal aligning agent comprising the radioactivity-sensitive polymer with light regiospecific base or the crystal aligning agent that comprises the polyimides not having light regiospecific base and obtain.In this case, become to form alignment film under the heating-up temperature below 200 DEG C.
Secondly, the liquid crystal display cells of this embodiment of the colored filter applying this embodiment is illustrated.
Fig. 2 is the mode sectional drawing of the color liquid crystal display device of the colored filter comprising this embodiment.
Liquid crystal display cells 1 shown in Fig. 2 is an example of the color liquid crystal display device of this embodiment, is the display element of TFT TN (TwistedNematic, twisted-nematic) the type liquid crystal mode driven.This color liquid crystal display device have above-mentioned driving substrate and constitute above-mentioned embodiment colored filter substrate be situated between every TN liquid crystal layer to structure.
As in figure 2 it is shown, in the side connected with liquid crystal 13 of transparent substrate 2, the transparent pixel electrode 3 comprising ITO is arranged with TFT (not shown) and constitutes driving substrate for clathrate.And, in the side connected with liquid crystal 13 of transparent substrate 5, it is configured with the above-mentioned colored pattern 6 etc. manufactured by hardening at subcritical temerature, constitutes colored filter 10.More specifically it is configured with colored filter 10; described colored filter 10 includes on the substrate 5: with pixel electrode 3 to position set by redness, green and blue colored pattern 6; black matrix" 7; protecting film 8 set on colored pattern 6; ITO electrode 4 set on protecting film 8; the distance piece 9 uprightly arranged in ITO electrode 4, alignment film 12.ITO electrode 4 constitutes public electrode in liquid crystal display cells 1.
It is provided with the alignment film 12 same with substrate 5 on a substrate 2.Process by the case of necessary each alignment film 12 being carried out the orientations such as such as friction treatment, it may be achieved the homogeneous orientation of liquid crystal 13 clamped between substrate 2, substrate 5.
In substrate 2 with substrate 5, it is each configured with Polarizer 14 in the opposition side of the side connected with liquid crystal 13.The interval of substrate 2 and substrate 5 is generally 2 μm～10 μm, and those elements interfix by being located at the encapsulant 16 of periphery.
In fig. 2, symbol 17 refers to the backlight light irradiated from back light unit (not shown) to liquid crystal 13.Back light unit such as can use the back light unit of fluorescent tubes such as being combined with cold cathode fluorescent tube (CCFL:ColdCathodeFluorescentLamp) and the structure of scatter plate.Moreover, it is also possible to use the back light unit being light source with White LED.nullWhite LED include, for example: uses the red LED with independent spectrum、Green LED、Blue led and obtain the White LED of white light，By red LED、Green LED、Blue led is combined and passes through colour mixture and obtain the White LED of white light，By blue led、Red LED、Green-emitting phosphor is combined and passes through colour mixture and obtain the White LED of white light，By blue led、Red light-emitting phosphor、Green-emitting phosphor body is combined and passes through colour mixture and obtain the White LED of white light，The White LED of white light is obtained by the colour mixture of blue led and YAG class fluorophor，By blue led、Orange luminescence fluorophor、Green-emitting phosphor body is combined and passes through colour mixture and obtain the White LED of white light，By ultraviolet LED、Red light-emitting phosphor、Green-emitting phosphor body、Blue-light-emitting fluorescent material is combined and passes through colour mixture and obtain the White LED etc. of white light.
In the color liquid crystal display device of this embodiment, except above-mentioned TN type, STN (SuperTwistedNematic can also be set to, super twisted nematic) type, IPS (In-PlanesSwitching, coplanar conversion) type, VA (VerticalAlignment, vertical orientation) liquid crystal mode such as type or OCB (OpticallyCompensatedBirefringence, optical compensation birefringence) type.In this case, LCD alignment alignment film selects optimum alignment film in each liquid crystal mode, for instance use the alignment film of vertical orientation type when VA type.
Secondly, the colored filter of this embodiment of the main composition key element of the liquid crystal display cells as this embodiment is described in more detail.
The colored filter of this embodiment is following colored filter: comprise on colored pattern, this colored pattern the distance piece uprightly arranged in set protecting film and the ITO electrode on protecting film as described above, and color characteristics is excellent and available hardening at subcritical temerature and manufacture.
Colored pattern can use colored composition to be formed on suitable substrate, and protecting film is to use the 1st radiation-sensitive resin composition to be formed on this colored pattern.In the ITO electrode that distance piece can use the 2nd radiation-sensitive resin composition and be formed on protecting film.That is, the colored filter of this embodiment can use colored composition, the 1st radiation-sensitive resin composition and the 2nd radiation-sensitive resin composition to manufacture.
In following, first the colored composition used in the colored pattern of the colored filter of this embodiment, particularly formation to colored pattern is illustrated.
<colored composition>
The colored composition used in the manufacture of the colored filter of this embodiment contains [I] alkali soluble resins, [II] polymerizable compound, [III] polymerization initiator and [IV] coloring agent.And, [V] compound can be contained further.And, as long as not undermining the effect of the present invention, then can also contain other any compositions.Hereinafter, each composition contained in colored composition is illustrated.
<[I] alkali soluble resins>
[I] if alkali soluble resins has carboxyl thus has the resin of alkali-developable, is then not particularly limited.Freely there is the construction unit of (methyl) acryloxy also, it is preferred that comprise choosing and there is the copolymer of at least one construction unit of the group that the construction unit of epoxy radicals is constituted.[I] alkali soluble resins has above-mentioned specific structure unit, therefore can form the indurative cured film of Surface hardened layer and deep with excellence.
[I] alkali soluble resins can by making following structure unit copolymerization synthesize, thus obtaining the copolymer comprising those construction units: the construction unit that construction unit that (I-1) is formed by least one (being also known as " (I-1) compound " below) of the group selecting free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute, (I-2) are formed by the unsaturated compound (being also known as " (I-2) compound " below) containing epoxy radicals.
[I] alkali soluble resins such as can by a solvent, make under the existence of polymerization initiator (I-1) compound of the construction unit that imparting contains carboxyl and (I-2) the compound copolymerization giving the construction unit containing epoxy radicals manufacture.Give the hydroxyl unsaturated compound (being also known as " (I-3) compound " below) of the construction unit containing hydroxyl moreover, it is also possible to add (I-3) further and make copolymer.Additionally, in the manufacture of [I] alkali soluble resins, it is also possible to together add (I-4) compound unsaturated compound of the construction unit beyond the construction unit of above-mentioned (I-1) compound, (I-2) compound and (I-3) compound (imparting be derived from) further with above-mentioned (I-1) compound, (I-2) compound and (I-3) compound and make copolymer.Hereinafter, each compound is described in detail.
[(I-1) compound]
(I-1) compound can enumerate unsaturated monocarboxylic, unsaturated dicarboxylic, the anhydride of unsaturated dicarboxylic, polybasic carboxylic acid list [(methyl) acryloxyalkyl] ester, at two ends, there are carboxyl and list (methyl) acrylate of polymer of hydroxyl, the unsaturated polycyclic compound with carboxyl and anhydride thereof etc..
Unsaturated monocarboxylic include, for example acrylic acid, methacrylic acid, butenoic acid etc.；
Unsaturated dicarboxylic include, for example maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc.；
The anhydride of unsaturated dicarboxylic include, for example the anhydride etc. of the compound illustrated as above-mentioned dicarboxylic acids；
List [(methyl) acryloxyalkyl] ester of polybasic carboxylic acid include, for example mono succinate [2-(methyl) acryloyl-oxyethyl] ester, phthalic acid list [2-(methyl) acryloyl-oxyethyl] ester etc.；
List (methyl) acrylate of the polymer having carboxyl and hydroxyl at two ends include, for example ω-carboxy-polycaprolactone list (methyl) acrylate etc.；
Unsaturated polycyclic compound and the anhydride thereof with carboxyl include, for example: 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" anhydride etc..
In those (I-1) compounds, preferred monocarboxylic acid, dicarboxylic anhydride, acrylic acid, methacrylic acid, maleic anhydride, from copolyreaction, for alkaline aqueous solution dissolubility and obtain easiness consider, more preferably acrylic acid, methacrylic acid, maleic anhydride.Those (I-1) compounds can be used alone and also can two or more mixing be used.
Usage ratio as (I-1) compound, total based on (I-1) compound and (I-2) compound (optionally for arbitrary (I-3) compound and (I-4) compound), it is preferably 5wt%～30wt%, more preferably 10wt%～25wt%.By making the usage ratio of (I-1) compound be 5wt%～30wt%, the dissolubility optimization for alkaline aqueous solution of [I] alkali soluble resins can be made, thus obtaining the colored composition that lonizing radiation sexuality luminosity is excellent.
[(I-2) compound]
(I-2) compound is to have the free-radical polymerised unsaturated compound containing epoxy radicals.Epoxy radicals can enumerate Oxyranyle (1,2-epoxy construction), expoxy propane base (1,3-epoxy construction).
The unsaturated compound with Oxyranyle include, for example glycidyl acrylate, glycidyl methacrylate, methacrylic acid-2-methylglycidyl esters, α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-n-butyl acryloyloxy ethyl acid glycidyl ester, acrylic acid-3, 4-epoxybutyl ester, methacrylic acid-3, 4-epoxybutyl ester, acrylic acid-6, 7-epoxy heptyl ester, methacrylic acid-6, 7-epoxy heptyl ester, α-ethylacrylate-6, 7-epoxy heptyl ester, adjacent vinylbenzyl glycidyl ether, between vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, methacrylic acid-3, 4-epoxycyclohexanecarboxylate etc..Consider from the viewpoint making the solvent resistance etc. of copolyreaction and colored pattern etc. improve, preferred glycidyl methacrylate, methacrylic acid-2-methylglycidyl esters, methacrylic acid-6 in those compounds, 7-epoxy heptyl ester, adjacent vinylbenzyl glycidyl ether, a vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, methacrylic acid-3,4-epoxycyclohexyl ester.
The unsaturated compound with expoxy propane base include, for example:
3-(acryloyloxymethyl) expoxy propane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-3-ethyl expoxy propane, 3-(acryloyloxymethyl)-2-benzyl ring Ethylene Oxide, 3-(2-acryloyl-oxyethyl) expoxy propane, 3-(2-acryloyl-oxyethyl)-2-ethyl expoxy propane, 3-(2-acryloyl-oxyethyl)-3-ethyl expoxy propane, the acrylate such as 3-(2-acryloyl-oxyethyl)-2-benzyl ring Ethylene Oxide；
3-(methacryloxymethyl) expoxy propane, 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryloxymethyl)-3-ethyl expoxy propane, 3-(methacryloxymethyl)-2-benzyl ring Ethylene Oxide, 3-(2-methacryloxyethyl) expoxy propane, 3-(2-methacryloxyethyl)-2-ethyl expoxy propane, 3-(2-methacryloxyethyl)-3-ethyl expoxy propane, 3-(2-methacryloxyethyl)-2-benzyl ring Ethylene Oxide, 3-(2-methacryloxyethyl)-2, the methacrylates etc. such as 2-difluoro expoxy propane.
Preferred (methyl) glycidyl acrylate in those (I-2) compounds.Those (I-2) compounds can be used alone and also can two or more mixing be used.
Usage ratio as (I-2) compound, total based on (I-1) compound and (I-2) compound (optionally for arbitrary (I-3) compound and (I-4) compound), it is preferably 5wt%～60wt%, more preferably 10wt%～50wt%.By making the usage ratio of (I-2) compound be 5wt%～60wt%, the cured film of the hardening etc. with excellence can be formed.
[(I-3) compound]
(I-3) compound first can enumerate (methyl) acrylate with hydroxyl, (methyl) acrylate with phenolic hydroxyl group, hydroxy styrenes.
The acrylate with hydroxyl can be enumerated: 2-Hydroxy ethyl acrylate, acrylic acid-3-hydroxy propyl ester, acrylic acid-4-hydroxybutyl, acrylic acid-5-hydroxyl pentyl ester, the acrylic acid-6-own ester of hydroxyl etc..
And, the methacrylate with hydroxyl can be enumerated: methacrylic acid-2-hydroxy methacrylate, methacrylic acid-3-hydroxy propyl ester, methacrylic acid-4-hydroxybutyl, methacrylic acid-5-hydroxyl pentyl ester, the methacrylic acid-6-own ester of hydroxyl etc..
The acrylate with phenolic hydroxyl group can be enumerated: acrylic acid-2-hydroxylphenyl ester, acrylic acid-4-hydroxylphenyl ester etc..The methacrylate with phenolic hydroxyl group can enumerate methacrylic acid-2-hydroxylphenyl ester, methacrylic acid-4-hydroxylphenyl ester etc..
Hydroxy styrenes is preferably o-hydroxystyrene, 4-Vinyl phenol, Alpha-Methyl-4-Vinyl phenol.Those (I-3) compounds can be used alone and also can two or more mixing be used.
Usage ratio as (I-3) compound, total based on (I-1) compound, (I-2) compound and (I-3) compound (optionally for arbitrary (I-4) compound), it is preferably 1wt%～30wt%, more preferably 5wt%～25wt%.
[(I-4) compound]
(I-4) compound is if the unsaturated compound beyond above-mentioned (I-1) compound, (I-2) compound and (I-3) compound, then there is no particular restriction.(I-4) compound include, for example methacrylic acid chain-like alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain-like alkyl ester, acrylic acid cyclic alkyl ester, aryl methacrylate, benzyl acrylate, unsaturated dicarboxylic diester, dicyclo unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, there are unsaturated compound and other unsaturated compounds etc. of oxolane skeleton, furan skeleton, Pentamethylene oxide. skeleton, pyrans skeleton etc..
Methacrylic acid chain-like alkyl ester include, for example methyl methacrylate, ethyl methacrylate, n-BMA, methacrylic acid second butyl ester, Tert-butyl Methacrylate, methacrylic acid-2-Octyl Nitrite, isodecyl methacrylate, the positive Lauryl Ester of methacrylic acid, Tridecyl methacrylate base ester, the positive stearyl of methacrylic acid etc..
Methacrylic acid cyclic alkyl ester include, for example cyclohexyl methacrylate, methacrylic acid-2-methyl cyclohexyl, methacrylic acid three ring [5.2.1.02,6] decane-8-base ester, methacrylic acid three ring [5.2.1.02,6] decane-8-base oxygen base ethyl ester, isobornyl methacrylate etc..
Acrylic acid chain-like alkyl ester include, for example acrylic acid methyl ester., ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, acrylic acid-2-ethyl caproite, isodecyl acrylate, the positive Lauryl Ester of acrylic acid, tridecyl acrylate, n-stearyl acrylate etc..
Acrylic acid cyclic alkyl ester include, for example cyclohexyl acrylate, acrylic acid-2-methyl cyclohexyl, acrylic acid three ring [5.2.1.02,6] decane-8-base ester, acrylic acid three ring [5.2.1.02,6] decane-8-base oxygen base ethyl ester, isobornyl acrylate etc..
Aryl methacrylate include, for example phenyl methacrylate, benzyl methacrylate etc..
Benzyl acrylate include, for example phenyl acrylate, benzyl acrylate etc..
Unsaturated dicarboxylic diester include, for example ethyl maleate., DEF, diethyl itaconate etc..
Dicyclo unsaturated compound include, for example dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-methoxyl group dicyclo [2.2.1] hept-2-ene", 5-ethyoxyl dicyclo [2.2.1] hept-2-ene" etc..
Maleimide compound include, for example N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-(4-hydroxy phenyl) maleimide, N-(4-hydroxybenzyl) maleimide, N-succinimido-3-maleimidobenzoyl ester, N-succinimido-4-malimidobutanoate, N-succinimido-6-maleimidohexanoic acid ester, N-succinimido-3-maleimidopropionic acid ester, N-(9-acridinyl) maleimide etc..
Unsaturated aromatic compound include, for example styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene etc..
Conjugated diene include, for example 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc..
Unsaturated compound containing oxolane skeleton include, for example (methyl) acrylic acid tetrahydrofuran methyl ester, 2-methacryloxy-propanoic acid tetrahydrofuran methyl ester, 3-(methyl) acryloxy oxolane-2-ketone etc..
Unsaturated compound containing furan skeleton include, for example 2-methyl-5-(3-furyl)-1-penten-3-one, (methyl) acrylic acid furfuryl group ester, 1-furan-2-butyl-3-alkene-2-ketone, 1-furan-2-butyl-3-methoxyl group-3-alkene-2-ketone, 6-(2-furyl)-2-methyl isophthalic acid-hexene-3-one, 6-furan-2-base-oneself-1-alkene-3-ketone, acrylic acid-2-furan-2-base-1-methyl-ethyl ester, 6-(2-furyl)-6-methyl isophthalic acid-teracrylic acid-one etc..
Unsaturated compound containing Pentamethylene oxide. skeleton include, for example methacrylic acid (Pentamethylene oxide .-2-base) methyl ester, 2,6-dimethyl-8-(Pentamethylene oxide .-2-base oxygen base)-Xin-1-alkene-3-ketone, 2-methacrylic acid Pentamethylene oxide .-2-base ester, 1-(Pentamethylene oxide .-2-oxygen base)-butyl-3-alkene-2-ketone etc..
Unsaturated compound containing pyrans skeleton include, for example 4-(Isosorbide-5-Nitrae-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyrans, 4-(1,5-dioxa-6-oxo-7-octenyl)-6-methyl-2-pyrans etc..
Other unsaturated compounds include, for example acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate etc..
In those (I-4) compounds, it is preferable that methacrylic acid chain-like alkyl ester, methacrylic acid cyclic alkyl ester, aryl methacrylate, maleimide compound, oxolane skeleton, furan skeleton, Pentamethylene oxide. skeleton, pyrans skeleton, unsaturated aromatic compound, acrylic acid cyclic alkyl ester.Deliquescent aspect from copolyreaction and for alkaline aqueous solution considers, in those compounds more preferably styrene, methyl methacrylate, Tert-butyl Methacrylate, the positive Lauryl Ester of methacrylic acid, benzyl methacrylate, methacrylic acid three ring [5.2.1.02,6] decane-8-base ester, to methoxy styrene, acrylic acid-2-methyl cyclohexyl, N-phenylmaleimide, N-N-cyclohexylmaleimide, (methyl) acrylic acid tetrahydrofuran methyl ester, Polyethylene Glycol (n=2～10) single (methyl) acrylate, 3-(methyl) acryloxy oxolane-2-ketone.Those (I-4) compounds can be used alone and also can two or more mixing be used.
Usage ratio as (I-4) compound, total based on (I-1) compound, (I-2) compound and (I-4) compound (and arbitrary (I-3) compound), it is preferred to 10wt%～80wt%.
<synthetic method 1 of [I] alkali soluble resins>
[I] alkali soluble resins such as can pass through in a solvent, under the existence of polymerization initiator, above-mentioned (I-1) compound and (arbitrary (I-3) compound and (I-4) compound) copolymerization of (I-2) compound is made to manufacture.By this synthetic method, the copolymer including at least the construction unit containing epoxy radicals can be synthesized.
Include, for example alcohol, glycol ethers, ethylene glycol alkyl ether acetas, diethylene glycol monoalky lether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, propylene-glycol monoalky lether propionic ester, ketone, ester etc. in order to manufacture the solvent used in the polyreaction of [I] alkali soluble resins.
The compound being known as radical polymerization initiator generally can be used in order to manufacture the polymerization initiator used in the polyreaction of [I] alkali soluble resins.Radical polymerization initiator include, for example 2,2 '-azobis isobutyronitrile (AIBN), 2,2 '-azo is double; two-(2,4-methyl pentane nitrile), 2, the azo-compounds such as 2 '-azo pair-(4-methoxyl group-2,4-methyl pentane nitrile).
In order to manufacture in the polyreaction of [I] alkali soluble resins, in order to adjust molecular weight, molecular weight regulator can be used.Molecular weight regulator include, for example the halogenated hydrocarbon such as chloroform, carbon tetrabromide；The thio-alcohols such as positive hexyl mercaptan, n-octyl mercaptan, n-dodecane mercaptan, tertiary dodecyl mercaptans, TGA；The xanthic acid esters such as dimethyl sulfide xanthate, dithiodiisopropyl xanthate；Terpinolene, α-methylstyrenedimer etc..
The weight average molecular weight (Mw) of [I] alkali soluble resins is preferably 1,000～30,000, more preferably 5,000～20,000.By making the Mw of [I] alkali soluble resins be above-mentioned scope, the light sensitivitys of colored composition and developability can be made to improve.It addition, the Mw of polymer in this specification and number average molecular weight (Mn) can measure by utilizing the gel permeation chromatography (GPC) of following condition.
Device: GPC-101 (Showa electrician manufacture)
Tubing string: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined
Mobile phase: oxolane
Tubing string temperature: 40 DEG C
Flow velocity: 1.0mL/min
Sample solution concentration: 1.0wt%
Sample injection rate: 100 μ L
Detector: differential refractometer
Standard substance: monodisperse polystyrene
<synthetic method 2 of [I] alkali soluble resins>
And, copolymer (being also known as " specific copolymer " below) and above-mentioned (I-2) compound that [I] alkali soluble resins such as can allow to use more than a kind of above-mentioned (I-1) compound and synthesize react and synthesize.Utilize this synthetic method, the copolymer including at least the construction unit with (methyl) acryloxy can be synthesized.
Shown in the construction unit such as following formula (3) with (methyl) acryloxy contained by [I] alkali soluble resins.This construction unit is derived from the epoxy reaction of the carboxyl in the specific copolymer of (I-1) compound and (I-2) compound, forms ester bond and obtains.
[changing 5]
In above-mentioned formula (3), R20And R21It is each independently hydrogen atom or methyl.C is the integer of 1～6.R22It it is the divalent base represented by following formula (4-1) or formula (4-2).
[changing 6]
In above-mentioned formula (4-1), R23For hydrogen atom or methyl.In above-mentioned formula (4-1) and formula (4-2), * represents and the position of oxygen atom bond.
About the construction unit represented by above-mentioned formula (3), such as make as the compounds such as the glycidyl methacrylate of (I-2) compound, methacrylic acid-2-methylglycidyl esters with when there is the situation of copolymer reaction of carboxyl, the R in formula (3)22Become formula (4-1).On the other hand, make methacrylic acid-3 as (I-2) compound, the compound such as 4-epoxycyclohexanecarboxylate with when there is the situation of copolymer reaction of carboxyl, the R in formula (3)22Become formula (4-2).
When synthesizing specific copolymer, the compound beyond (I-1) compound also can be used, for instance above-mentioned (I-3) compound, (I-4) compound etc. are as copolymer composition.Considering from the aspect of copolyreaction, those compounds are preferably methyl methacrylate, n-BMA, benzyl methacrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid three ring [5.2.1.02,6] decane-8-base ester, styrene, to methoxy styrene, methacrylic acid oxolane-2-base ester, 1,3-butadiene.
The copolymerization process of specific copolymer include, for example and uses radical polymerization initiator in a solvent, makes the method that (I-1) compound and (I-3) compound etc. optionally carry out being polymerized.Radical polymerization initiator can enumerate person identical with radical polymerization initiator illustrated in the project of above-mentioned [I] alkali soluble resins.Make consumption as radical polymerization initiator, for polymerizable unsaturated compound 100wt%, be generally 0.1wt%～50wt%, it is preferred to 0.1wt%～20wt%.Specific copolymer can the form of polymeric reaction solution directly be supplied in the manufacture of [I] alkali soluble resins, it is also possible to is being supplied in the manufacture of [I] alkali soluble resins after temporarily being separated in solution by copolymer.
The Mw of specific copolymer is preferably 2,000～100, and 000, more preferably 5,000～50,000.By making Mw be 2, more than 000, can obtain the sufficient development latitude of colored composition, and the reduction of the residual film ratio (ratio of pattern-like thin film suitably remaining) of the film formed can be prevented, keep shape or the thermostability etc. of the pattern of gained further well.On the other hand, by making Mw be less than 100,000, the light sensitivitys of height can be kept, it is thus achieved that good pattern form.And, the molecular weight distribution (Mw/Mn) of specific copolymer is preferably less than 5.0, more preferably less than 3.0.By making Mw/Mn be less than 5.0, the shape of the spacer pattern of gained can be kept well.And, the colored composition of the specific copolymer comprising the Mw/Mn with above-mentioned particular range has the developability of height, in development step, can not produce development residual ground and be readily formed predetermined pattern shape.
The containing ratio of the construction unit being derived from (I-1) compound of [I] alkali soluble resins is preferably 5wt%～60wt%, more preferably 7wt%～50wt%, it is particularly preferred to for 8wt%～40wt%.
The containing ratio of the construction unit being derived from the compounds such as (I-3) compound beyond (I-1) compound, (I-4) compound of [I] alkali soluble resins is preferably 10wt%～90wt%, more preferably 20wt%～80wt%.
In the specific copolymer reaction with (I-2) compound, under existence if necessary in suitable catalyst, preferably in, in the copolymer solution comprising polymerization inhibitor, putting into the unsaturated compound with epoxy radicals, carry out the stirring of the scheduled time under heating.Above-mentioned catalyst include, for example tetrabutyl ammonium bromide etc..Above-mentioned polymerization inhibitor include, for example p methoxy phenol etc..Reaction temperature is preferably 70 DEG C～100 DEG C.Response time is preferably 8 hours～12 hours.
As the usage ratio of (I-2) compound, for the carboxyl being derived from (I-2) compound in copolymer, it is preferred to 5wt%～99wt%, more preferably 10wt%～97wt%.By making the usage ratio of (I-2) compound be above-mentioned scope, the hardening etc. of the reactivity with copolymer, cured film can be made to improve further.(I-2) compound can be used alone or two or more mixing be used.
<[II] polymerizable compound>
[II] polymerizable compound contained in the colored composition used in the manufacture of the colored filter of this embodiment is illustrated.
[II] polymerizable compound is the polymerizable compound with ethylene unsaturated bond.
nullThe compound that can use as [II] polymerizable compound include, for example: ω-carboxy-polycaprolactone list (methyl) acrylate、Ethylene glycol (methyl) acrylate、1，6-hexanediol two (methyl) acrylate、1，9-nonanediol two (methyl) acrylate、TEG two (methyl) acrylate、Polyethylene Glycol two (methyl) acrylate、Polypropylene glycol two (methyl) acrylate、Double; two phenyl phenol fluorenes two (methyl) acrylate、Dihydroxymethyl tristane two (methyl) acrylate、Methacrylic acid-2-hydroxyl-3-(methyl) acryloxypropyl ester、(methyl) acrylic acid-2-(2 '-vinyloxyethoxy) ethyl ester、Trimethylolpropane tris (methyl) acrylate、Tetramethylolmethane three (methyl) acrylate、Tetramethylolmethane four (methyl) acrylate、Dipentaerythritol five (methyl) acrylate、Dipentaerythritol six (methyl) acrylate、Tricresyl phosphate (2-(methyl) acryloyl-oxyethyl) ester、Ethylene-oxide-modified dipentaerythritol acrylate、Succinate modified pentaerythritol triacrylate etc.，Can also enumerate in addition to there is straight chain alkylen and alicyclic structure and there is the compound of more than 2 NCOs and react and the polyurethane of gained (methyl) acrylate compounds etc. with there is more than 1 hydroxyl in molecule and there is the compound of 3～5 (methyl) acryloxies.
The commercially available product of spendable [II] polymerizable compound include, for example:
nullARONIX (registered trade mark) M-400、ARONIXM-402、ARONIXM-405、ARONIXM-450、ARONIXM-1310、ARONIXM-1600、ARONIXM-1960、ARONIXM-7100、ARONIXM-8030、ARONIXM-8060、ARONIXM-8100、ARONIXM-8530、ARONIXM-8560、ARONIXM-9050、ARONIX (registered trade mark) TO-756、ARONIXTO-1450、ARONIXTO-1382 (is manufactured by East Asia Synesis Company) above、KAYARAD (registered trade mark) DPHA、KAYARADDPCA-20、KAYARADDPCA-30、KAYARADDPCA-60、KAYARADDPCA-120、KAYARADMAX-3510 (is manufactured by chemical medicine company of Japan) above、Viscoat295、Viscoat300、Viscoat360、ViscoatGPT、Viscoat3PA、Viscoat400 (is manufactured by Osaka Organic Chemical Industry company) above、Newfrontier (registered trade mark) R-1150 (the first industrial pharmaceutical company) as urethane acrylate compounds、KAYARAD (registered trade mark) DPHA、KAYARAD (registered trade mark) DPHA-40H、UX-5000 (chemical medicine company of Japan)、UN-9000H (Gen Shang industrial group)、ARONIX (registered trade mark) M-5300、ARONIXM-5600、ARONIXM-5700、ARONIXM-210、ARONIXM-220、ARONIXM-240、ARONIXM-270、ARONIXM-6200、ARONIXM-305、ARONIXM-309、ARONIXM-310、ARONIXM-315 (is manufactured by East Asia Synesis Company) above、KAYARAD (registered trade mark) HDDA、KAYARAD (registered trade mark) HX-220、KAYARADHX-620、KAYARADR-526、KAYARADR-167、KAYARADR-604、KAYARADR-684、KAYARADR-551、KAYARADR-712、UX-2201、UX-2301、UX-3204、UX-3301、UX-4101、UX-6101、UX-7101、UX-8101、UX-0937、MU-2100、MU-4001 (is manufactured by chemical medicine company of Japan) above、ArtresinUN-9000PEP、ArtresinUN-9200A、ArtresinUN-7600、ArtresinUN-333、ArtresinUN-1003、ArtresinUN-1255、ArtresinUN-6060PTM、ArtresinUN-6060P、ArtresinSH-500B (is manufactured by Gen Shang industrial group) above、Viscoat260、Viscoat312、Viscoat335HP (is manufactured by Osaka Organic Chemical Industry company) above.
[II] polymerizable compound can be used alone or two or more mixing be used.As the usage ratio of [II] polymerizable compound in colored composition, for [I] alkali soluble resins 100 weight portion, it is preferably 10 weight portion～700 weight portions, more preferably 20 weight portion～600 weight portions.By making the usage ratio of [II] polymerizable compound be above-mentioned scope, even if then colored composition also can form the colored pattern etc. with sufficient thermostability, solvent resistance, voltage retention under low light exposure.
<[III] polymerization initiator>
[III] polymerization initiator contained in the colored composition used in the manufacture of the colored filter of this embodiment is illustrated.
[III] polymerization initiator is radioactivity-sensitive polymerization initiator, is the composition sensing lonizing radiation and generating the spike of the polymerization that can cause [II] polymerizable compound.This kind [III] polymerization initiator can enumerate O-acyl group oxime compound, acetophenone compound, united imidazole etc..Those compounds can be used alone and also can two or more mixing be used.
nullO-acyl group oxime compound include, for example 1，2-octadione-1-[4-(thiophenyl)-2-(O-benzoyl oxime)]、Ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime)、1-[9-ethyl-6-benzoyl-9H-carbazole-3-base]-octane-1-ketoxime-O-acetas、1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-ethane-1-ketoxime-O-benzoate、1-[9-normal-butyl-6-(2-ethylamino benzonitrile acyl group)-9H-carbazole-3-base]-ethane-1-ketoxime-O-benzoate、Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime)、Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime)、Ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base benzoyl)-9H.-carbazole-3-base]-1-(O-acetyl oxime)、Ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2，2-dimethyl-1，3-dioxolane base) anisoyl }-9H-carbazole-3-base]-1-(O-acetyl oxime) etc..
Those compounds are preferably 1, 2-octadione-1-[4-(thiophenyl)-2-(O-benzoyl oxime)], ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base anisoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime) or ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxolane base) anisoyl }-9H-carbazole-3-base]-1-(O-acetyl oxime).
Acetophenone compound include, for example α-aminoketone compound, alpha-hydroxyacetone compounds.
α-aminoketone compound include, for example 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone, 2-methyl isophthalic acid-(4-methylthiophene base)-2-morpholino propane-1-ketone etc..
Alpha-hydroxyacetone compounds include, for example 1-phenyl-2-hydroxy-2-methyl propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexylphenylketone etc..
Preferred α-aminoketone compound in those compounds, more preferably 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone, 2-methyl isophthalic acid-(4-methylthiophene base)-2-morpholino propane-1-ketone.
United imidazole such as preferably 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline or 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, wherein more preferably 2,2 '-bis-(2,4-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
As the usage ratio of [III] polymerization initiator, for [I] alkali soluble resins 100 weight portion, it is preferred to 1 weight portion～40 weight portion, more preferably 5 weight portion～30 weight portions.By making the usage ratio of [III] polymerization initiator be 1 weight portion～40 weight portion, even if this colored composition also can form the colored pattern with high solvent resistance etc. and colored filter in low light exposure when.
<[IV] coloring agent>
As it has been described above, colored pattern and colored filter to be strongly required high excitation, brightness, contrast etc..Accordingly, as [IV] coloring agent contained in the colored composition used in the manufacture of the colored filter of this embodiment, become the coloring agent that must select to be adapted for carrying out this kind of characteristic.[IV] coloring agent such as can use any number of of pigment, dyestuff and natural pigment, if but consider the high excitation required by colored pattern and colored filter or brightness etc., then preferably select pigment and dyestuff.And particularly preferably select dyestuff.
About the dyestuff that can use as [IV] coloring agent, for instance oil-soluble dyes, acid stain or derivatives thereof, direct dyes, mordant dyes etc. can be enumerated.As dyestuff, as long as dissolving in organic solvent, then can use known dyestuff.
C.I. oil-soluble dyes include, for example:
C.I. solvent yellow 4 (record of " C.I. solvent yellow " omitted below and only record numbering.Other dyestuffs are recorded similarly), 14,15,23,24,38,62,63,68,82,88,94,98,99,162,179；
C.I. solvent red 45,49,125,130；
C.I. solvent orange 2,7,11,15,26,56；
C.I. solvent blue 35,37,59,67；
C.I. solvent green 1,3,4,5,7,28,29,32,33,34,35 etc..
C.I. acid stain include, for example:
nullC.I. Indian yellow 1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251；
Valifastyellow1101、1109、1151、3108、3120、3130、3150、3170、4120；
nullC.I. azogeramine、4、8、14、17、18、26、27、29、31、34、35、37、42、44、50、51、52、57、66、73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、182、183、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、274、277、280、281、195、308、312、315、316、339、341、345、346、349、382、383、394、401、412、417、418、422、426；
C.I. acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169,173；
C.I. Blue VRS, 7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103,108,112,113,120,129,138,147,150,158,171,182,192,210,242,249,243,256,259,267,278,280,285,290,296,315,324,335,340；
C.I. acid violet 6B, 7,9,17,19,49；
C.I. acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109；
C.I. acid black 24 dyestuff such as grade.
C.I. direct dyes include, for example:
C.I. direct Huang 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129,136,138,141；
C.I. directly red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250；
C.I. direct orange 34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107；
nullC.I. sun blue 57、77、80、81、84、85、86、90、93、94、95、97、98、99、100、101、106、107、108、109、113、114、115、117、119、137、149、150、153、155、156、158、159、160、161、162、163、164、166、167、170、171、172、173、188、189、190、192、193、194、196、198、199、200、207、209、210、212、213、214、222、228、229、237、238、242、243、244、245、247、248、250、251、252、256、257、259、260、268、274、275、293；
C.I. direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104；
C.I. direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82 etc..
C.I. mordant dyes include, for example:
C.I. medium Huang 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65；
C.I. medium red 1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37,38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94,95；
C.I. medium orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47,48；
C.I. medium indigo plant 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39,40,41,43,44,48,49,53,61,74,77,83,84；
C.I. medium purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53,58；
C.I. medium green 1,3,4,5,10,15,19,26,29,33,34,35,41,43,53 etc..
About the pigment that can use as [IV] coloring agent, can use organic pigment, inorganic pigment any number of.Organic pigment include, for example at Colour Index (C.I.；Dyeing association of man (TheSocietyofDyersandColourists) distribution) in be categorized as the compound of pigment.Specifically can enumerate the pigment with Colour Index (C.I.) name as described below.
Can enumerate: C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 17, C.I. pigment yellow 20, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 55, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 166, C.I. pigment yellow 168, C.I. pigment yellow 180, C.I. pigment yellow 185, C.I. pigment yellow 211；
C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 61, C.I. pigment orange 64, C.I. pigment orange 68, C.I. pigment orange 70, C.I. pigment orange 71, C.I. pigment orange 72, C.I. pigment orange 73, C.I. pigment orange 74；
nullC.I. paratonere 1、C.I. paratonere 2、C.I. paratonere 5、C.I. paratonere 17、C.I. pigment red 31、C.I. pigment red 32、C.I. pigment red 41、C.I. pigment red 122、C.I. pigment red 123、C.I. paratonere 144、C.I. pigment red 149、C.I. paratonere 166、C.I. paratonere 168、C.I. paratonere 170、C.I. paratonere 171、C.I. paratonere 175、C.I. paratonere 176、C.I. paratonere 177、C.I. paratonere 178、C.I. pigment red179、C.I. paratonere 180、C.I. paratonere 185、C.I. paratonere 187、C.I. paratonere 202、C.I. paratonere 206、C.I. Pigment Red 207、C.I. paratonere 209、C.I. pigment red 21 4、C.I. paratonere 220、C.I. paratonere 221、C.I. paratonere 224、C.I. paratonere 242、C.I. paratonere 243、C.I. paratonere 254、C.I. paratonere 255、C.I. paratonere 262、C.I. paratonere 264、C.I. paratonere 272；
C.I. pigment violet 1, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29, C.I. pigment violet 32, C.I. pigment violet 36, C.I. pigment violet 38；
C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. pigment blue 60, C.I. alizarol saphirol 80；
C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58；
C.I. pigment brown 23, C.I. pigment brown 25；
C.I. pigment black 1, C.I. pigment black 7 etc..
Secondly, the chemical constitution of [IV] coloring agent as dyestuff or pigment etc. is illustrated.About chemical constitution, azo, triarylmethane class, Anthraquinones, benzylidene class, oxonols class, flower cyanines class, phenothiazines, pyrrolo-pyrazole azomethine type, oxa anthracenes, phthalocyanines, benzo pyran, indigoid type, diketopyrrolopyrroles etc. can be enumerated.Those coloring agent preferably select the coloring agent of triarylmethane class, barbiturates azo, pyrazoles azo, anilino-azo, Pyrazolotriazole azo, pyridone azo, phthalocyanines, Anthraquinones, anthrapyridones and diketopyrrolopyrroles.
Triarylmethane based colorant as the example of preferred [IV] coloring agent is in coloring agent blue, purple.
It is belonging to the pigment such as C.I. alizarol saphirol, C.I. pigment violet in coloring agent blue, purple, C.I. the basic stain such as alkali blue, C.I. alkalescence purple, C.I. the acid stain such as the oil-soluble dyes such as solvent blue, C.I. solvent violet, C.I. acid blue, C.I. acid violet, C.I. disperse blue, C.I. disperse violet isodispersity dyestuff etc., the edible indigo plant of C.I., C.I. eat the coloring agent of the edible coloring agents etc. such as purple.
It addition, belong to the salt forming dye those acid staiies (also including direct dyes), basic stain being modified with counter ion.
Triphenyl methane based colorant as the example of triarylmethane based colorant is the NH owing to being located relative to the position that center carbon is para-position2Or OH base is oxidized and becomes quinone structure, thus carrying out the coloring agent developed the color.And, it is mainly basic stain, but has imported sulfonic dyestuff and become acid stain.
According to NH2, the number of OH base and be divided into following 3 kinds of types, wherein the form of triaminotriphenyl methylmethane class dyestuff is in demonstrating good blue aspect for preferred form.
A) diaminourea triphenylmethane dye
B) triaminotriphenyl methylmethane class dyestuff
C) there is the rhodo type dye of OH base
Triaminotriphenyl methylmethane class dyestuff bright, excellent in light-resistance and be preferably used.And, wherein particularly preferable as the Bisphenylnaphthylmethane dyes of basic stain.
Triarylmethane based colorant can use dyestuff and the pigment of following 5 kinds of forms.
1) basic stain (triarylmethane class basic stain) of triarylmethane class dyestuff
2) salt-forming compound of triarylmethane class basic stain and the salt-forming compound of organic sulfonic acid, triarylmethane class basic stain and aromatic hydroxy-carboxylic
3) acid stain of triarylmethane class dyestuff
4) salt-forming compound of triarylmethane acid dye and quaternary ammonium
5) mordant pigment (particularly the metallic lakes pigment of triarylmethane class dyestuff) of triarylmethane class dyestuff
As those forms, the metallic lakes pigment of the basic stain of triarylmethane class dyestuff, triarylmethane class basic stain and the salt-forming compound of organic sulfonic acid, triarylmethane class basic stain and the salt-forming compound of aromatic hydroxy-carboxylic, triarylmethane class dyestuff is wherein preferably used.
Triarylmethane class dyestuff has following dichroism: have high absorbance in 400nm～430nm.But, even if having good dichroism, also thermostability extreme difference in the same manner as general dyestuff.When using in the Color Liquid Crystal Display image display device requiring high reliability, in previously, characteristic is also insufficient.It is therefore preferable that use in the colored filter of this embodiment.Moreover, it is also possible to dyestuff is alkalized as the problem points previously improving triarylmethane class dyestuff, become salinization, oil-soluble, utilize the modified of resin to use.Or Dye lake can also be made pigment.
The basic stain of triarylmethane class dyestuff, oil-soluble dyes mix preferably by with the resin with acidic group as such in carboxyl or rosin ester, Abietyl modified maleic acid resin (Abietyl modified fumaric resin also synonym) and improve toleration.Those have the resin of acidic group, rosin ester, Abietyl modified maleic acid resin acid number be preferably 20～200.Herein, acid number is utilize the method for JISK-0070 and the value that measures.
Triarylmethane class basic stain can enumerate C.I. alkali blue 1,5,7,26, C.I. alkaline purple 1,3 etc..C.I. Blue 7 is wherein preferably used.
Secondly, the salt-forming compound of triarylmethane class basic stain Yu organic sulfonic acid is illustrated.It is medium that triarylmethane class basic stain and organic sulfonic acid can pass through to make both to be dissolved in aqueous solution, alcoholic solution, thus reacting and obtaining salt-forming compound.
Organic sulfonic acid can use naphthalene class sulfonated bodies, aphthols sulfonated bodies etc..
Naphthalene class sulfonated bodies is the general name that bond has sulfonic compound on the carbon atom of naphthalene, and aphthols sulfonated bodies is the general name that bond has sulfonic compound on the carbon atom of naphthols.
Naphthalene class sulfonated bodies has: bond has 1 sulfonic naphthalene list sulfonic acid, bond to have 2 sulfonic naphthalenedisulfonic acids, bond to have 3 sulfonic naphthalene trisulfonic acids.Specifically 1-naphthalene sulfonic aicd, 2-LOMAR PWA EINECS 246-676-2,1,3-naphthalenedisulfonic acid, 1,5-naphthalenedisulfonic acid, 1,6-naphthalenedisulfonic acid, 1,7-naphthalenedisulfonic acid, 2,6-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acids, 1,3,5-naphthalene trisulfonic acid, 1,3,6-naphthalene trisulfonic acids, 1,3,7-naphthalene trisulfonic acid etc..
And, naphthalene class sulfonated bodies also comprises naphthylamine sulfonic acid except aforesaid LOMAR PWA EINECS 246-676-2.And have: bond has 1 sulfonic naphthylamines list sulfonic acid, bond to have 2 sulfonic naphthylamine disulfonic acids, bond to have 3 sulfonic naphthylamines trisulfonic acids.Specifically 1, 4-naphthylamine sulfonic acid (naphthonic acid), 1, 5-naphthylamine sulfonic acid (1-Naphthylamine-5-sulfonic), 1, 6-naphthylamine sulfonic acid (6-Cleve's acid), 1, 7-naphthylamine sulfonic acid (7-Cleve's acid), 1, 8-naphthylamine sulfonic acid (Schollkopf acid), 2, naphthalidine sulfonic acid (tobias acid), 2, 5-naphthylamine sulfonic acid, 2, 6-naphthylamine sulfonic acid (Broenner's acid), 1, 3, 6-naphthylamine disulfonic acid (freund's acid), 1, 3, 7-naphthylamine disulfonic acid, 2, 3, 6-naphthylamine disulfonic acid (amido-R-acid), 2, 4, 6-naphthylamine disulfonic acid (C-acid), 2, 5, 7-naphthylamine disulfonic acid (amido-J-acid), 2, 6, 8-naphthylamine disulfonic acid (Amino-G Acid), 1, 3, 6, 8-naphthylamines trisulfonic acid (Koch's acid) etc..
Aphthols sulfonated bodies also has: bond has 1 sulfonic naphthols list sulfonic acid, bond to have 2 sulfonic naphthol disulfonic acids, bond to have 3 sulfonic naphthol trisulfonic acids.Specifically 1-naphthols-2-sulfonic acid, Neville acid (NW acid), 1-naphthol-5-sulfonic acid (L acid), 1-naphthols-8-sulfonic acid, oxy-Tobias acid, beta naphthal-6-sulfonic acid (Xue Fo Shi acid), 2-naphthol-8-sulfonic acid (crocetin), 1-naphthols-2, 4-disulfonic acid, 1-naphthols-3, 6-disulfonic acid, 1-naphthols-3, 8-disulfonic acid (ε acid), beta naphthal-3, 6-disulfonic acid (R-acid), beta naphthal-3, 8-disulfonic acid, beta naphthal-6, 8-disulfonic acid (G-acid), 1-naphthols-2, 4, 7-trisulfonic acid, 1-naphthols-3, 6, 8-trisulfonic acid (oxo Koch's acid), beta naphthal-3, 6, 8-trisulfonic acid etc..
Wherein preferably bond has 2 sulfonic naphthalenedisulfonic acids and naphthol disulfonic acid.Wherein preferably 1,5-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acids, beta naphthal-3,6-disulfonic acid, beta naphthal-3,8-disulfonic acid.
It addition, the salt-forming compound comprising Victoria pure blue BO (C.I. Blue 7) and naphthalenedisulfonic acid, the salt-forming compound that comprises Victoria pure blue BO (C.I. Blue 7) and naphthol disulfonic acid are preferred dyestuffs.
Make two sulfonated bodiess of naphthalene class, two sulfonated bodiess of aphthols react with triarylmethane class basic stain, and when making the situation of [IV] coloring agent of this embodiment, two sulfonated bodiess of 1 mole form salt relative to triarylmethane class dyestuff 2 molar reactive.It has neutralized electric charge, and has the coloring agent component of 2 times amount with the molar ratio computing of counter ion composition, is therefore the preferred component becoming the colour developing not undermining dyestuff as coloring agent.That is, it is preferred to use there are at least 2 sulfonic organic sulfonic acids.
And, the salt-forming compound of triarylmethane class basic stain and organic sulfonic acid, (aromatic hydroxy-carboxylic) can be synthesized by itself previously known method.Japanese Patent Laid-Open 2003-215850 publication etc. discloses concrete maneuver.
And, aromatic hydroxy-carboxylic can be used in the same manner as above-mentioned organic sulfonic acid to obtain salt-forming compound.As preferred aromatic hydroxy-carboxylic, 3,5-di-tert-butyl salicylic acids, 3-hydroxy-2-naphthoic acid, 3-phenylo salicylic acid are wherein preferably used.When using the situation of aromatic hydroxy-carboxylic, it is thus achieved that the amino (-NHC in triarylmethane class dyestuff2H5) salt-forming compound of part and carboxylic acid (-COOH) the part bond of aromatic hydroxy-carboxylic.And, hydroxyl (-OH) and salt-forming reaction unrelated class ground remaining.
It addition, the salt-forming compound comprising Victoria pure blue BO (C.I. Blue 7) and 3,5-di-tert-butyl salicylic acids is preferred dyestuff.
The acid stain of triarylmethane class dyestuff is preferably used edible blue No. 101 (C.I. Blue VRSs), acid ethereal blue (C.I. acid blue 3), color lake indigo plant I (C.I. acid blue 5), color lake indigo plant II (C.I. Acid Blue 7), edible blue No. 1 (C.I. acid blue 9), C.I. acid blue 22, C.I. acid blue 83, C.I. acid blue 90, C.I. acid blue 93, C.I. Blue VRS 00, C.I. Blue VRS 03, C.I. Blue VRS 04, C.I. Blue VRS 09.
The salt-forming compound of triarylmethane acid dye and quaternary ammonium compound can be synthesized by itself previously known method.
If row are as an example, then after being dissolved in the water by triarylmethane acid dye, adding quaternary ammonium compound, one side is stirred simultaneously carrying out into salinization and processes.Herein, it is thus achieved that the sulfonic group (-SO in triarylmethane acid dye3H) part and the ammonium (NH of quaternary ammonium compound4 +) salt-forming compound of part bond.Quaternary ammonium compound is preferably used triethylbenzyl ammonium chlorine etc..
In this embodiment, triarylmethane mordant pigment can be used as triarylmethane based colorant.
The color lake carried out in pigmentation is to utilize precipitant to be obtained insoluble salt by the dyestuff of solubility, is have chemical reaction, and dye component is adsorbed in the state on precipitant particle.
Triaminotriphenyl methylmethane class dyestuff improves weatherability, thermostability by carrying out color lake, becomes stable good coloring agent.
Precipitant in order to triarylmethane class dyestuff to carry out color lake can be enumerated barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminium acetate, lead acetate, tannic acid, mucositis promise (Katanol), be referred to as the compound heteropoly acid (phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, silicon tungsten molybdic acid, silico-tungstic acid, silicomolybdic acid) etc. of complex acid.Wherein, due to distinctness and tinting strength, tinting power is big, light resistance significantly improves, and is therefore preferred pigment for the mordant pigment of use compound heteropoly acid.
Triarylmethane class pigment specifically can enumerate C.I. pigment blue 1, C.I. alizarol saphirol 2, C.I. alizarol saphirol 9, C.I. pigment blue 10, C.I. pigment blue 14, C.I. alizarol saphirol 62, C.I. pigment violet 3, C.I. pigment violet 27, C.I. pigment violet 39 etc..
If specifically enumerating preferred triarylmethane class pigment, it is then:
C.I. pigment blue 1.
With phosphotungstomolybdic acid, C.I. alkali blue 26, C.I. Blue 7 are carried out color lake.
C.I. pigment violet 3.
With phosphotungstomolybdic acid, C.I. alkaline purple 1 is carried out color lake.
C.I. pigment violet 39.
With phosphotungstomolybdic acid, C.I. alkaline purple 3 (crystal violet) is carried out color lake.
C.I. pigment blue 1 is wherein preferably used.
Secondly, barbiturates azo dyes and pyridone azo as the example of preferred [IV] coloring agent such as have following structure.But, the barbiturates azo dyes and the pyridone azo that use in this embodiment are not limited to those structures.
[changing 7]
In formula (101), T1And T2Separately represent oxygen atom or sulphur atom.
R101～R104Separately represent hydrogen atom, also can have the aliphatic alkyl that carbon number is 1～10 of substituent group, also can have the aryl that carbon number is 6～20 of substituent group, also can have the aralkyl that carbon number is 7～20 of substituent group or also can have the acyl group that carbon number is 2～10 of substituent group.
R105～R112Separately represent alkoxyl, carboxyl, sulfo group, sulfamoyl or N position-replacement sulfamoyl that aliphatic alkyl that hydrogen atom, carbon number are 1～10, carbon number are 1～8.Hydrogen atom contained in above-mentioned aliphatic alkyl also can be substituted with halogen atoms.
If being described in more detail, then in formula (101), R101～R104In the aliphatic alkyl that carbon number is 1～10 can be any number of of straight-chain, branch-like or ring-type.The carbon number that carbon number is the aliphatic alkyl of 1～10 is preferably 2～8, more preferably 3～6.Carbon number be 1～10 aliphatic alkyl include, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, ethylhexyl (2-ethylhexyl etc.), cyclopenta, cyclohexyl and cyclohexylalkyl etc..
And, carbon number be 1～10 aliphatic alkyl in contained hydrogen atom also can be replaced by (preferred carbon number is 1～4) alkoxyl that hydroxyl, carbon number are 1～8 or (preferred carbon number is 1～4) thio alkoxy that carbon number is 1～8.The aliphatic alkyl being substituted include, for example hydroxyethyl (2-hydroxyethyl etc.), ethoxyethyl group (2-ethoxyethyl group etc.), ethyl hexyl oxy propyl group (3-(2-ethyl hexyl oxy) propyl group etc.) and methylthio (3-methylthio etc.) etc..
R101～R104In the aryl that carbon number is 6～20 can be unsubstituted, also can have the substituent groups such as aliphatic alkyl, alkoxyl, carboxyl, sulfo group or the base that comprises ester bond.Carbon number that the carbon number of described aryl comprises substituent group and count, it is preferred to 6～10.Aryl include, for example phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl and carboethoxyphenyl (4-(COOC2H5) Ph base (Ph basis representation phenyl) etc.) etc..
R101～R104In the moieties of the aralkyl that carbon number is 7～20 can be straight-chain, branch-like or ring-type any number of.Carbon number that the carbon number of aralkyl comprises substituent group and count, it is preferred to 7～10.Carbon number be 7～20 aralkyl can enumerate benzyl and phenethyl etc..
R101～R104In the acyl group that carbon number is 2～10 can be unsubstituted, also can the substituent group such as bond aliphatic alkyl or alkoxyl.Carbon number that the carbon number of acyl group comprises substituent group and count, its number is preferably 2～10.Acyl group include, for example acetyl group, benzoyl, anisoyl (to anisoyl etc.) etc..
R105～R112In the aliphatic alkyl that carbon number is 1～10 can enumerate and R101～R104When identical base.R105～R112Aliphatic alkyl in contained hydrogen atom also can be substituted with halogen atoms, halogen atom preferably enumerates fluorine atom.The concrete example of the aliphatic alkyl being substituted with halogen atoms can enumerate trifluoromethyl etc..
R105～R112In the carbon number of the alkoxyl that carbon number is 1～8 be preferably 1～4.Alkoxyl include, for example methoxyl group, ethyoxyl, isopropoxy, positive propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy etc..
R105～R112In N position-replacement sulfamoyl such as be preferably N position-monosubstituted sulfamoyl, with-SO2NHR140And represent.
-SO2NHR140In contained R140Represent the aliphatic alkyl that carbon number is 1～10 also can with substituent group, also can have the aryl that carbon number is 6～20 of substituent group, also can have the aralkyl that carbon number is 7～20 of substituent group or also can have the acyl group that carbon number is 2～10 of substituent group.
R140In the aliphatic alkyl that carbon number is 1～10 can be straight-chain, branch-like or ring-type any number of.The carbon number of aliphatic alkyl does not comprise the carbon number of substituent group, and its number is preferably 6～10.
R140In the aliphatic alkyl that carbon number is 1～10 include, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, methyl butyl (1,1,3,3-tetramethyl butyl etc.), methylhexyl (1-methylhexyl, 1,5-dimethylhexanyl etc.), ethylhexyl (2-ethylhexyl etc.), cyclopenta, cyclohexyl, methylcyclohexyl (2-methylcyclohexyl etc.) and cyclohexylalkyl etc..
-SO2NHR140In contained R140In the aliphatic alkyl that carbon number is 1～10 also can be replaced by (be preferably carbon number be 1～4) alkoxyl that carbon number is 1～8, for instance propoxypropyl (3-(isopropoxy) propyl group etc.) etc. can be enumerated.
R140In the aryl that carbon number is 6～20 can be unsubstituted, also can have the substituent group such as aliphatic alkyl or hydroxyl.Carbon number that the carbon number of described aryl comprises substituent group and count, it is preferred to 6～10.Aryl include, for example phenyl, hydroxy phenyl (4-hydroxy phenyl etc.), trifluoromethyl (4-trifluoromethyl etc.) etc..
R140In the moieties of the aralkyl that carbon number is 7～20 can be any number of of straight-chain or branch-like.The carbon number of aralkyl is generally 7～20, it is preferred to 7～10.This aralkyl can enumerate the phenylalkyls etc. such as benzyl, phenyl propyl (1-methyl-3-phenyl propyl etc.), phenyl butyl (3-amino-1-phenyl butyl etc.).
R140In the acyl group that carbon number is 2～10 can be unsubstituted, hydrogen atom contained in acyl group also can be replaced by aliphatic alkyl or alkoxyl.Carbon number that the carbon number of acyl group comprises substituent group and count, its number is preferably 6～10.Acyl group include, for example acetyl group, benzoyl, adjacent toluyl groups, a toluyl groups, to toluyl groups and anisoyl (to anisoyl etc.) etc..
Pyridone azo as the example of preferred [IV] coloring agent such as has following structure.
[changing 8]
In formula (102), Z represents halogen atom, also can have the aliphatic alkyl that carbon number is 1～12 of substituent group, carbon number is the alkoxyl of 1～8, there is 1 or 2 and select free hydroxyl, carboxyl, carbamyl, sulfo group, the phenyl of at least one substituent group of the group that sulfamoyl and N position-replacement sulfamoyl are constituted, or there are 1～3 and select free halogen atom, also can have the aliphatic alkyl that carbon number is 1～12 of substituent group, carbon number is the alkoxyl of 1～8, hydroxyl, carboxyl, carbamyl, sulfo group, the naphthyl of at least one substituent group of the group that sulfamoyl and N position-replacement sulfamoyl are constituted.
R121Representing hydrogen atom, the carbon number of straight-chain, branch-like or ring-type is aliphatic alkyl, carboxyl or the trifluoromethyl of 1～10.
R122Represent hydrogen atom, cyano group, carbamyl, N position-replacement carbamyl, sulfamoyl or sulfo group.
R123Represent hydrogen atom, also can have the straight-chain that carbon number is 1～10 of substituent group, the aliphatic alkyl of branch-like or ring-type, also can have the aryl that carbon number is 6～30 of substituent group, also can have the aralkyl that carbon number is 7～20 of substituent group, also can have the heterocyclic radical that carbon number is 3～20 of substituent group, carbamyl, N position-replacement carbamyl, also can have the alkoxy carbonyl that carbon number is 2～20 of substituent group, also can have the aryloxycarbonyl that carbon number is 7～30 of substituent group, also can have the acyl group that carbon number is 2～20 of substituent group, also can have the aliphaticsulfonyl that carbon number is 1～30 of substituent group or also can have the aryl sulfonyl that carbon number is 6～30 of substituent group.
If being described in more detail, then in formula (102), the carbon number in Z is the aliphatic alkyl of 1～12 can be any number of of straight-chain, branch's chain or ring-type.The carbon number of aliphatic alkyl includes the carbon number of all of substituent group, and its number is generally 1～12, it is preferred to 2～11.Aliphatic alkyl include, for example n-octyl, methylhexyl (1,5-dimethylhexanyl etc.), ethylhexyl (2-ethylhexyl etc.), ring octyl group, methylcyclohexyl (2,2-Dimethylcyclohexyls etc.) and cyclohexylalkyl etc..Hydrogen atom contained in aliphatic alkyl also can be replaced by alkoxyl or the carboxyl that carbon number is 1～8.The aliphatic alkyl with substituent group can enumerate alkoxyl propyl group (3-(2 '-ethyl hexyl oxy) propyl group etc.) and 8-(carboxyl) octyl group etc..
Carbon number in Z be 1～8 alkoxyl include, for example methoxyl group, ethyoxyl, isopropoxy, positive propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy etc..
Halogen atom in Z can enumerate fluorine atom, bromine atoms, chlorine atom and atomic iodine.
N position-replacement sulfamoyl in Z is with-SO2N(R141)R142And represent.R141And R142Separately represent hydrogen atom, also can have the aliphatic alkyl that carbon number is 1～16 of substituent group, also can have the aryl that carbon number is 6～20 of substituent group, also can have the aralkyl that carbon number is 7～20 of substituent group or also can have acyl group (wherein, the R that carbon number is 2～15 of substituent group141And R142It is not hydrogen atom) simultaneously.
Carbon number is the aliphatic alkyl of 1～16 can be any number of of straight-chain, branch-like or ring-type, and the carbon number of aliphatic alkyl is preferably 6～16.
R141And R142In the aliphatic alkyl that carbon number is 1～16 can be straight-chain, branch's chain or ring-type any number of.The carbon number of aliphatic alkyl does not comprise the carbon number of substituent group, and its number is generally 1～16, it is preferred to 6～10.Aliphatic alkyl include, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, methyl butyl (1,1,3,3-tetramethyl butyl etc.), methylhexyl (1,5-dimethylhexanyl etc.), ethylhexyl (2-ethylhexyl etc.), cyclopenta, cyclohexyl, methylcyclohexyl (2-methylcyclohexyl etc.) and cyclohexylalkyl etc..Hydrogen atom contained in aliphatic alkyl also can be replaced by alkoxyl or the carboxyl that carbon number is 1～8.The aliphatic alkyl with substituent group can enumerate propoxypropyl (3-(isopropoxy) propyl group etc.), 2-(carboxyl) ethyl, 3-(carboxyl) ethyl and 4-carboxy ethyl etc..
R141And R142In the aryl that carbon number is 6～20 also can have the substituent group such as aliphatic alkyl or hydroxyl.Carbon number that the carbon number of aryl comprises substituent group and count, be generally 6～20, it is preferred to 6～10.Aryl can enumerate phenyl, carboxyl phenyl (2-carboxyl phenyl, 2,4-dicarboxyphenyi etc.), hydroxy phenyl (4-hydroxy phenyl etc.), trifluoromethyl (4-trifluoromethyl etc.) and methoxyphenyl (4-methoxyphenyl) etc..
R141And R142In the moieties of the aralkyl that carbon number is 7～20 can be any number of of straight-chain or branch-like.The carbon number of aralkyl is generally 7～20, it is preferred to 7～10.Aralkyl can enumerate the phenylalkyls such as benzyl, phenylethyl (2-phenylethyl, 2-(4-hydroxy phenyl) ethyl etc.), phenyl ethylene (2-phenyl ethylene etc.), phenyl propyl (1-methyl-3-phenyl propyl etc.) and phenyl butyl (3-amino-1-phenyl butyl etc.).
R141And R142In the acyl group that carbon number is 2～15 can be unsubstituted, also can have the substituent groups such as aliphatic alkyl, alkoxyl or carboxyl.Carbon number that the carbon number of acyl group comprises substituent group and count, its number is generally 2～15, it is preferred to 6～10.Acyl group include, for example acetyl group, benzoyl, anisoyl (to anisoyl etc.), carboxyacetyl, 2-carboxypropanoyl, 3-carboxypropanoyl, 2-carboxybutanoyl, 3-carboxybutanoyl and 4-carboxybutanoyl etc..
R121Representing hydrogen atom, the carbon number of straight-chain, branch-like or ring-type is the aliphatic alkyl of 1～10, carboxyl or trifluoromethyl.
R121In the carbon number of the aliphatic alkyl that carbon number is 1～10 do not comprise the carbon number of substituent group.Its carbon number is preferably 2～8, more preferably 3～6.Aliphatic alkyl can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, cyclopenta and cyclohexyl etc..
R122Represent hydrogen atom, cyano group, carbamyl or N position-replacement carbamyl, sulfamoyl or sulfo group.
R122In N position-replacement carbamyl can enumerate-CON (R143)R144。R143And R144Independently represent hydrogen atom, also can have the aliphatic alkyl that carbon number is 1～10 of substituent group, also can have the aryl that carbon number is 6～20 of substituent group, also can have the aralkyl that carbon number is 7～20 of substituent group or also can have the acyl group that carbon number is 2～10 of substituent group.
R143And R144Aliphatic alkyl, aryl, the explanation of aralkyl and acyl group and concrete example and aforesaid R141And R142Identical.Wherein, acyl group also can have halogen atom.The acyl group also can with halogen atom include, for example benzoyl bromide (to benzoyl bromide etc.) etc..
R123Represent hydrogen atom, also can have the straight-chain that carbon number is 1～10 of substituent group, the aliphatic alkyl of branch-like or ring-type, also can have the aryl that carbon number is 6～30 of substituent group, also can have the aralkyl that carbon number is 7～20 of substituent group, also can have the heterocyclic radical that carbon number is 3～20 of substituent group, carbamyl, N position-replacement carbamyl, also can have the alkoxy carbonyl that carbon number is 2～20 of substituent group, also can have the aryloxycarbonyl that carbon number is 7～30 of substituent group, also can have the acyl group that carbon number is 2～20 of substituent group, also can have the aliphaticsulfonyl that carbon number is 1～30 of substituent group or also can have the aryl sulfonyl that carbon number is 6～30 of substituent group.
R123In aliphatic alkyl can enumerate and above-mentioned R121In the identical base of aliphatic alkyl.
As R123In aryl, carbon number is generally 6～30, it is preferred to 6～20, more preferably 6～16.The concrete example of aryl can enumerate phenyl, 4-nitrobenzophenone, 2-nitrobenzophenone, 2-chlorphenyl, 2,4-Dichlorobenzene base, 2,4-3,5-dimethylphenyls, 2-aminomethyl phenyl, 4-methoxyphenyl, 2-methoxyphenyl and 2-methoxycarbonyl-4-nitrobenzophenone etc..
R123In aralkyl can be any number of of straight-chain or branch-like, carbon number is preferably 7～10.The concrete example of aralkyl can enumerate the phenylalkyls such as benzyl, phenyl propyl (1-methyl-3-phenyl propyl etc.) and phenyl butyl (3-amino-1-phenyl butyl etc.).
R123In the heterocyclic radical saturable that carbon number is 3～20 also can be unsaturated, carbon number is preferably 3～20, more preferably 5～15.The concrete example of heterocyclic radical can enumerate pyrazolyl, 1,2,4-triazolyl, isothiazolyl, benzisothiazole base, thiazolyl, benzothiazolyl, azoles base and 1,2,4-thiadiazolyl group etc..And, also can have substituent group further.
R123In N position-replacement carbamyl with about R122And described N position-replacement carbamyl is identical.
R123In alkoxy carbonyl can be unsubstituted and also can have substituent group, also can be ring-type.The carbon number of alkoxy carbonyl is generally 2～20, it is preferred to 2～16, more preferably 2～10.Alkoxy carbonyl can enumerate methoxycarbonyl, ethoxy carbonyl and butoxy carbonyl etc..
R123In aryloxycarbonyl can be unsubstituted and also can have substituent group, carbon number is generally 7～30, it is preferred to 7～20, more preferably 7～16.Aryloxycarbonyl can enumerate phenyloxycarbonyl and 4-methylphenoxy carbonyl etc..
R123In acyl group can be aliphatic Oxo can be also aryl carbonyl, and can be saturated or undersaturated any number of, also can be ring-type, also can have substituent group further.Carbon number is generally 2～20, it is preferred to 2～15, more preferably 2～10.Acyl group can enumerate acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, pivaloyl group, benzoyl etc..
R123In aliphaticsulfonyl saturable also can be unsaturated, also can be ring-type.Carbon number is generally 1～30, it is preferred to 1～20, more preferably 1～16.Aliphaticsulfonyl can enumerate mesyl, fourth sulfonyl, methoxy methyl sulfonyl, methoxyl group ethylsulfonyl and ethyoxyl ethylsulfonyl etc..
R123In aryl sulfonyl also can have substituent group, carbon number is generally 6～30, it is preferred to 6～20, more preferably 6～18.Aryl sulfonyl can enumerate benzenesulfonyl and tosyl etc..
Secondly, diketopyrrolopyrroles and phthalocyanines as the example of preferred [IV] coloring agent such as have following structure.But the diketopyrrolopyrroles used in this embodiment and phthalocyanine-based colorant are not limited in those.
[changing 9]
In formula (103), Y represents oxygen atom or sulphur atom.R131With R132Can identical also can be different, represent hydrogen atom, alkyl, cycloalkyl, thiazolinyl, alkynyl, aryl, aralkyl, carbamyl, alkylcarbamoyl group, aromatic yl ammonia methanoyl or alkoxy carbonyl.R133、R134Can identical also can be different, represent alkyl, cycloalkyl, aralkyl or carbocyclic ring or hetero ring type aromatic residue.
If being described in more detail, then in formula (103), R131、R132、R133And R134In alkyl can branch also can be non-limbed, it is preferable that have and be preferably 1～18, more preferably 1～12, be particularly preferably the carbon atom of 1～6.Specifically can enumerate methyl, ethyl, isopropyl, sec-butyl, the tert-butyl group, tertiary pentyl, octyl group, decyl, dodecyl or octadecyl etc..
R131、R132、R133And R134In cycloalkyl preferably have and be preferably 3～8, be more preferably the carbon atom of 3～6, specifically can enumerate cyclopenta, cyclohexyl etc..R131、R132In thiazolinyl preferably have and be preferably 2～8, be more preferably the carbon atom of 2～6, specifically can enumerate vinyl, pi-allyl etc..R131、R132In alkynyl preferably have and be preferably 2～8, be more preferably the carbon atom of 2～6, specifically can enumerate acetenyl etc..
R131、R132In aryl preferably have and be preferably the carbon atom of 6～10, specifically can enumerate phenyl, naphthyl etc..R131、R132In the alkyl of alkylcarbamoyl group can enumerate the alkyl identical with abovementioned alkyl.R131、R132In the aryl of aromatic yl ammonia methanoyl can enumerate the aryl identical with above-mentioned aryl.R131、R132In the alkoxyl of alkoxy carbonyl can enumerate the alkoxyl that carbon number is 1～4, specifically can enumerate methoxyl group, ethyoxyl, butoxy etc..
In formula (103), R131、R132、R133And R134When representing aralkyl, it is particularly preferred to containing monocycle～three-ring type, be more preferably monocyclic or the aromatic yl residue of two ring types.Specifically include, for example benzyl and phenylethyl.In above-mentioned formula (103), work as R133And R134When representing the situation of carbon-ring type aromatic residue, the desirably residue of monocycle～tetra-ring type, particularly monocyclic or two ring types, that is phenyl, xenyl or naphthyl.
In formula (103), R133And R134When representing hetero ring type aromatic residue, the desirably residue of monocycle～three-ring type.Those bases can be pure hetero ring type, and also can contain 1 heterocycle and one or more condensation phenyl ring, specifically include, for example pyridine radicals, pyrimidine radicals, pyrazinyl, triazine radical, furyl, pyrrole radicals, thienyl, quinolyl, coumarin base, benzofuranyl, benzimidazolyl or benzoxazolyl group etc..
In formula (103), R131、R132It is preferably hydrogen atom.And, R133、R134Preferably it is each independently alkyl that carbon number is 1～4, dialkyl amido, alkylhalide group or also can have the phenyl of halogen atom alternatively base.
Secondly, as the phthalocyanine-based colorant preferably zinc halide phthalocyanine-based colorant of the example of preferred [IV] coloring agent, for instance have following structure.
[changing 10]
In formula (104), X1～X16Separately represent hydrogen atom, chlorine atom or bromine atoms.
More specifically, in formula (104), X1～X16It is 0～6 that the number of represented substituent group is preferably chlorine atom, and bromine atoms is 10～16, and chlorine atom and bromine atoms and be 10～16；Be more preferably chlorine atom be 0～3, bromine atoms be 13～16, and chlorine atom and bromine atoms and be 13～16；Be more preferably further chlorine atom be 1～3, bromine atoms be 13～15, and chlorine atom and bromine atoms and be 14～16.
Secondly, about the inorganic pigment that can use in [IV] coloring agent, for instance can enumerate titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, chrome yellow, zinc yellow, colcother (red iron oxide (III)), cadmium red, ultramarine, Prussian blue, chrome oxide green, cobalt green, umber, titanium are black, synthesis is iron black, carbon black etc..
Secondly, the content of [IV] coloring agent contained in colored composition is illustrated.
As the content of [IV] coloring agent, for [I] alkali soluble resins 100 weight portion, it is preferably 1 weight portion～400 weight portion, more preferably 5 weight portion～350 weight portions.By making the content of [IV] coloring agent be above-mentioned scope, it is possible to using high level, balance reaches the alkali-developable of colored composition, the thermostability of pixel, solvent resistance and as the high brightness of colored pattern and colored filter or high-contrast well.
<[V] compound>
The colored composition used in the manufacture of the colored filter of this embodiment can contain [V] compound.[V] compound is the compound playing the function as sclerosing agent.Therefore, sometimes referred to as [V] sclerosing agent.
[V] compound is chosen from least one compound of the group that the compound represented by following formula (1), the compound represented by following formula (2), tertiary amine compound, amine salt, salt, amidine salt, amide compound, mercaptan compound, block isocyanate compound and the compound containing imidazole ring are constituted.Colored composition can by containing the hardening at subcritical temerature realizing colored pattern selected from [V] compound of this specific compound group.In a word, the storage stability that also can make colored composition improves.Hereinafter each compound is described in detail.
[changing 11]
[changing 12]
[above-mentioned formula (1) and the compound represented by formula (2)]
[V] compound is preferably selected from least one compound of the group that the compound represented by above-mentioned formula (1) and formula (2) is constituted.As [V] compound, can by selecting the above-mentioned specific compound with amino and short of electricity subbase to realize the hardening at subcritical temerature of colored pattern.In a word, the storage stability that also can make colored composition improves.Can further improve the voltage retention of the liquid crystal display cells of the colored filter using gained.
In formula (1), R1～R6It is each independently hydrogen atom, electron-withdrawing group or amino.Wherein, R1～R6In at least 1 be electron-withdrawing group, and R1～R6In at least 1 be amino, all or part of of the hydrogen atom of above-mentioned amino also can be replaced by the alkyl that carbon number is 1～6.
In above-mentioned formula (2), R7～R16It is each independently hydrogen atom, electron-withdrawing group or amino.Wherein, R7～R16In at least 1 be amino.And, all or part of of the hydrogen atom of this amino can also be replaced by the alkyl that carbon number is 1～6.And, during the situation of [V] compound used in colored composition, this amino also can be replaced by the alkyl that carbon number is 1～6.A is singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number is the alkylene of 2～6.Wherein, all or part of of the hydrogen atom of above-mentioned methylene and alkylene also can be replaced by cyano group, halogen atom or fluoroalkyl.
Above-mentioned R1～R16Represented electron-withdrawing group include, for example halogen atom, cyano group, nitro, trifluoromethyl, carboxyl, acyl group, alkyl sulphonyl, alkyloxysulfonyl, dicyanoethenyl, tricyano vinyl, sulfonyl etc..Those bases are preferably nitro, alkyloxysulfonyl, trifluoromethyl.Base represented by A is preferably sulfonyl, the methylene that also can be replaced by fluoroalkyl.
As the compound represented by above-mentioned formula (1) and formula (2),
nullIt is preferably 2，Double; two (4-aminophenyl) HFC-236fa of 2-、2，Double; two (4-aminophenyl) succinonitrile of 3-、4，4 '-diaminobenzophenone、4，4 '-diaminobenzoic acid phenyl ester、4，4 '-diamino diphenyl sulfone、1，4-diaminourea-2-chlorobenzene、1，4-diaminourea-2-bromobenzene、1，4-diaminourea-2-iodobenzene、1，4-diaminourea-2-Nitrobenzol、1，4-diaminourea-2-trifluoromethylbenzene、2，5-diaminourea benzonitrile、2，5-diaminobenzene ethyl ketone、2，5-diaminobenzoic acid、2，2 '-dichloro-benzidine、2，2 '-'-dibromobiphenyl amine、2，2 '-diiodobiphenyl amine、2，2 '-dinitrobenzidine、2，2 '-bis-(trifluoromethyl) benzidine、3-amino phenyl sulfonyl acetoacetic ester、3，5-bis trifluoromethyl-1，2-diaminobenzene、4-aminonitrobenzene、N，N-dimethyl-4-nitroaniline，It is more preferably 4，4 '-diamino diphenyl sulfone、2，Double; two (4-aminophenyl) HFC-236fa of 2-、2，2 '-bis-(trifluoromethyl) benzidine、3-amino phenyl sulfonyl acetoacetic ester、3，5-bis trifluoromethyl-1，2-diaminobenzene、4-aminonitrobenzene、N，N-dimethyl-4-nitroaniline.
Compound represented by above-mentioned formula (1) and formula (2) can be used alone or two or more mixing be used.As the content ratio of the compound represented by above-mentioned formula (1) and formula (2), for [I] alkali soluble resins 100 weight portion, it is preferably 0.1 weight portion～20 weight portion, more preferably 0.2 weight portion～10 weight portion.It is above-mentioned scope by making the content ratio of the compound represented by above-mentioned formula (1) and formula (2), it is possible to take into account storage stability and the hardening at subcritical temerature of colored composition with higher level.
[tertiary amine compound]
If making reactive high general primary amine or secondary amine compound and epoxide coexist, then in the preservation of constituent solution, due to amine, the nucleophilic attack of epoxy radicals is carried out sclerous reaction, thus having the possibility of the quality that harm is goods.But, when using tertiary amine, owing to reactivity is relatively low or coexists with epoxide in composition portion, storage stability becomes good.
Tertiary amine compound can use at least one of the group selecting the compound represented by free following formula (5) to constitute.
[changing 13]
In above-mentioned formula (5), R24～R26Be each independently alkyl that carbon number is 1～20, carbon number be 6～18 aryl or carbon number be the aralkyl of 7～30.Wherein, R24And R25Also can bond mutually, together form circulus with the nitrogen-atoms of those bonds.Part or all of the hydrogen atom of abovementioned alkyl, aryl and aralkyl also can be replaced.
Above-mentioned R24～R26The represented alkyl that above-mentioned carbon number is 1～20 include, for example straight-chain or the methyl of branch-like, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, lauryl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc..
Above-mentioned R24～R26The represented aryl that carbon number is 6～18 include, for example phenyl, naphthyl etc..
Above-mentioned R24～R26The represented aralkyl that carbon number is 7～30 include, for example benzyl, phenethyl etc..
nullTertiary amine compound include, for example N，N-dimethyl benzyl amine、Triphenylamine、Tri-butylamine、Trioctylphosphine amine、Tridodecylamine、Dibutyl benzyl amine、Three naphthylamines、N-ethyl-N-methylaniline、N，N-diethylaniline、N-phen yl-N-meth aniline、N，N-dimethyl-paratoluidine、N，N-dimethyl-4-bromaniline、N，N-dimethyl-4-aminoanisole、N-Phenylpiperidine、N-(4-methoxyphenyl) piperidines、N-phenyl-1，2，3，4-tetrahydroisoquinoline、6-benzyl oxygen base-N-phenyl-7-methoxyl group-1，2，3，4-tetrahydroisoquinoline、N，N '-lupetazin、N，N-dimethylcyclohexylam,ne、2-dimethylaminomethyl phenol、2，4，6-tri-(dimethylaminomethyl) phenol etc..
In those tertiary amine compounds, it is preferable that trioctylphosphine amine, 2-dimethylaminomethyl phenol, N, N-diethylaniline etc..Tertiary amine compound can be used alone or two or more mixing be used.As the content ratio of the tertiary amine compound in colored composition, for [I] alkali soluble resins 100 weight portion, it is preferably 0.1 weight portion～10 weight portion, more preferably 0.5 weight portion～5 weight portion.By making the content ratio of tertiary amine compound be above-mentioned particular range, it is possible to take into account storage stability and the hardening at subcritical temerature of colored composition with higher level.
[amine salt and salt]
Amine salt and salt can use at least one of the group selecting the compound represented by free following formula (6) to constitute.
[changing 14]
In above-mentioned formula (6), A1For nitrogen-atoms or phosphorus atoms.R27～R30Be each independently hydrogen atom, carbon number be 1～20 alkyl, carbon number be 6～18 aryl or carbon number be the aralkyl of 7～30.Wherein, part or all of the hydrogen atom of those bases also can be replaced.Q-It it is 1 valency anion.
Above-mentioned R27～R30The represented alkyl that carbon number is 1～20 include, for example straight-chain or the methyl of branch-like, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, lauryl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc..
Above-mentioned R27～R30The represented aryl that carbon number is 6～18 include, for example phenyl, naphthyl etc..
Above-mentioned R27～R30The represented aralkyl that carbon number is 7～30 include, for example benzyl, phenethyl etc..
Above-mentioned Q-1 represented valency anion include, for example chloride ion, bromide ion, iodide ion, cyanide ion, nitrate ion, nitrite ion, hypochlorite ion, chlorition, chloranion, cross chloranion, high manganese ion, bicarbonate ion, dihydrogen phosphate ions, hydrogen sulfide radical ion, thiocyanate ion, Carboxylic Acid Ions, azochlorosulfonate acid ion, phenoxy group ion, Tetrafluoroboric acid salt ion, four aryl boric acid salt ions, hexafluoro-antimonic acid salt ion etc..
Work as A1During for the situation of nitrogen-atoms, that is ammonium salt include, for example tetramethyl ammonium chloride, tetrabutylammonium chloride, dodecyl dimethyl benzyl ammonium chloride, octyltrimethylammonium chloride, decyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, CTAB, stearyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammoinium chloride, benzalkonium chloride, benzalkonium bromide, DDAC, VARISOFT TA100.
Work as A1nullDuring for the situation of phosphorus atoms，That is salt include, for example tetraphenyl tetraphenyl borate salts、Tetraphenyl four (p-methylphenyl) borate、Tetraphenyl four (to ethylphenyl) borate、Tetraphenyl four (p-methoxyphenyl) borate、Tetraphenyl four (to ethoxyl phenenyl) borate、Tetraphenyl four (to tert .-butoxyphenyl) borate、Tetraphenyl four (tolyl) borate、Tetraphenyl four (m-methoxyphenyl) borate、Three (p-methylphenyl) phenyl four (p-methylphenyl) borate、Four (p-methylphenyl) four (p-methylphenyl) borate、Three (p-methoxyphenyl) phenyl four (p-methylphenyl) borate、Tetraphenyl rhodanate、Butyl triphenyl rhodanate、Methyl triphenyl rhodanate、P-methylphenyl triphenyl rhodanate etc..
Preferred tetramethyl ammonium chloride, butyl triphenyl rhodanate in those amine salt and salt.Amine salt and salt can be used alone or two or more mixing be used.As the content ratio of the amine salt in colored composition and salt, for [I] alkali soluble resins 100 weight portion, it is preferably 0.05 weight portion～10 weight portion, more preferably 0.1 weight portion～5 weight portion.By making the content ratio of amine salt and salt be above-mentioned particular range, it is possible to take into account storage stability and the hardening at subcritical temerature of colored composition with higher level.
[amidine salt]
Amidine salt can use at least one of the group that the salt selecting the compound represented by free following formula (7) constitutes.
[changing 15]
In above-mentioned formula (7), m is the integer of 2～6.Wherein, part or all of the hydrogen atom that alkylene has also can be replaced by organic group.It addition, above-mentioned alkylene refers to the alkylene in tetrahydropyrimidine ring and with (CH in formula (7)2)mAnd both the alkylenes represented.
Above-mentioned alkylene the organic group of alternatively base that also can have include, for example:
The carbon numbers such as methyl, ethyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl are the alkyl of 1～6；
The carbon numbers such as hydroxymethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxyisopropyl, 3-hydroxy-tert-butyl, 6-hydroxyl hexyl are the hydroxy alkyl of 1～6；
The carbon numbers such as dimethylamino, methylethylamine, diethylamino, diisopropylaminoethyl, dibutylamino, tertbutyl methyl amino, di-n-hexyl amino are the dialkyl amido etc. of 2～12.
Compound represented by above-mentioned formula (7) can enumerate 1,5-diazabicyclo [4,3,0]-nonene-5 (DBN), 1,5-diazabicyclo [4,4,0]-decene-5,1,8-diazabicyclo [5,4,0]-endecatylene-7 (DBU), 5-hydroxypropyl-1,8-diazabicyclo [5,4,0]-endecatylene-7,5-dibutylamino-1,8-diazabicyclo [5,4,0]-endecatylene-7 etc..Preferred DBN and DBU in those compounds.
Compound represented by above-mentioned formula (7) can enumerate organic acid and mineral acid in order to the acid forming salt.
Organic acid include, for example carboxylic acid, monoalkyl carbonic acid, aromatic hydroxy compound, sulfonic acid etc..
Optimization acid, aromatic hydroxy compound, sulfonic acid in those acid, more preferably satisfied fatty acid, aromatic hydroxy compound, sulfonic acid, it is particularly preferred to as the sulfonic acid of strong acid, it is most preferred that toluenesulfonic acid, methanesulfonic acid, octyl benzene sulfonic acid.Amidine salt is preferably the salt of DBU and the salt of toluenesulfonic acid, DBU and the salt of the salt of octyl benzene sulfonic acid, DBN and toluenesulfonic acid, DBN and octyl benzene sulfonic acid.
Amidine salt can be used alone or two or more mixing be used.As the content ratio of the amidine salt in colored composition, for [I] alkali soluble resins 100 weight portion, it is preferably 0.1 weight portion～10 weight portion, more preferably 0.5 weight portion～5 weight portion.By making the content ratio of amidine salt be above-mentioned particular range, it is possible to take into account storage stability and the hardening at subcritical temerature of colored composition with higher level.
[amide compound]
Amide compound can use at least one of the group selecting the compound freely with the amide groups represented by following formula (8)～formula (10) to constitute.
[changing 16]
[changing 17]
[changing 18]
In above-mentioned formula (8), R31And R32Be each independently hydrogen atom, carbon number be 1～12 alkyl, cyclohexyl, phenyl, naphthyl, vinyl or 2-pyridine radicals.Wherein, above-mentioned carbon number is the alkyl of 1～12, phenyl and naphthyl also can replace by alkyl, halogen atom, hydroxyl, carboxyl or the acetyl group that carbon number is 1～6.
In above-mentioned formula (9), R33And R34Be each independently hydrogen atom, carbon number be 1～12 alkyl or cyclohexyl.A2For alkylene, penylene, naphthylene or vinylene that methylene, carbon number are 2～12.Wherein, above-mentioned methylene, carbon number are the alkylene of 2～12, penylene and naphthylene also can replace by alkyl, the halogen atom that carbon number is 1～6.
In above-mentioned formula (10), R35And R36Be each independently hydrogen atom, carbon number be 1～12 alkyl or cyclohexyl.A3For alkylene, penylene, naphthylene or vinylene that methylene, carbon number are 2～12.Wherein, above-mentioned methylene, carbon number are the alkylene of 2～12, penylene and naphthylene also can replace by alkyl, the halogen atom that carbon number is 1～6.
Amide compound represented by above-mentioned formula (8) is the compound in molecule with an amido link.Its concrete example include, for example acetamide, N-methylacetamide, N-ethyl acetamide, phthalamic acid, acrylamide, Benzoylamide, naphthalenecarboxamide, nicotiamide, Pyrazinamide etc..
The viewpoint improved from the storage stability that can make at room temperature, the thermostability of the colored pattern etc. of gained, voltage retention etc. considers, preferred acetamide, N-methylacetamide, phthalamic acid in those compounds.
Compound represented by above-mentioned formula (9) and formula (10) is the compound in molecule with 2 amido links.Its concrete example include, for example phthalic amide, isophtalamide, terephthalamide, Malondiamide, succinamide, N; N '-diacetyl-p-phenylenediamine, N; N '-diacetyl-hexamethylene diamine, N, N '-diacetyl-dodecyl methylene diamine etc..
Consider from the viewpoint of storage stability and hardening at subcritical temerature can be taken into account with high level, preferred isophtalamide, adipamide, N, N '-diacetyl-p-phenylenediamine, N, N '-diacetyl-hexamethylene diamine in those compounds.
Amide compound can be used alone or two or more mixing be used.As the content ratio of the amide compound in colored composition, for [I] alkali soluble resins 100 weight portion, it is preferably 0.1 weight portion～10 weight portion, more preferably 0.5 weight portion～5 weight portion.By making the content ratio of amide compound be above-mentioned particular range, it is possible to take into account storage stability and the hardening at subcritical temerature of colored composition with higher level.
[mercaptan compound]
Mercaptan compound is the compound in 1 molecule with more than 2 sulfydryls.Just it is not particularly limited as long as mercaptan compound has more than 2 sulfydryls in 1 molecule, at least one of the group selecting the compound represented by free following formula (11) to constitute can be used.
[changing 19]
In formula (11), R37It is the alkylene of 2～10 for methylene, carbon number.Wherein, part or all of the hydrogen atom of those bases can also be replaced by alkyl.Y1For singly-bound ,-CO-or O-CO-*.Wherein, with the key of * and R37Bond.N is the integer of 2～10.A4For also having the n valency alkyl that carbon number is 2～70 of one or more ehter bonds, or it is the base represented by following formula (12) when the situation that n is 3.
[changing 20]
In above-mentioned formula (12), R38～R40It is each independently methylene or carbon number is the alkylene of 2～6." * " represents key respectively.
As the compound represented by above-mentioned formula (11), it is typical that the carboxylate etc. of mercaptan carboxylic acid and polyhydric alcohol can be used.The mercaptan carboxylic acid constituting carboxylate include, for example TGA, 3-mercaptopropionic acid, 3-mercaptobutyric acid, 3-mercaptopentanoic acid etc..And, the polyhydric alcohol constituting carboxylate include, for example ethylene glycol, propylene glycol, trimethylolpropane, tetramethylolmethane, TEG, dipentaerythritol, BDO, tetramethylolmethane etc..
Compound represented by above-mentioned formula (11) is preferably trimethylolpropane tris (3-mercaptopropionic acid) ester, tetramethylolmethane four (3-mercaptopropionic acid) ester, double, two (3-mercaptopropionic acid) ester of TEG, dipentaerythritol six (3-mercaptopropionic acid) ester, tetramethylolmethane four (TGA) ester, 1, double, two (the 3-sulfydryl butyryl acyloxy) butane of 4-, tetramethylolmethane four (3-mercaptobutyric acid) ester, tetramethylolmethane four (3-mercaptopentanoic acid) ester, 1, 3, 5-tri-(3-sulfydryl butoxyethyl group)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone.
The compound in 1 molecule with more than 2 sulfydryls of mercaptan compound also can use the compound represented by following formula (13)～formula (15).
[changing 21]
[changing 22]
In above-mentioned formula (13), R41It is the alkylene of 2～20 for methylene or carbon number.R42For methylene or straight chain that carbon number is 2～6 or branch's alkylene.K is the integer of 1～20.
In above-mentioned formula (14), R43～R46It is each independently the base represented by hydrogen atom, hydroxyl or following formula (15).Wherein, R43～R46At least 1 be base represented by following formula (15).
[changing 23]
In above-mentioned formula (15), R47For methylene or straight chain that carbon number is 2～6 or branch's alkylene.
Mercaptan compound can be used alone or two or more mixing be used.As the content ratio of the mercaptan compound in colored composition, for [I] alkali soluble resins 100 weight portion, it is preferably 1 weight portion～20 weight portion, more preferably 5 weight portion～15 weight portions.By making the content ratio of mercaptan compound be above-mentioned particular range, it is possible to take into account storage stability and the hardening at subcritical temerature of colored composition with higher level.
[block isocyanate compound]
Block polyisocyanate compound is the compound making NCO and the compound (blocker) containing activity hydrogen-based react and becoming inertia at room temperature, if having the property that and it being heated, then blocker dissociates and regenerates NCO.Colored composition contains block polyisocyanate, to carry out isocyanate-hydroxyl cross-linking reaction as effective cross-linking agent such that it is able to take into account storage stability and the hardening at subcritical temerature of colored composition with high level.
Block polyisocyanate compound can be obtained by the polyisocyanate derivative by aliphatic or the alicyclic diisocyanate known reaction with the compound (blocker) of active hydrogen.
nullDiisocyanate include, for example tetramethylene diisocyanate、Pentane diisocyanate、Hexamethylene diisocyanate (HDI)、2，2，4-trimethyl-1，6-bis-isocyanate group hexane、2，4，4-trimethyl-1，6-bis-isocyanate group hexane、Lysinediisocyanate、Isophorone diisocyanate (IPDI)、1，Double; two (isocyanatomethyl) hexamethylene of 3-、4，4-dicyclohexyl methyl hydride diisocyanate、Norborene diisocyanate、Methylene phenylene diisocyanate、4，4 '-methyl diphenylene diisocyanate、1，5-naphthalene diisocyanate、Tolidine diisocyanate、Dimethylaniline isocyanates、1，4-tetramethylene diisocyanate、1，5-pentamethylene diisocyanate、1，6-hexamethylene diisocyanate、3-isocyanatomethyl-3，5，5-3-methyl cyclohexanol group diisocyanate etc..
As commercially available product, for instance:
With the oxime of butanone, NCO is carried out the block person of forming and can enumerate Duranate (registered trade mark) TPA-B80E, TPA-B80X, E402-B80T, MF-B60XN, MF-B60X, MF-B80M (being manufactured by industrial group of Asahi Chemical Industry above)；
With active methylene group, NCO is carried out the block person of forming and can enumerate Duranate (registered trade mark) MF-K60X (industrial group of Asahi Chemical Industry)；
There is the block body of the isocyanate compound of (methyl) acryloyl group and can enumerate Karenz (registered trade mark) MOI-BP, Karenz (registered trade mark) MOI-BM (being manufactured by Showa electrician company above).In those commercially available products, use Duranate (registered trade mark) E402-B80T, MF-K60X situation time show high pliability, by make with the mixing class of other compounds and use, can freely control its hardness, it is thus preferred to use.
The polyisocyanate derivative by diisocyanate include, for example fulminuric acid ester type polyisocyanate, biuret form polyisocyanate, carbamate types polyisocyanate, allophanic acid ester type polyisocyanate etc..The viewpoint of self-hardening considers, it is preferable that fulminuric acid ester type polyisocyanate.
Blocker include, for example alcohol compound, phenolic compound, active methylene group compounds, sulfur alcohol compound, amides compound, imide analog compounds, glyoxaline compound, pyrazole compound, carbamide compounds, oxime compound, aminated compounds, imine compound, pyridine compounds and their etc..
Alcohol compound include, for example methanol, ethanol, propanol, butanol, 2-Ethylhexyl Alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, Hexalin etc.；
Phenolic compound include, for example phenol, cresol, ethyl-phenol, butylphenol, nonyl phenol, dinonyl phenol, styrenated phenol, hydroxybenzoate etc.；
Active methylene group compounds include, for example dimethyl malenate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone,2,4-pentanedione etc.；
Sulfur alcohol compound include, for example butanethiol, lauryl mercaptan etc.；
Amides compound include, for example acetanilide, acetamide, epsilon-caprolactams, δ-valerolactam, butyrolactam etc.；
Imide analog compounds include, for example butanimide, maleimide etc.；
Glyoxaline compound include, for example imidazoles, 2-methylimidazole etc.；
Pyrazole compound include, for example 3-methylpyrazole, 3，5-dimethylpyrazole, 3,5-ethylpyrazol etc.；
Carbamide compounds include, for example carbamide, thiourea, ethylene-urea etc.；
Oxime compound include, for example formaldoxime, aldoxime, acetone oxime, diacetylmonoxime, cyclohexanone-oxime etc.；
Aminated compounds include, for example diphenylamine, aniline, carbazole etc.；
Imine compound include, for example Ethylenimine, polymine etc.；
Pyridine compounds and their include, for example 2 hydroxy pyrimidine, 2-hydroxyquinoline etc..
Block polyisocyanate compound can be used alone or two or more mixing be used.As the content ratio of the block polyisocyanate compound in colored composition, for [I] alkali soluble resins 100 weight portion, it is preferably 0.1 weight portion～10 weight portion, more preferably 0.5 weight portion～5 weight portion.By making the content ratio of block polyisocyanate compound be above-mentioned scope, it is possible to take into account storage stability and the hardening at subcritical temerature of colored composition with higher level.
[compound containing imidazole ring]
Compound containing imidazole ring can use at least one of the group selecting the compound represented by free following formula (16) to constitute.
[changing 24]
In above-mentioned formula (16), A5、A6、A7And R48It is each independently hydrogen atom or also can have the alkyl of the straight-chain that carbon number is 1～20 of substituent group, branch-like or ring-type.And, A6With A7Also can be interconnected and form ring.
A5、A6、A7And R48The alkyl of the represented straight-chain that carbon number is 1～20, branch-like or ring-type include, for example:
The carbon numbers such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, AI3-36122 base, AI3-28404 base are the alkyl of 1～20；
The carbon numbers such as cyclobutyl, cyclopenta, cyclohexyl are the cycloalkyl of 3～20；
The carbon numbers such as phenyl, toluyl groups, benzyl, methyl-benzyl, xylyl, sym-trimethylbenzene. base, naphthyl, anthryl are the aryl of 6～20；
The crosslinking ester ring type alkyl etc. that carbon number is 6～20 such as norborny, tricyclodecyl, tetracyclododecyl group, adamantyl, methyl adamantane base, ethyl adamantyl, butyl adamantyl.
Above-mentioned alkyl also can be replaced, and the concrete example of this substituent group can be enumerated:
Hydroxyl；
Carboxyl；
The carbon numbers such as hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl are the hydroxy alkyl of 1～4；
The carbon numbers such as methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, 2-methyl propoxyl group, 1-methyl propoxyl group, tert-butoxy are the alkoxyl of 1～4；
Cyano group；
The carbon numbers such as cyano methyl, 2-cyano ethyl, 3-cyanopropyl, 4-cyanobutyl are the cyanoalkyl of 2～5；
The carbon numbers such as methoxycarbonyl, ethoxy carbonyl, tert-butoxycarbonyl are the alkoxy carbonyl of 2～5；
The carbon numbers such as methoxyvarbonyllnethoxy, ethoxycarbonyl methoxy, tert-butoxycarbonyl methoxyl group are the Alkoxycarbonylalkoxy of 3～6；
The halogen atom such as fluorine, chlorine；
The fluoroalkyls etc. such as methyl fluoride, trifluoromethyl, pentafluoroethyl group.
Above-mentioned A6With A7Saturated or the undersaturated nitrogen heterocyclic ring that ring that is interconnected and that formed preferably enumerates aromatic rings, carbon number is 2～20.A6With A7Interconnected and formed the situation that ring is phenyl ring time can enumerate the compound represented by following formula (17) containing the compound of imidazole ring.
[changing 25]
In above-mentioned formula (17), R48And A5With above-mentioned formula (16) synonym.R49～R52It is each independently the alkyl also can with the straight-chain that carbon number is 1～20 of substituent group, branch-like or ring-type.It addition, R49～R52Represented alkyl can enumerate the base same with the alkyl in above-mentioned formula (16).
Compound containing imidazole ring is preferably 2-Phenylbenzimidazole, 2-methylimidazole, 2-tolimidazole.Compound containing imidazole ring can be used alone or two or more mixing be used.As the content ratio of the compound containing imidazole ring, for [I] alkali soluble resins 100 weight portion, it is preferably 0.1 weight portion～10 weight portion, more preferably 0.5 weight portion～5 weight portion.By making the content ratio of the compound containing imidazole ring be above-mentioned particular range, it is possible to take into account storage stability and the hardening at subcritical temerature of colored composition with higher level.
<other any compositions>
The colored composition used in the colored filter manufacture of this embodiment is except above-mentioned [I] alkali soluble resins, [II] polymerizable compound, [III] polymerization initiator, [IV] coloring agent and [V] compound (sclerosing agent), it is also possible to optionally contain other any compositions such as surfactant, preserving stabilizer, then auxiliary agent, thermostability accelerator in the scope of effect of the present invention not undermining.Those each any compositions can be used alone and also can two or more mixing be used.Hereinafter each composition is described in detail.
[surfactant]
Surfactant can with so that the film formative of colored composition improves further.Surfactant include, for example fluorine class surfactant, silicone surfactant and other surfactants.
Fluorine class surfactant has fluoroalkyl and/or the compound of halothane support preferably at least any part of end, main chain and side chain.
The commercially available product of fluorine class surfactant include, for example Ftergent (registered trade mark) FT-100, FtergentFT-110, FtergentFT-140A, FtergentFT-150, FtergentFT-250, FtergentFT-251, FtergentFT-300, FtergentFT-310, FtergentFT-400S, Ftergent (registered trade mark) FTX-218, FtergentFTX-251 (being manufactured above) etc. by Neos company.
nullThe commercially available product of silicone surfactant include, for example ToraySiliconeDC3PA、ToraySiliconeDC7PA、ToraySiliconeSH11PA、ToraySiliconeSH21PA、ToraySiliconeSH28PA、ToraySiliconeSH29PA、ToraySiliconeSH30PA、ToraySiliconeSH-190、ToraySiliconeSH-193、ToraySiliconeSZ-6032、ToraySiliconeSF-8428、ToraySiliconeDC-57、ToraySiliconeDC-190 is (above by DOW CORNING Dong Li silica gel company (DowCorningToraySiliconeCo.，Ltd.) manufacture) etc..
Make consumption as surfactant, for [I] alkali soluble resins 100 weight portion, be preferably below 1.0 weight portions, more preferably below 0.7 weight portion.If surfactant make consumption more than 1.0 weight portions, then become easily to produce film uneven.
[preserving stabilizer]
Preserving stabilizer include, for example sulfur, quinones, hydroquinone type, polyoxy compounds, amine, nitro nitroso compound etc., more specifically can enumerate 4-methoxyphenol, N-nitroso-group-N-Phenylhydroxylamine aluminum etc..
Make consumption as preserving stabilizer, for [I] alkali soluble resins 100 weight portion, be preferably below 3.0 weight portions, more preferably below 1.0 weight portions.If the allotment amount of preserving stabilizer is more than 3.0 weight portions, the then situation that there is light sensitivitys reduction and cause pattern form to deteriorate.
[then auxiliary agent]
Then auxiliary agent can with so that the colored pattern of gained and the adherence of colored filter and substrate improve further.Then auxiliary agent preferably has the functional silanes coupling agent of carboxyl, methylacryloyl, vinyl, NCO, Oxyranyle isoreactivity functional group; include, for example trimethoxy silane yl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-NCO propyl-triethoxysilicane, γ-glycidoxypropyltrimewasxysilane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc..
Make consumption as then auxiliary agent, for [I] alkali soluble resins 100 weight portion, be preferably below 20 weight portions, more preferably below 15 weight portions.If then auxiliary agent make consumption more than 20 weight portions, then there is the tendency becoming easily to produce development residual.
<modulator approach of colored composition>
The colored composition used in the colored filter manufacture of this embodiment can by by [I] alkali soluble resins, [II] polymerizable compound, [III] polymerization initiator, [IV] coloring agent, [V] compound (sclerosing agent) and optionally and add other any uniform component mixing and modulate.This colored composition is preferably dissolved in suitable solvent and uses with solution shape.
As the solvent used in the modulation of colored composition, use the solvent that can dissolve required composition and any composition equably and not react with each composition.This kind of solvent can be enumerated with above-mentioned as can be used for manufacturing the solvent of [I] alkali soluble resins and the identical solvent of illustration person.
In those solvents, dissolubility from each composition, reactivity with each composition, the viewpoints such as the easiness that film is formed consider, include, for example: glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol list positive propyl ether, dipropylene glycol mono-n-butyl ether, Tripropylene glycol monomethyl Ether, (gathering) alkane glycol monoalkyl ethers such as tripropylene glycol list ether；
(gathering) alkane glycol monoalkyl ether acetate esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol propyl ether acetas, ethylene glycol mono-n-butyl ether acetas, diethylene glycol monomethyl ether acetas, diethylene glycol monoethyl ether acetas, diethylene glycol list positive propyl ether acetas, diethylene glycol mono-n-butyl ether acetas, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, acetic acid-3-methoxybutyl, acetic acid-3-methyl-3-methoxybutyl；
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether, oxolane；
The ketones such as butanone, Ketohexamethylene, 2-heptanone, 3-heptanone, DAA (4-hydroxy-4-methyl pentane-2-ketone), 4-hydroxy-4-methyl hexane-2-one；
The oxalic acid esters such as propylene-glycol diacetate, 1,3 butylene glycol diacetate esters, 1,6-hexanediol diacetate esters；
The lactic acid alkyl ester class such as methyl lactate, ethyl lactate；
Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, acetic acid-3-methoxybutyl, acetic acid-3-methyl-3-methoxybutyl, n-butyl propionate, acetic acid-3-methoxybutyl, propanoic acid-3-methyl-3-methoxybutyl, ethyl n-butyrate., propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butanoic acid, hydroxyl ethyl acetate, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, methyl pyruvate, ethyl pyruvate, acetone acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-hydroxy-2-methyl ethyl propionate, 2-hydroxy-3-methyl methyl butyrate, other esters such as 2-Oxobutyric acid ethyl；
Toluene, dimethylbenzene etc. are aromatic hydrocarbon based；
The amide-types etc. such as N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide.
In those solvents, from dissolubility, pigment-dispersing, the viewpoints such as coating consider, it is preferably propylene glycol monomethyl ether, dihydroxypropane single-ether, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, acetic acid-3-methoxybutyl, diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, Ketohexamethylene, 2-heptanone, 3-heptanone, 1, 3-butanediol diacetate esters, 1, 6-hexanediol diacetate esters, ethyl lactate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, propanoic acid-3-methyl-3-methoxy butyl acrylate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl n-butyrate., isopropyl isobutyrate, the positive butyl ester of butanoic acid, ethyl pyruvate.Solvent can be used alone or use two or more.
It addition, also can with above-mentioned solvent together and with the high boiling solvent such as benzylisoeugenol, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-capryl alcohol, 1 nonyl alcohol, acetic acid benzyl ester, ethyl benzoate, diethyl oxalate, ethyl maleate., gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethyleneglycol monophenylether acetas.Above-mentioned high boiling solvent can be used alone or use two or more.
The content of solvent indefinite, consider from viewpoints such as the coating of the colored composition of gained, stability, and the total concentration removing each composition of the solvent of colored composition preferably becomes the amount of 5wt%～50wt%, more preferably becomes the amount of 10wt%～40wt%.When colored composition is modulated to the situation of solution state, solid concentration (composition beyond solvent shared in constituent solution) can be set as any concentration (such as 5wt%～50wt%) according to the value of application target or desired thickness etc..Preferred solid concentration according to forming the forming method of film and different on substrate, in hereinafter it being described.The microfilter etc. that the constituent solution so modulated can use aperture to be about 0.5 μm is supplied to use after being filtered.
The colored composition of above composition and modulator approach may utilize hardening at subcritical temerature and forms colored pattern.Specifically, even if under the hardening temperature below 200 DEG C, further under hardening temperature below 180 DEG C, the colored pattern with good reliabilitys such as solvent resistances also can be obtained.And, available hardening at subcritical temerature and the colored filter of this embodiment is provided.
Secondly, the colored filter of this embodiment comprises the protecting film being located on colored pattern.This protecting film uses the 1st radiation-sensitive resin composition to be formed on colored pattern.Hereinafter, the 1st radiation-sensitive resin composition used in the formation of the protecting film of the colored filter of this embodiment is illustrated.
<the 1st radiation-sensitive resin composition>
The 1st radiation-sensitive resin composition used in the formation of the protecting film of the colored filter of this embodiment contains [A] compound, [B] polymerizable compound, [C] polymerization initiator and [D] compound, also can contain any composition further.1st radiation-sensitive resin composition can by utilizing the exposure of radioactivity-sensitive, development to be readily formed fine and exquisite pattern, thus realizing hardening at subcritical temerature.In a word, there is storage stability and there is sufficient resolution and lonizing radiation light sensitivitys.Hereinafter, each composition is described in detail.
<[A] compound>
[A] compound contained in 1st radiation-sensitive resin composition is the compound with epoxy radicals.[A] compound include, for example the compound etc. in 1 molecule with more than 23,4-epoxycyclohexyls.
nullThere are more than 23 in 1 molecule，The compound of 4-epoxycyclohexyl include, for example 3，4-epoxycyclohexyl-methyl-3 '，4 '-7-oxa-bicyclo[4.1.0 formic acid esters、2-(3，4-epoxycyclohexyl-5，5-spiral shell-3，4-epoxy) a hexamethylene-dioxane、Double; two (3，4-epoxycyclohexyl-methyl) adipate ester、Double; two (3，4-epoxy-6-methylcyclohexylmethyl) adipate ester、3，4-epoxy-6-methylcyclohexyl-3 '，4 '-epoxy-6 '-cyclohexanecarboxylic acid ester、Di-2-ethylhexylphosphine oxide (3，4-7-oxa-bicyclo[4.1.0)、Bicyclopentadiene diepoxide、The two (3 of ethylene glycol，4-epoxycyclohexyl-methyl) ether、Ethylene double; two (3，4-7-oxa-bicyclo[4.1.0 formic acid) ester、Lactone-modified 3，4-epoxycyclohexyl-methyl-3 '，4 '-7-oxa-bicyclo[4.1.0 formic acid esters etc..
Other [A] compound include, for example:
The diglycidyl ether of the bisphenol compounds such as bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, bisphenol-S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, A Hydrogenated Bisphenol A F diglycidyl ether, hydrogenated bisphenol A D diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether；
The polyglycidyl ether of the polyhydric alcohol such as BDDE, 1,6-hexanediol diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether；
The polyglycidyl ether of the polyether polyol of gained by addition one kind or two or more alkylene oxide on the aliphatic polyols such as ethylene glycol, propylene glycol, glycerol；
Phenol novolak type epoxy；
Cresol novolak type epoxy resin；
Many phenol-type epoxy resins；
Cyclic aliphatic epoxy resin；
The 2-glycidyl ester of aliphatic long-chain binary acid；
The ethylene oxidic ester of higher fatty acids；
Epoxidised soybean oil, epoxidation Semen Lini wet goods.
Commercially available product as those, for instance:
Bisphenol A type epoxy resin can enumerate Epikote1001, Epikote1002, Epikote1003, Epikote1004, Epikote1007, Epikote1009, Epikote1010, Epikote828 (being manufactured above) etc. by epoxy resin company of Japan (JapanEpoxyResinsCo., Ltd)；
Bisphenol f type epoxy resin can enumerate Epikote807 (epoxy resin company of Japan) etc.；
Phenol novolak type epoxy can enumerate Epikote152, Epikote154, Epikote157S65 (being manufactured above), EPPN201, EPPN202 (being manufactured by chemical medicine company of Japan above) etc. by epoxy resin company of Japan；
Cresol novolak type epoxy resin can enumerate EOCN (registered trade mark) 102, EOCN103S, EOCN104S, EOCN1020, EOCN1025, EOCN1027 (being manufactured above), Epikote180S75 (epoxy resin company of Japan) etc. by chemical medicine company of Japan；
Many phenol-type epoxy resins can enumerate Epikote1032H60, EpikoteXY-4000 (being manufactured above) etc. by epoxy resin company of Japan；
nullCyclic aliphatic epoxy resin can enumerate CY-175、CY-177、CY-179、AralditeCY-182、AralditeCY-192、AralditeCY-184 (is manufactured by Ciba company limited) above、ERL-4234、ERL-4299、ERL-4221、ERL-4206 (is manufactured by U.C.C company) above、Shodyne509 (Showa electrician company)、Epiclon200、Epiclon400 (is manufactured by big Japanese ink company) above、Epikote871、Epikote872 (is manufactured by epoxy resin company of Japan) above、ED-5661、ED-5662 (is manufactured by Celanesecoating company) above；
Aliphatic polyglycidyl ether can enumerate Epolight100MF (chemical company of common prosperity society), EPIOLTMP (Nof Corp.) etc..
Preferred phenol novolak type epoxy and many phenol-type epoxy resins in those.
When above-mentioned illustrated [A] compound together contains the situation in radiation-sensitive composition with [A] compound as the copolymer with carboxyl described later, consumption is made as above-mentioned illustrated [A] compound, relative to described later as have carboxyl copolymer [A] compound 100 weight portion for, it is preferably below 50 weight portions, it is more preferably below 30 weight portions, it is particularly preferred to be in the scope of 2 weight portion～15 weight portions.
[A] compound is preferably polymer, and more preferably this polymer has carboxyl further.And, [A] compound more preferably has the copolymer of carboxyl.[A] compound has the structure of carboxyl, and therefore the 1st radiation-sensitive resin composition can form the more excellent cured films such as thermostability, light resistance, chemical-resistant, absorbance, flatness.
[A] compound can use the copolymer comprising the construction unit formed by least one of the group selecting free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute and the construction unit formed by the unsaturated compound containing epoxy radicals.In this case, [A] compound can use the copolymer identical with [I] alkali soluble resins contained in the colored composition used in the colored filter manufacture of above-mentioned embodiment.Such as can use at least one ((I-1) compound) of the group that above-mentioned (I-1) select free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute and the alkali soluble resins of (I-2) unsaturated compound ((I-2) compound) copolymerization containing epoxy radicals.
<[B] polymerizable compound>
[B] polymerizable compound is the polymerizable compound with ethylene unsaturated bond.[B] polymerizable compound can use the compound identical with [II] polymerizable compound contained in the colored composition used in the colored filter manufacture of above-mentioned embodiment.
[B] polymerizable compound can be used alone or two or more mixing be used.Content ratio as [B] polymerizable compound in radiation-sensitive resin composition, relative to as have carboxyl copolymer [A] compound 100 weight portion for be preferably 20 weight portion～200 weight portions, more preferably 40 weight portion～160 weight portions.By making the content ratio of [B] polymerizable compound be above-mentioned scope, even if radiation-sensitive resin composition can form adhesion excellence and also have the cured film of sufficient hardness under low light exposure, and excellent protecting film can be provided.
<[C] polymerization initiator>
[C] polymerization initiator is radioactivity-sensitive polymerization initiator, is can sense lonizing radiation and produce can the composition of spike of initiated polymerization.The compound that [III] polymerization initiator contained in the colored composition that can use and use in the colored filter manufacture of above-mentioned embodiment is identical.
[C] polymerization initiator can be used alone or two or more mixing be used.Content ratio as [C] polymerization initiator in radiation-sensitive resin composition, relative to as have carboxyl copolymer [A] compound 100 weight portion for, it is preferably 1 weight portion～40 weight portion, more preferably 5 weight portion～30 weight portions.By making the content ratio of [C] polymerization initiator be 1 weight portion～40 weight portion, even if the 1st radiation-sensitive resin composition also can form the cured film with high hardness and adhesion when the situation of low light exposure, it is possible to provide excellent protecting film.
<[D] compound>
The hardening of cured film when the 1st radiation-sensitive resin composition used in the formation of the protecting film of the colored filter of this embodiment can realize the hardening at subcritical temerature of radiation-sensitive resin composition by containing [D] compound with amino and electron-withdrawing group promotes.In a word, also can realize storage stability, additionally be able to the voltage retention keeping comprising the liquid crystal display cells of colored filter (described colored filter has rewarding cured film) with high level.
[D] compound is chosen from least one compound of the group that the compound represented by above-mentioned formula (1) and formula (2) is constituted.About structure detailed of the compound represented by above-mentioned formula (1) and formula (2), during contained in above-mentioned colored composition is described [V] compound, have been carried out explanation.Therefore, R7～R16In at least 1 be amino, all or part of of the hydrogen atom of this amino also can be replaced by the alkyl that carbon number is 1～6, during the situation of [D] compound used in for the 1st radiation-sensitive resin composition, all or part of of the hydrogen atom of this amino also can be replaced by the alkylene that carbon number is 2～6.
As [D] compound,
nullPreferably 2，Double; two (4-aminophenyl) HFC-236fa of 2-、2，Double; two (4-aminophenyl) succinonitrile of 3-、4，4 '-diaminobenzophenone、4，4 '-diaminobenzoic acid phenyl ester、4，4 '-diamino diphenyl sulfone、1，4-diaminourea-2-chlorobenzene、1，4-diaminourea-2-bromobenzene、1，4-diaminourea-2-iodobenzene、1，4-diaminourea-2-Nitrobenzol、1，4-diaminourea-2-trifluoromethylbenzene、2，5-diaminourea benzonitrile、2，5-diaminobenzene ethyl ketone、2，5-diaminobenzoic acid、2，2 '-dichloro-benzidine、2，2 '-'-dibromobiphenyl amine、2，2 '-diiodobiphenyl amine、2，2 '-dinitrobenzidine、2，2 '-bis-(trifluoromethyl) benzidine、3-amino phenyl sulfonyl acetoacetic ester、3，5-bis trifluoromethyl-1，2-diaminobenzene、4-aminonitrobenzene、N，N-dimethyl-4-nitroaniline，More preferably 4，4 '-diamino diphenyl sulfone、2，Double; two (4-aminophenyl) HFC-236fa of 2-、2，2 '-bis-(trifluoromethyl) benzidine、3-amino phenyl sulfonyl acetoacetic ester、3，5-bis trifluoromethyl-1，2-diaminobenzene、4-aminonitrobenzene、N，N-dimethyl-4-nitroaniline.
Content ratio as [D] compound in the 1st radiation-sensitive resin composition, relative to as have carboxyl copolymer [A] compound 100 weight portion for, it is preferably 0.1 weight portion～20 weight portion, more preferably 0.2 weight portion～10 weight portion.By making the content ratio of [D] compound be 0.1 weight portion～10 weight portion, it may be achieved the hardening of the protecting film formed by the 1st radiation-sensitive resin composition promotes.In a word, make the storage stability of the 1st radiation-sensitive resin composition improve, additionally be able to the voltage retention keeping comprising the liquid crystal display cells of colored filter (described colored filter has rewarding protecting film) with high level.
<other any compositions>
The 1st radiation-sensitive resin composition used in the formation of the protecting film of the colored filter of this embodiment, except above-mentioned [A] compound, [B] polymerizable compound, [C] polymerization initiator and [D] compound, also can optionally contain the arbitrarily composition such as [J-1] then auxiliary agent, [J-2] surfactant, [J-3] preserving stabilizer and [J-4] thermostability accelerator in the scope not undermining desired effect.Those each any compositions can be used alone and also can two or more mixing be used.Hereinafter, sequentially described in detail.
[[J-1] then auxiliary agent]
[J-1] then auxiliary agent can with so that the protecting film of gained and the adherence of substrate improve further.This kind [J-1] then auxiliary agent can use the compound identical with the then auxiliary agent in other any compositions of above-mentioned colored composition.
Make consumption as [J-1] then auxiliary agent, relative to as have carboxyl copolymer [A] compound 100 weight portion for, it is preferred to below 20 weight portions, more preferably below 15 weight portions.[if J-1] then auxiliary agent make consumption more than 20 weight portions, then there is the tendency becoming easily to produce development residual.
[[J-2] surfactant]
[J-2] surfactant can with so that the film formative of the 1st radiation-sensitive resin composition improves further.[J-2] surfactant include, for example fluorine class surfactant, silicone surfactant and other surfactants, can use the compound identical with the surfactant in other any compositions of above-mentioned colored composition.
Make consumption as [J-2] surfactant, relative to as have carboxyl copolymer [A] compound 100 weight portion for be preferably below 1.0 weight portions, more preferably below 0.8 weight portion.[if J-2] surfactant make consumption more than 1.0 weight portions, then become easily to produce film uneven.
[[J-3] preserving stabilizer]
[J-3] preserving stabilizer can use the compound identical with the preserving stabilizer in other any compositions of above-mentioned colored composition, include, for example sulfur, quinones, hydroquinone type, polyoxy compounds, amine, nitro nitroso compound etc., more specifically can enumerate 4-methoxyphenol, N-nitroso-group-N-Phenylhydroxylamine aluminum etc..
Make consumption as [J-3] preserving stabilizer, relative to as have carboxyl copolymer [A] compound 100 weight portion for, it is preferred to below 3.0 weight portions, more preferably below 1.0 weight portions.If the allotment amount of [J-3] preserving stabilizer is more than 3.0 weight portions, then the situation that the light sensitivitys that there is the 1st radiation-sensitive resin composition reduces and causes pattern form to deteriorate.
[[J-4] thermostability accelerator]
[J-4] thermostability accelerator can use the compound identical with the heat-resisting stabilizing agent in other any compositions of above-mentioned colored composition.
Make consumption as [J-4] thermostability accelerator, relative to as have carboxyl copolymer [A] compound 100 weight portion for be preferably below 50 weight portions, more preferably below 30 weight portions.If the allotment amount of [J-4] thermostability accelerator is more than 50 weight portions, then the situation that the light sensitivitys that there is the 1st radiation-sensitive resin composition reduces and causes pattern form to deteriorate.
<modulation of the 1st radiation-sensitive resin composition>
The 1st radiation-sensitive resin composition forming the protecting film that the colored filter of this embodiment has can be modulated in the following way: by [A] compound, [B] polymerizable compound, [C] polymerization initiator and [D] compound, and any composition optionally is mixed with predetermined ratio in the scope not undermining desired effect.1st radiation-sensitive resin composition is preferably dissolved in suitable solvent under solution state and uses.
The solvent used in the modulation of the 1st radiation-sensitive resin composition can use the solvent that can dissolve or disperse [A] compound, [B] polymerizable compound, [C] polymerization initiator, [D] compound and any composition equably and not react with each composition.This kind of solvent can enumerate the solvent used in the modulation of the colored composition of the colored filter as above-mentioned embodiment and the solvent illustrated.Solvent can be used alone or two or more mixing be used.
As the solvent of the 1st radiation-sensitive resin composition, when and during by the situation of high boiling solvent, it makes consumption be preferably below 50wt% for total solvent amount, more preferably below 40wt%, it is particularly preferred to for below 30wt%.When to make consumption be below 50wt% of high boiling solvent, the thickness homogeneity of film, light sensitivitys and residual film ratio become good.
When the 1st radiation-sensitive resin composition is modulated to the situation of solution state, solid concentration (composition beyond solvent shared in constituent solution) can be set as any concentration (such as 5wt%～50wt%) according to the value of application target or desired thickness etc..As preferred solid concentration, different because forming the forming method of film on substrate, in hereinafter it being described.About so constituent solution modulated, after the microfilter etc. that aperture can be used to be about 0.5 μm is filtered, it is supplied to use.
1st radiation-sensitive resin composition of above composition and modulator approach may utilize hardening at subcritical temerature and forms protecting film.Specifically, even under the hardening temperature below 200 DEG C, be, under the hardening temperature of less than 180 DEG C, also can obtain the protecting film with good reliability furthermore.And, available hardening at subcritical temerature and the colored filter of this embodiment is provided.
Secondly, the colored filter of this embodiment has ITO electrode on protecting film.ITO electrode uses the known methods such as sputtering method to form ito film on protecting film and formed.It addition, the transparency electrode on colored pattern is except ITO, the transparent material that visible ray has high absorbance and electric conductivity can be used to constitute.Such as can use IZO (IndiumZincOxide, indium zinc oxide) or ZnO (zinc oxide) etc. and constitute.
Secondly, the colored filter of this embodiment comprises the column spacer in the ITO electrode being uprightly arranged on protecting film.This distance piece can use the 2nd radiation-sensitive resin composition to be formed.Hereinafter, the 2nd radiation-sensitive resin composition used in the formation of the distance piece of the colored filter of this embodiment is illustrated.
<the 2nd radiation-sensitive resin composition>
The 2nd radiation-sensitive resin composition used in the formation of the distance piece of the colored filter of this embodiment contains [E] compound, [F] polymerizable compound, [G] polymerization initiator and [H] compound, also can contain any composition further.2nd radiation-sensitive resin composition can by utilizing the exposure of radioactivity-sensitive, development to be readily formed fine and exquisite pattern, thus realizing hardening at subcritical temerature.In a word, there is storage stability, and there is sufficient resolution and lonizing radiation light sensitivitys.Hereinafter, each composition is described in detail.
<[E] compound>
As [E] compound contained in the 2nd radiation-sensitive resin composition, it is considered preferred to the patterning of the distance piece of the colored filter of this embodiment and select alkali soluble resins.Alkali soluble resins if having the resin of alkali-developable owing to having carboxyl, is then not particularly limited.And, the compound with epoxy radicals can be contained in alkali soluble resins.
The compound with epoxy radicals include, for example the compound etc. in 1 molecule with more than 2 Oxyranyles, expoxy propane base, glycidyl, 3,4-epoxycyclohexyls.
nullThere are more than 23 in 1 molecule，The compound of 4-epoxycyclohexyl include, for example 3，4-epoxycyclohexyl-methyl-3 '，4 '-7-oxa-bicyclo[4.1.0 formic acid esters、2-(3，4-epoxycyclohexyl-5，5-spiral shell-3，4-epoxy) a hexamethylene-dioxane、Double; two (3，4-epoxycyclohexyl-methyl) adipate ester、Double; two (3，4-epoxy-6-methylcyclohexylmethyl) adipate ester、3，4-epoxy-6-methylcyclohexyl-3 '，4 '-epoxy-6 '-cyclohexanecarboxylic acid ester、Di-2-ethylhexylphosphine oxide (3，4-7-oxa-bicyclo[4.1.0)、Bicyclopentadiene diepoxide、The two (3 of ethylene glycol，4-epoxycyclohexyl-methyl) ether、Ethylene double; two (3，4-7-oxa-bicyclo[4.1.0 formic acid) ester、Lactone-modified 3，4-epoxycyclohexyl-methyl-3 '，4 '-7-oxa-bicyclo[4.1.0 formic acid esters etc..
1 molecule has more than 2 expoxy propane bases (1,3-epoxy construction) compound include, for example Isosorbide-5-Nitrae-bis-[(3-ethyl-3-expoxy propane ylmethoxy) methyl] benzene, double; two { [1-ethyl (3-expoxy propane base)] methyl } ether, double; two (3-ethyl-3-expoxy propane ylmethyl) ether etc..
As other epoxides that can contain in [E] compound, the compound with glycidyl include, for example:
The diglycidyl ether of the bisphenol compounds such as bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, bisphenol-S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, A Hydrogenated Bisphenol A F diglycidyl ether, hydrogenated bisphenol A D diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether；
The polyglycidyl ether of the polyhydric alcohol such as BDDE, 1,6-hexanediol diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether；
The polyglycidyl ether of the polyether polyol of gained by addition one kind or two or more alkylene oxide on the aliphatic polyols such as ethylene glycol, propylene glycol, glycerol；
Phenol novolak type epoxy；
Cresol novolak type epoxy resin；
Many phenol-type epoxy resins；
Cyclic aliphatic epoxy resin；
The 2-glycidyl ester of aliphatic long-chain binary acid；
The ethylene oxidic ester of higher fatty acids；
Epoxidised soybean oil, epoxidation Semen Lini wet goods.
Commercially available product as those, for instance:
Bisphenol A type epoxy resin can enumerate Epikote1001, Epikote1002, Epikote1003, Epikote1004, Epikote1007, Epikote1009, Epikote1010, Epikote828 (being manufactured above) etc. by epoxy resin company of Japan；
Bisphenol f type epoxy resin can enumerate Epikote807 (epoxy resin company of Japan) etc.；
Phenol novolak type epoxy can enumerate Epikote152, Epikote154, Epikote157S65 (being manufactured above), EPPN201, EPPN202 (being manufactured by chemical medicine company of Japan above) etc. by epoxy resin company of Japan；
Cresol novolak type epoxy resin can enumerate EOCN (registered trade mark) 102, EOCN103S, EOCN104S, EOCN1020, EOCN1025, EOCN1027 (being manufactured above), Epikote180S75 (epoxy resin company of Japan) etc. by chemical medicine company of Japan；
Many phenol-type epoxy resins can enumerate Epikote1032H60, EpikoteXY-4000 (being manufactured above) etc. by epoxy resin company of Japan；
nullCyclic aliphatic epoxy resin can enumerate CY-175、CY-177、CY-179、AralditeCY-182、AralditeCY-192、AralditeCY-184 (is manufactured by Ciba company limited) above、ERL-4234、ERL-4299、ERL-4221、ERL-4206 (is manufactured by U.C.C company) above、Shodyne509 (Showa electrician company)、Epiclon200、Epiclon400 (is manufactured by big Japanese ink company) above、Epikote871、Epikote872 (is manufactured by epoxy resin company of Japan) above、ED-5661、ED-5662 (is manufactured by Celanesecoating company) above；
Aliphatic polyglycidyl ether can enumerate Epolight100MF (chemical company of common prosperity society), EPIOL (registered trade mark) TMP (Nof Corp.) etc..
Preferred phenol novolak type epoxy and many phenol-type epoxy resins in those.
The alkali soluble resins as [E] compound contained in 2nd radiation-sensitive resin composition can use the alkali soluble resins of the copolymer comprising following construction unit: the construction unit that construction unit that (E-1) is formed by least one ((E-1) compound) of the group selecting free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute, (E-2) are formed by the unsaturated compound ((E-2) compound) containing epoxy radicals.And, the copolymer identical with [I] alkali soluble resins contained in the colored composition used in the colored filter manufacture of this above-mentioned embodiment can be used.At least one ((I-1) compound) of above-mentioned (I-1) group selecting free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute such as can be used as (E-1) compound, use (I-2) unsaturated compound ((I-2) compound) containing epoxy radicals as (E-2) compound.And, the alkali soluble resins of the copolymer comprising following construction unit can be used as the alkali soluble resins of [E] compound: the construction unit that formed by (I-1) compound, the construction unit formed by (I-2) compound.
<[F] polymerizable compound>
[F] polymerizable compound is the polymerizable compound with ethylene unsaturated bond.And, [F] polymerizable compound can use the compound identical with [II] polymerizable compound contained in the colored composition used in the colored filter manufacture of this above-mentioned embodiment.
[F] polymerizable compound can be used alone or two or more mixing be used.As the content ratio of [F] polymerizable compound in the 2nd radiation-sensitive resin composition, for [E] compound 100 weight portion, it is preferably 20 weight portion～200 weight portions, more preferably 40 weight portion～160 weight portions.By making the content ratio of [F] polymerizable compound be above-mentioned scope, even if the 2nd radiation-sensitive resin composition can form adhesion excellence and also have the cured film of sufficient hardness under low light exposure, and excellent distance piece can be provided.
<[G] polymerization initiator>
[G] polymerization initiator is radioactivity-sensitive polymerization initiator.[G] polymerization initiator can use the compound identical with [III] polymerization initiator contained in the colored composition used in the colored filter manufacture of this above-mentioned embodiment.
[G] polymerization initiator can be used alone or two or more mixing be used.As the content ratio of [G] polymerization initiator in the 2nd radiation-sensitive resin composition, for [F] compound 100 weight portion, it is preferably 1 weight portion～40 weight portion, more preferably 5 weight portion～30 weight portions.By making the content ratio of [G] polymerization initiator be 1 weight portion～40 weight portion, even if the 2nd radiation-sensitive resin composition can form the cured film also in low light exposure when with high hardness and adhesion, and the distance piece of excellence can be formed.
<[H] compound>
The 2nd radiation-sensitive resin composition used in the formation of the distance piece of the colored filter of this embodiment can realize the hardening at subcritical temerature by the 2nd radiation-sensitive resin composition by containing [H] compound with amino and electron-withdrawing group and promote the hardening of cured film.In a word, also can realize storage stability, additionally be able to the voltage retention keeping comprising the liquid crystal display cells of colored filter (described colored filter has rewarding distance piece) with high level.
[H] compound is chosen from least one compound of the group that the compound represented by above-mentioned formula (1) and formula (2) is constituted.About structure detailed of the compound represented by formula (1) and formula (2), during contained in above-mentioned colored composition is described [V] compound, have been carried out explanation.Therefore, R7～R16In at least 1 be amino, all or part of of the hydrogen atom of this amino also can be replaced by the alkyl that carbon number is 1～6, during the situation of [H] compound used in for the 2nd radiation-sensitive resin composition, all or part of of the hydrogen atom of this amino also can be replaced by the alkylene that carbon number is 2～6.
As [H] compound,
nullPreferably 2，Double; two (4-aminophenyl) HFC-236fa of 2-、2，Double; two (4-aminophenyl) succinonitrile of 3-、4，4 '-diaminobenzophenone、4，4 '-diaminobenzoic acid phenyl ester、4，4 '-diamino diphenyl sulfone、1，4-diaminourea-2-chlorobenzene、1，4-diaminourea-2-bromobenzene、1，4-diaminourea-2-iodobenzene、1，4-diaminourea-2-Nitrobenzol、1，4-diaminourea-2-trifluoromethylbenzene、2，5-diaminourea benzonitrile、2，5-diaminobenzene ethyl ketone、2，5-diaminobenzoic acid、2，2 '-dichloro-benzidine、2，2 '-'-dibromobiphenyl amine、2，2 '-diiodobiphenyl amine、2，2 '-dinitrobenzidine、2，2 '-bis-(trifluoromethyl) benzidine、3-amino phenyl sulfonyl acetoacetic ester、3，5-bis trifluoromethyl-1，2-diaminobenzene、4-aminonitrobenzene、N，N-dimethyl-4-nitroaniline，More preferably 4，4 '-diamino diphenyl sulfone、2，Double; two (4-aminophenyl) HFC-236fa of 2-、2，2 '-bis-(trifluoromethyl) benzidine、3-amino phenyl sulfonyl acetoacetic ester、3，5-bis trifluoromethyl-1，2-diaminobenzene、4-aminonitrobenzene、N，N-dimethyl-4-nitroaniline.
As the content ratio of [H] compound in the 2nd radiation-sensitive resin composition, for [E] compound 100 weight portion, it is preferred to 0.1 weight portion～20 weight portion, more preferably 0.2 weight portion～10 weight portion.By making the content ratio of [H] compound be 0.1 weight portion～10 weight portion, it may be achieved the hardening of the distance piece formed by the 2nd radiation-sensitive resin composition promotes.In a word, make the storage stability of the 2nd radiation-sensitive resin composition improve, additionally be able to the voltage retention keeping comprising the liquid crystal display cells of colored filter (described colored filter has rewarding distance piece) with high level.
<other any compositions>
The 2nd radiation-sensitive resin composition used in the formation of the distance piece of the colored filter of this embodiment, except above-mentioned [E] compound, [F] polymerizable compound, [G] polymerization initiator and [H] compound, also can optionally contain the arbitrarily composition such as [K-1] then auxiliary agent, [K-2] surfactant, [K-3] preserving stabilizer and [K-4] thermostability accelerator in the scope not undermining desired effect.Those each any compositions can be used alone and also can two or more mixing be used.Hereinafter, sequentially described in detail.
[[K-1] then auxiliary agent]
[K-1] then auxiliary agent can with so that the distance piece of gained and the adherence of substrate improve further.This kind [K-1] then auxiliary agent can use the compound identical with the then auxiliary agent in other any compositions of above-mentioned colored composition.
Consumption is made, for [E] compound 100 weight portion, it is preferred to below 20 weight portions, more preferably below 15 weight portions as [K-1] then auxiliary agent.[if K-1] then auxiliary agent make consumption more than 20 weight portions, then there is the tendency becoming easily to produce development residual.
[[K-2] surfactant]
[K-2] surfactant can with so that the film formative of the 2nd radiation-sensitive resin composition improves further.[K-2] surfactant include, for example fluorine class surfactant, silicone surfactant and other surfactants, can use the compound identical with the surfactant in other any compositions of above-mentioned colored composition.
Make consumption as [K-2] surfactant, for [E] compound 100 weight portion, be preferably below 1.0 weight portions, more preferably below 0.8 weight portion.[if K-2] surfactant make consumption more than 1.0 weight portions, then become easily to produce film uneven.
[[K-3] preserving stabilizer]
[K-3] preserving stabilizer can use the compound identical with the preserving stabilizer in other any compositions of above-mentioned colored composition, include, for example sulfur, quinones, hydroquinone type, polyoxy compounds, amine, nitro nitroso compound etc., more specifically can enumerate 4-methoxyphenol, N-nitroso-group-N-Phenylhydroxylamine aluminum etc..
Consumption is made, for [E] compound 100 weight portion, it is preferred to below 3.0 weight portions, more preferably below 1.0 weight portions as [K-3] preserving stabilizer.If the allotment amount of [K-3] preserving stabilizer is more than 3.0 weight portions, then the situation that the light sensitivitys that there is the 2nd radiation-sensitive resin composition reduces and causes pattern form to deteriorate.
[[K-4] thermostability accelerator]
[K-4] thermostability accelerator can use the compound identical with the heat-resisting stabilizing agent in other any compositions of above-mentioned colored composition.
Make consumption as [K-4] thermostability accelerator, for [E] compound 100 weight portion, be preferably below 50 weight portions, more preferably below 30 weight portions.If the allotment amount of [K-4] thermostability accelerator is more than 50 weight portions, then the situation that the light sensitivitys that there is the 2nd radiation-sensitive resin composition reduces and causes pattern form to deteriorate.
<modulation of the 2nd radiation-sensitive resin composition>
The 2nd radiation-sensitive resin composition forming the distance piece that the colored filter of this embodiment has can be modulated in the following way: by [E] compound, [F] polymerizable compound, [G] polymerization initiator and [H] compound, and any composition optionally is mixed with predetermined ratio in the scope not undermining desired effect.2nd radiation-sensitive resin composition is preferably dissolved in suitable solvent under solution state and uses.
The solvent used in the modulation of the 2nd radiation-sensitive resin composition can use the solvent that can dissolve or disperse [E] compound, [F] polymerizable compound, [G] polymerization initiator, [H] compound and any composition equably and not react with each composition.This kind of solvent can enumerate the solvent used in the modulation of the colored composition of the colored filter as above-mentioned embodiment and the solvent illustrated.Solvent can be used alone or two or more mixing be used.
As the solvent of the 2nd radiation-sensitive resin composition, when and during by the situation of high boiling solvent, it makes consumption be preferably below 50wt% for total solvent amount, more preferably below 40wt%, it is particularly preferred to for below 30wt%.When to make consumption be below 50wt% of high boiling solvent, the thickness homogeneity of film, light sensitivitys and residual film ratio become good.
When the 2nd radiation-sensitive resin composition is modulated to the situation of solution state, solid concentration (composition beyond solvent shared in constituent solution) can be set as any concentration (such as 5wt%～50wt%) according to the value of application target or desired thickness etc..As preferred solid concentration, different because forming the forming method of film on substrate, in hereinafter it being described.About so constituent solution modulated, after the microfilter etc. that aperture can be used to be about 0.5 μm is filtered, it is supplied to use.
2nd radiation-sensitive resin composition of above composition and modulator approach may utilize hardening at subcritical temerature and forms distance piece.Specifically, even under the hardening temperature below 200 DEG C, be, under the hardening temperature of less than 180 DEG C, also can obtain the distance piece with good reliability furthermore.And, available hardening at subcritical temerature and the colored filter of this embodiment is provided.
The colored filter of this embodiment can as described above constitute liquid crystal display cells time liquid crystal layer side face on LCD alignment alignment film is set.Alignment film can use the crystal aligning agent comprising the radioactivity-sensitive polymer with light regiospecific base or the crystal aligning agent that comprises the polyimides not having light regiospecific base and obtain.In this case, become to form alignment film under the heating-up temperature below 200 DEG C.Secondly, the formation crystal aligning agent of alignment film, particularly its main component are illustrated.
<crystal aligning agent>
Form the crystal aligning agent of the alignment film that the colored filter of this embodiment has contain [L] the radioactivity-sensitive polymer with light regiospecific base as described above or do not have [M] polyimides of light regiospecific base as main component.The crystal aligning agent particularly forming the alignment film that the colored filter of this embodiment has preferably comprises [L] the radioactivity-sensitive polymer with light regiospecific base.Those compositions all can form alignment film under the heating-up temperature of such as 200 DEG C of such as the following low temperature.And, as long as not undermining the effect of the present invention, then can contain [N] other compositions.Hereinafter those compositions are illustrated.
[[L] radioactivity-sensitive polymer]
Forming [L] radioactivity-sensitive polymer contained in the crystal aligning agent of the alignment film of the colored filter of this embodiment is the polymer with light regiospecific base.The light regiospecific base that this [L] radioactivity-sensitive polymer has is to be irradiated by light and give film anisotropic functional group, in this embodiment, give film anisotropic base especially by least arbitrarily person producing photoisomerization reaction and light dimerization reaction.
As light regiospecific base, specifically there is the base of the structure of at least one compound being derived from the group selecting free diphenyl diimide, stilbene, alpha-imino-'beta '-ketoester, spiro-pyrans, spiral shell piperazine, cinnamic acid, chalcone derivative, stilbene azoles, benzylidene phthalimide, coumarin, dibenzenyl and anthracene to constitute.As above-mentioned smooth regiospecific base, those particularly preferably have the base of the structure being derived from cinnamic acid.
As [L] the radioactivity-sensitive polymer with light regiospecific base, it is preferred to above-mentioned smooth regiospecific base is directly or via the polymer of concatenating group bond.This kind of polymer include, for example: at least arbitrarily polymer of polyamic acid and polyimides, bond has the compound of above-mentioned smooth regiospecific base；On the polymer different from polyamic acid and polyimides, bond has the compound of above-mentioned smooth regiospecific base.When the situation of the latter, the basic framework with the polymer of light regiospecific base include, for example poly-(methyl) acrylate, poly-(methyl) acrylamide, polyvinylether, polyolefin, polysiloxane etc..
As radioactivity-sensitive polymer, it is preferable that the radioactivity-sensitive polymer being basic framework with polyamic acid, polyimides or polysiloxane.And, particularly preferably polysiloxane in those, for instance can be obtained by method described in International Publication (WO) the 2009/025386th.
[[M] polyimides]
Forming [M] polyimides contained in the crystal aligning agent of the alignment film of the colored filter of this embodiment is the polyimides not having light regiospecific base.
This kind does not have [M] polyimides of light regiospecific base can carry out imidizate by making not have the polyamic acid dehydration closed-loop of light regiospecific base and obtain.This kind of polyamic acid such as can by making tetracarboxylic dianhydride and diamine reactant obtain, can described in Japanese Patent Laid-Open 2010-97188 publication and obtain.
[M] polyimides can the complete acid imide compound of amic acid structure fully dehydrating closed loop for having as the polyamic acid of its predecessor, also can be the only only a part dehydration closed-loop of amic acid structure, amic acid structure and imide ring structure the part acid imide compound deposited.[M] polyimides preferably its acid imide rate is more than 30%, more preferably 50%～99%, is more preferably 65%～99% further.This acid imide rate is to represent, with percentage rate, the ratio that imide ring structure number is shared with the total of imide ring structure number relative to the amic acid structure number of polyimides.Herein, a part for imide ring also can be different imide ring, for instance can described in Japanese Patent Laid-Open 2010-97188 publication and obtain.
[[N] other compositions]
The crystal aligning agent of the alignment film forming the colored filter of this embodiment can containing having the radioactivity-sensitive polymer of light regiospecific base and not having [N] other compositions beyond the polyimides of light regiospecific base.[N] other compositions include, for example [L] the radioactivity-sensitive polymer with light regiospecific base and do not have the polymer beyond [M] polyimides of light regiospecific base, sclerosing agent, hardening catalyst, hardening accelerator, epoxide, functional silanes compound, surfactant, photosensitizer etc..
<colored pattern, protecting film, distance piece, colored filter and those manufacture method>
In the manufacture of the colored filter of this embodiment, comprise the steps as main manufacturing step: in order to be formed the step of colored pattern by above-mentioned colored composition, in order to be formed the step of protecting film by above-mentioned 1st radiation-sensitive resin composition, in order to be formed the step of distance piece by above-mentioned 2nd radiation-sensitive resin composition.Hereinafter, colored pattern, protecting film, distance piece, colored filter and those manufacture method are illustrated.
The manufacture method of the colored filter of this embodiment at least comprises following step [1]～step [11] with following order:
[1] formed on substrate the film of colored composition step (hereinafter sometimes referred to " [1] step "),
[2] colored composition film formed colored pattern step (hereinafter sometimes referred to " [2] step "),
The step (hereinafter sometimes referred to " [3] step ") [3] below 200 DEG C, the film being formed with colored pattern hardened,
[4] on the substrate after [3] step formed the 1st radiation-sensitive resin composition film step (hereinafter sometimes referred to " [4] step "),
[5] the 1st radiation-sensitive resin composition film on this substrate at least some of is irradiated lonizing radiation step (hereinafter sometimes referred to " [5] step "),
The step (hereinafter sometimes referred to " [6] step ") [6] film having irradiated lonizing radiation developed,
The step (hereinafter sometimes referred to " [7] step ") of the film hardening [7] making to have developed below 200 DEG C,
[8] on the substrate of hardened coating film with [7] step formed the 2nd radiation-sensitive resin composition film step (hereinafter sometimes referred to " [8] step "),
[9] the 2nd radiation-sensitive resin composition film formed in [8] step at least some of is irradiated lonizing radiation step (hereinafter sometimes referred to " [9] step "),
The step (hereinafter sometimes referred to " [10] step ") [10] film having irradiated lonizing radiation developed,
[11] film developed hardening is made to form the step (hereinafter sometimes referred to " [11] step ") of distance piece below 200 DEG C.
And, when the colored filter in this embodiment has the situation of LCD alignment alignment film, it is also possible to [12] are set after [11] step and form the step (hereinafter sometimes referred to " [12] step ") of alignment film.
Manufacture method by the colored filter of this embodiment above; above-mentioned colored composition can be used to form colored pattern on substrate; use above-mentioned 1st radiation-sensitive resin composition to form protecting film, use above-mentioned 2nd radiation-sensitive resin composition to form distance piece.And, when the colored filter of this embodiment has the situation of alignment film, above-mentioned crystal aligning agent can be used to form alignment film.Its result, can form the good colored filters such as thermostability, chemical-resistant, voltage retention.In such cases, it may be achieved hardening at subcritical temerature.In above-mentioned [3] step, above-mentioned [7] step and above-mentioned [11] step, can harden under 200 DEG C of temperature below respectively.Therefore, can there is the dyestuff of problem in being used in thermostability in above-mentioned colored composition as coloring agent.Therefore, the colored filter that color characteristics is excellent can be manufactured.It addition, in above-mentioned [12] step, it is also possible to carry out the formation of alignment film under the heating-up temperature below 200 DEG C.And, considering from energy-conservation viewpoint, the colored filter manufactured as mentioned above also becomes suitable colored filter when expecting hardening at subcritical temerature.Hereinafter, each step is described in detail.
[[1] step]
In this step, substrate is formed the film of above-mentioned colored composition.
On the surface of the substrate, optionally in the way of dividing the part forming pixel, light shield layer (black matrix") is formed.Secondly, it is coated with the colored composition of [IV] coloring agent such as containing redness on the substrate, then carries out preliminary drying and make solvent evaporate, thus forming film.The additive method forming colored pattern on substrate can adopt the method utilizing ink-jetting style and obtaining each color pixel disclosed in Japanese Patent Laid-Open 7-318723 publication and Japanese Patent Laid-Open 2000-310706 publication etc..The method forms the dividing plate having shade function concurrently first on the surface of the substrate.Secondly, utilize ink discharge device to be ejected in the dividing plate formed by the colored composition such as containing red stain, then carry out preliminary drying and make solvent evaporate.Secondly, optionally this film is exposed and forms red pattern of pixels.It addition, aforementioned barriers not only plays shade function, and play to make the function of the assorted colored composition not colour mixture being ejected in partition, therefore thicker with above-mentioned black matrix" Comparatively speaking thickness.
The material of substrate include, for example the glass such as soda-lime glass or alkali-free glass, silicon, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, Merlon, aromatic polyamide, polyamidoimide, polyimides etc..And, also can optionally those substrates be implemented in advance the pretreatment utilizing the chemicals treatment of silane coupler etc., Cement Composite Treated by Plasma, ion plating, sputtering, gas-phase reaction method, vacuum evaporation etc. suitable.
The method on substrate of being coated by colored composition can enumerate nebulization, rolling method, method of spin coating (spin-coating method), slit die rubbing method, bar type rubbing method etc..Preferably spun on method, slit die rubbing method in those methods.
Preliminary drying is generally undertaken by being combined with heat drying by drying under reduced pressure.Drying under reduced pressure generally carries out in the way of arriving 50Pa～200Pa.And, the condition of heat drying is usually 1 minute～about 10 minutes at 70 DEG C～110 DEG C.
Dried thickness is generally 0.6 μm～8.0 μm, it is preferred to 1.2 μm～5.0 μm.
[[2] step]
In [2] step, it is situated between and every photomask, the film formed in [1] step is exposed, alkaline-based developer is used to develop, dissolve the unexposed portion removing film, thereby can form the pel array of the pattern of pixels being configured with redness with predetermined arrangement, thus obtaining colored pattern.
Secondly, use each colored composition of green or blueness, be repeatedly performed above-mentioned [1] step and [2] step and sequentially form green pixel array and blue pixel array on the same substrate.Obtain the colored filter being configured with redness, green and blue three primary colors pel array on substrate therefrom.Wherein, in this embodiment, the order and the number of colours that form each color pixel are not limited to said sequence and number of colours.
And, black matrix" can be formed by utilizing photoetching process that the metallic film of the chromium etc. formed by sputter or evaporation is made desired pattern, uses the colored composition containing black colorant to be identically formed with the situation of the formation of above-mentioned pixel.
The light source of lonizing radiation include, for example the LASER Light Sources etc. such as lamp source or argon ion laser, YAG laser, XeCl quasi-molecule laser, nitrogen laser such as xenon lamp, Halogen light, tengsten lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, Metal halogen lamp, middle medium pressure mercury lamp, low pressure mercury lamp.Optimal wavelength is in the lonizing radiation of the scope of 190nm～450nm.The light exposure of lonizing radiation is preferably 10J/m2～10,000J/m2。
The preferred sodium carbonate of alkaline-based developer, sodium hydroxide, potassium hydroxide, Tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-endecatylene, 1,5-diazabicyclo-[4.3.0]-5-nonene.
Alkaline-based developer can add the such as water-miscible organic solvent such as methanol, ethanol or surfactant etc. in right amount.It addition, generally wash after alkaline development.Development treatment method can be applied spray development method, spray developing method, dipping (dip) development method, cover liquid (puddle) development method etc..Development conditions is preferably 5 seconds～300 seconds at normal temperatures.
[[3] step]
After [2] step forms colored pattern, colored pattern can be made to harden by carrying out hardening (being also known as after bake), thus the formation of colored pattern can be made to terminate.The heating condition of after bake is less than 200 DEG C.The heat time heating time of after bake is 10 minutes～60 minutes.In this embodiment, even if after bake temperature is low temperature, also can obtain the good colored patterns such as solvent resistance.Specifically, even if after bake temperature is less than 200 DEG C, is less than 180 DEG C further, the colored filter with sufficient solvent resistance etc. can also be obtained.The thickness of pixel is generally 0.5 μm～5.0 μm, it is preferred to 1.0 μm～3.0 μm.It addition, in order to make hardness etc. be increased to actually commercial required level, typically required cure step at the temperature more than 120 DEG C.And, in the scope below 180 DEG C, it is preferable that hardening at a higher temperature.
[[4] step]
After forming colored pattern by [3] step, define the film forming the 1st radiation-sensitive resin composition on the colored pattern on the substrate of colored pattern at this.
When utilizing rubbing method and form the situation of film, after the substrate define colored pattern is coated with the 1st radiation-sensitive resin composition solution, it is preferable that coated face is heated (preliminary drying), thus can form film.The solid concentration of the constituent solution used in rubbing method is preferably 5wt%～50wt%, more preferably 10wt%～40wt%, it is particularly preferred to for 15wt%～35wt%.The coating process of the 1st radiation-sensitive resin composition solution such as can adopt the method that nebulization, rolling method, method of spin coating (spin-coating method), slot coated method (slit die rubbing method), bar type rubbing method, ink-jet application method etc. are suitable.Preferably spun on method or slot coated method in those methods.
Above-mentioned preliminary drying condition is different because of the kind of each composition, allotment ratio etc., it is preferable that 70 DEG C～120 DEG C, 1 minute～about 15 minutes.The pre-baked thickness of film is preferably 0.5 μm～10 μm, more preferably 1.0 μm～about 7.0 μm.
[[5] step]
Secondly, the film formed irradiated lonizing radiation at least partially.Now, when only a part for film being irradiated, for instance available be situated between every the method that there is the photomask of predetermined pattern and be irradiated.
The lonizing radiation used in irradiation can enumerate luminous ray, ultraviolet, far ultraviolet rays etc..Wherein optimal wavelength is in the lonizing radiation of the scope of 250nm～550nm, more preferably comprises the ultraviolet lonizing radiation of 365nm.
Lonizing radiation irradiation dose (light exposure) is the value utilizing illumination meter (OAImodel356, OpticalAssociatesInc. manufacture) and measuring intensity under the wavelength 365nm of the lonizing radiation irradiated, it is preferable that 100J/m2～5,000J/m2, more preferably 200J/m2～3,000J/m2。
The protecting film of the colored filter of this embodiment formed middle the 1st used radiation-sensitive resin composition have the advantage that with in itself previously known protecting film formed constituent Comparatively speaking lonizing radiation light sensitivitys is higher.Therefore, even if being 700J/m at above-mentioned lonizing radiation irradiation dose2Below, it is 600J/m further2Time following, also can obtain the protecting film of desired thickness, good shape, excellent adhesion and high rigidity.
[[6] step]
Secondly, developed by the film after lonizing radiation are irradiated, remove unnecessary portion, form predetermined pattern.
The aqueous solution of the alkali compoundss such as the developer solution used in development such as can use the inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, the quaternary ammonium salt such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide.The aqueous solution of above-mentioned alkali compounds also can add the water-miscible organic solvents such as the methanol of appropriate amount, ethanol and use.It addition, also can only add the surfactant of appropriate amount and use, or the surfactant of appropriate amount and above-mentioned water-miscible organic solvent are together added and uses.
Developing method can for cover any number of of liquid method, infusion process, spray process etc., and developing time is preferably 10 seconds～about 180 seconds at normal temperatures.After development treatment, for instance the flowing water carried out 30 seconds～90 seconds cleans, then carry out air-dry with compression air or compressed nitrogen, obtain desired pattern therefrom.
[[7] step]
Secondly, by the heater utilizing hot plate, baking oven etc. suitable, the pattern-like film of gained is hardened (being also known as after bake), make cured film and obtain protecting film.Hardening temperature is preferably less than 200 DEG C.And, even less than 180 DEG C also can obtain the protecting film with sufficient characteristic.Specifically it is preferably 100 DEG C～200 DEG C, when being intended to the situation taking into account hardening at subcritical temerature and unfailing performance with high level, more preferably 150 DEG C～180 DEG C.As firm time, for instance be preferably 5 minutes～30 minutes on hot plate, it is preferably 30 minutes～180 minutes in an oven.1st radiation-sensitive resin composition contains [D] compound as described above, therefore can realize so low hardening at subcritical temerature.In a word, it may be achieved storage stability, and there is sufficient resolution and lonizing radiation light sensitivitys.
Therefore, the 1st radiation-sensitive resin composition, when forming the situation of protecting film, uses aptly as the formation material of protecting film (described protecting film uses with using the colored pattern having dyestuff ideal for hardening at subcritical temerature combination).
In the manufacture of the colored filter of this embodiment, after forming [7] step of protecting film, it is included in the step forming ITO electrode on this protecting film.The method forming ITO electrode can use sputtering method to form ito film and carry out.As the ITO electrode of patterning, the ito film formed is patterned and is formed by available photoetching process in the case of necessary.
[[8] step]
Form protecting film by [7] step, on this protecting film, form thereafter ITO electrode, then the ITO electrode on the substrate being formed with this protecting film is formed the film of the 2nd radiation-sensitive resin composition.
When utilizing rubbing method and form the situation of film, after the substrate define colored pattern etc. is coated with the 2nd radiation-sensitive resin composition solution, it is preferable that coated face is heated (preliminary drying), thus can form film.The solid concentration of the constituent solution used in rubbing method is preferably 5wt%～50wt%, more preferably 10wt%～40wt%, it is particularly preferred to for 15wt%～35wt%.The coating process of the 2nd radiation-sensitive resin composition solution such as can adopt the method that nebulization, rolling method, method of spin coating (spin-coating method), slot coated method (slit die rubbing method), bar type rubbing method, ink-jet application method etc. are suitable.Preferably spun on method or slot coated method in those methods.
Above-mentioned preliminary drying condition is different because of the kind of each composition, allotment ratio etc., it is preferable that 70 DEG C～120 DEG C, 1 minute～about 15 minutes.The pre-baked thickness of film is preferably 0.5 μm～10 μm, more preferably 1.0 μm～about 7.0 μm.
[[9] step]
Secondly, the film formed in [8] step irradiated lonizing radiation at least partially.Now, in order to form distance piece in desired position, the part of film is irradiated lonizing radiation, for instance available be situated between every the method that there is the photomask of predetermined pattern and be irradiated.
The lonizing radiation used in irradiation can enumerate luminous ray, ultraviolet, far ultraviolet rays etc..Wherein optimal wavelength is in the lonizing radiation of the scope of 250nm～550nm, more preferably comprises the ultraviolet lonizing radiation of 365nm.
Lonizing radiation irradiation dose (light exposure) is the value utilizing illumination meter (OAImodel356, OpticalAssociatesInc. manufacture) and measuring intensity under the wavelength 365nm of the lonizing radiation irradiated, it is preferable that 100J/m2～5,000J/m2, more preferably 200J/m2～3,000J/m2。
The distance piece of the colored filter of this embodiment formed middle the 2nd used radiation-sensitive resin composition have the advantage that with in itself previously known distance piece formed constituent Comparatively speaking lonizing radiation light sensitivitys is higher.Therefore, even if being 700J/m at above-mentioned lonizing radiation irradiation dose2Below, it is 600J/m further2Time following, also can be made into the cured film of desired thickness, good shape, excellent adhesion and high rigidity and obtain distance piece.
[[10] step]
Secondly, developed by the film after lonizing radiation are irradiated, remove unnecessary portion, form the pattern of predetermined distance piece.
The aqueous solution of the alkali compoundss such as the developer solution used in development such as can use the inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, the quaternary ammonium salt such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide.The aqueous solution of above-mentioned alkali compounds also can add the water-miscible organic solvents such as the methanol of appropriate amount, ethanol and use.It addition, also can only add the surfactant of appropriate amount and use, or the surfactant of appropriate amount and above-mentioned water-miscible organic solvent are together added and uses.
Developing method can for cover any number of of liquid method, infusion process, spray process etc., and developing time is preferably 10 seconds～about 180 seconds at normal temperatures.After development treatment, for instance the flowing water carried out 30 seconds～90 seconds cleans, then carry out air-dry with compression air or compressed nitrogen, obtain the pattern of desired distance piece therefrom.
[[11] step]
Secondly, by the heater utilizing hot plate, baking oven etc. suitable, the pattern-like film of gained is hardened (being also known as after bake), make cured film and obtain distance piece.Hardening temperature is preferably less than 200 DEG C.And, even less than 180 DEG C also can obtain the distance piece with sufficient characteristic.Specifically it is preferably 100 DEG C～200 DEG C, when being intended to the situation taking into account hardening at subcritical temerature and unfailing performance with high level, more preferably 150 DEG C～180 DEG C.As firm time, for instance be preferably 5 minutes～30 minutes on hot plate, it is preferably 30 minutes～180 minutes in an oven.2nd radiation-sensitive resin composition contains [H] compound as described above, therefore can realize so low hardening at subcritical temerature.In a word, it may be achieved storage stability, and there is sufficient resolution and lonizing radiation light sensitivitys.
Therefore, the 2nd radiation-sensitive resin composition can use aptly as the formation material of distance piece (described distance piece uses with using the colored pattern having dyestuff ideal for hardening at subcritical temerature combination).
According to above manufacture method, colored pattern, protecting film and distance piece can be manufactured, and the colored filter of this embodiment can be manufactured.As it has been described above, the colored pattern of the colored filter of this embodiment is after colored composition is coated on suitable substrate and is patterned, carry out hardening and being formed.Protecting film is similarly after being coated with the 1st radiation-sensitive resin composition and being patterned, and carries out hardening and being formed.Distance piece is similarly after being coated with the 2nd radiation-sensitive resin composition and being patterned, and carries out hardening and being formed.And, colored composition, the 1st radiation-sensitive resin composition and the 2nd radiation-sensitive resin composition can all be set to use the radiation-sensitive resin composition with based material as described above.And, those constituents can form colored pattern or protecting film or distance piece respectively by the hardening at subcritical temerature of less than 200 DEG C.
Therefore, in the colored filter of this embodiment, it is possible to formed colored pattern and protecting film and distance piece respectively by the hardening at subcritical temeratures of less than 200 DEG C.The colored filter of this embodiment can be manufactured by hardening at subcritical temerature.
And, in the colored filter of this embodiment, it is subsequently formed protecting film in forming colored pattern.Protecting film can be formed by the hardening at subcritical temerature of less than 200 DEG C, and therefore colored pattern is without being exposed to after its formation under the state forming the high-temperature heating of protecting film.Similarly, in the colored filter of this embodiment, it is subsequently formed distance piece in forming colored pattern.Distance piece can be formed by the hardening at subcritical temerature of less than 200 DEG C, and therefore colored pattern is without being exposed to after its formation under the state forming the high-temperature heating of distance piece.Therefore, even if although using color characteristics excellent but there is the dyestuff of problem in thermostability as coloring agent, step deterioration also can be reduced.
It addition, as it has been described above, colored composition and the 1st radiation-sensitive resin composition and the 2nd radiation-sensitive resin composition can all be set to use the radiation-sensitive resin composition with based material.Therefore, during formation colored pattern in time manufacturing the colored filter of this embodiment, it is contemplated that protecting film thereafter is formed or distance piece is formed and adjusts hardening temperature.That is, on substrate, utilize with when independently forming colored pattern institute optimum hardening temperature Comparatively speaking less hardening temperature and form colored pattern.Thereafter, it is possible to the hardening heating of protecting film or the hardening of distance piece by being formed on colored pattern are heated and colored pattern is also carried out heating.
Such as, when colored pattern is with the optimum hardening temperature respectively less than 200 DEG C, specifically 180 DEG C of protecting film and distance piece, it is possible to be pre-formed colored pattern by the hardening temperatures of such as 150 DEG C.Secondly, on this colored pattern, form the film of the 1st radiation-sensitive resin composition, carry out hardening at optimum 180 DEG C and form protecting film.Its result, the colored pattern also its lower floor formed is heated, thus the colored filter of this embodiment of colored pattern and the protecting film comprising desired state can be obtained.And, for instance under the hardening temperature of 150 DEG C, it is pre-formed colored pattern and protecting film, under the hardening temperature of optimum 180 DEG C, distance piece can be formed by the film of the 2nd radiation-sensitive resin composition thereafter.Its result, also colored pattern and protecting film to being formed before are heated, thus the colored filter of colored pattern and the protecting film with this embodiment of distance piece comprising desired state can be obtained.
[[12] step]
Secondly, in the autofrettage of the colored filter of this embodiment, it is possible to [12] are set as described above after [11] step and form the step of alignment film.The alignment film with LCD alignment ability can be set therefrom in colored filter.
Above-mentioned crystal aligning agent is used in [12] step.And, it is being formed by above-mentioned [1] step～[11] step on colored pattern and the protecting film substrate with distance piece, is utilizing the suitable coating process of such as rolling method, spin-coating method, print process, ink-jet method etc. to be coated with above-mentioned crystal aligning agent.Secondly, the substrate being coated with crystal aligning agent is carried out preliminary drying, forms film followed by after bake.Preliminary drying condition is such as be 0.1 minute～5 minutes at 40 DEG C～120 DEG C.As after bake condition, temperature is preferably 120 DEG C～230 DEG C, more preferably 150 DEG C～200 DEG C, is more preferably 150 DEG C～180 DEG C further, and the time is preferably 5 minutes～200 minutes, more preferably 10 minutes～100 minutes.The thickness of the film after after bake is preferably 0.001 μm～1 μm, more preferably 0.005 μm～0.5 μm.
The solid concentration of the crystal aligning agent used when crystal aligning agent is coated on substrate (ratio that the total weight of the composition except solvent of crystal aligning agent is shared in the gross weight of crystal aligning agent) it is contemplated that viscosity, volatility etc. and suitable select, it is preferred to the scope of 1wt%～10wt%.
When using the situation of crystal aligning agent comprising [L] the radioactivity-sensitive polymer with light regiospecific base, give LCD alignment ability by above-mentioned film is irradiated linear polarization or the lonizing radiation of part polarisation or the lonizing radiation of non-polarized.The method so processing the orientation process previous with friction treatment etc. is corresponding, can carry out more easily.Herein, lonizing radiation such as can use ultraviolet and the luminous ray of the wavelength light comprising 150nm～800nm.Particularly preferably use the ultraviolet of the wavelength light comprising 300nm～400nm as lonizing radiation.When the situation that the lonizing radiation used are linear polarization or part polarisation, irradiate the direction that can certainly be perpendicular to real estate and carry out, it is also possible to carry out giving tilt angle from tilted direction, and also those Combination of Methods can be carried out.When irradiating the situation of lonizing radiation of non-polarized, direction of illumination is tilted direction necessarily.
The irradiation dose of lonizing radiation is preferably 1J/m2Above and less than 10,000J/m2, more preferably 10J/m2～3,000J/m2。
When using the situation of crystal aligning agent comprising [M] polyimides not having light regiospecific base, also the film after after bake can be directly used as alignment film.And, also optionally the film after after bake can be implemented the process (friction treatment) such as rubbed on fixed-direction with the roller being wound with the cloth comprising the fibers such as nylon, artificial silk, cotton, thus giving LCD alignment ability.
As it has been described above, in the method for manufacturing colored filtering substrate of this embodiment, can use above-mentioned crystal aligning agent and heating-up temperature below 200 DEG C, be form alignment film under the heating-up temperature of less than 180 DEG C further.Therefore, the colored pattern that can avoid the colored filter formed in above-mentioned [1] step～[3] step is exposed to high temperature in [12] step forming alignment film.
[example]
Hereinafter, the embodiment of the present invention is described in detail by Case-based Reasoning, but with this example, limiting the invention property is not explained.
<formation of colored pattern and evaluation>
Example 1
[synthesis of [I] alkali soluble resins (IA)]
Loading 2 in there is the flask of condensing tube and blender, double; two (2,4-methyl pentane nitrile) 5 weight portions of 2 '-azo and diethylene glycol ethylmethyl ether 220 weight portion.Secondly, methacrylic acid 18 weight portion of (I-1) compound it is loaded as, as methacrylic acid-2-methylglycidyl esters 14 weight portion of (I-2) compound and glycidyl methacrylate 20 weight portion, as styrene 10 weight portion of (I-4) compound, methacrylic acid three ring [5.2.1.02,6] decane-8-base ester 23 weight portion and methyl methacrylate 15 weight portion, after carrying out nitrogen displacement, one side gently stirring one side makes the temperature of solution rise to 70 DEG C, keep this temperature 5 hours to be polymerized, obtain the solution containing the alkali soluble resins (IA) as copolymer therefrom.The solid concentration of the polymer solution of gained is 31.5%, and the Mw as the alkali soluble resins (IA) of copolymer is 10,100.
Example 2
[synthesis of [I] alkali soluble resins (IB)]
AIBN4 weight portion and diethylene glycol ethylmethyl ether 300 weight portion is loaded in there is the flask of condensing tube and blender, next is loaded as methacrylic acid 23 weight portion of (I-1) compound, styrene 10 weight portion as (I-4) compound, benzyl methacrylate 32 weight portion and methyl methacrylate 35 weight portion, load α-methylstyrenedimer 2.7 weight portion further, one side gently stirring one side makes the temperature of solution rise to 80 DEG C, this temperature is kept to make it rise to 100 DEG C after 4 hours, this temperature 1 hour is kept to be polymerized, obtain the solution containing copolymer therefrom.The solid concentration of the polymer solution of gained is 24.9%, and Mw is 12,500.Secondly, the solution comprising copolymer of gained adds tetrabutyl ammonium bromide 1.1 weight portion, 4-methoxyphenol 0.05 weight portion as polymerization inhibitor, under air ambient, at 90 DEG C after stirring 30 minutes, put into glycidyl methacrylate 16 weight portion as (I-2) compound and keep 90 DEG C to make it react 10 hours, obtain the alkali soluble resins (IB) as copolymer therefrom.The solid concentration of the polymer solution of gained is 29.0%, and Mw is 14,200.
Example 3
[modulation of colored composition]
nullMixture (KAYARAD (registered trade mark) DPHA-40H of the ethylene-oxide-modified dipentaerythritol acrylate (II-1) as [II] polymerizable compound and polyfunctional acrylic ester compound is mixed relative to (IA) 90 weight portions of the alkali soluble resins as copolymer of gained in example 1、Chemical medicine company of Japan) mixture (blending ratio ((II-1)/(II-2))=4) 100 weight portions of (II-2)、2-methyl isophthalic acid-(4-methylthiophene base)-2-morpholino propane-1-ketone (Irgacure907 as [III] polymerization initiator、Ciba company limited) (III-1) 25 weight portion、Red stain (IV-1) 100 weight portion comprising orchil as [IV] coloring agent、Mixture (blending ratio ((V-1)/(V-2)=5)) 6 weight portions as tetramethylolmethane four (3-mercaptopropionic acid) ester (V-1) and 3-amino phenyl sulfonyl acetoacetic ester (V-2) of [V] compound、As alkali soluble resins (IB) 10 weight portion of gained in the example 2 of other alkali soluble resins.Secondly, using Ketohexamethylene as solvent, after adding solvent in the way of the solid concentration of colored composition becomes 30wt%, the microfilter utilizing aperture to be 0.5 μm is filtered, and modulates red colored constituent therefrom.
Except with comprising beyond green colourant (IV-2) conduct [IV] coloring agent of green colouring material, carry out as described above and modulate green coloring constituent.And, except with comprising beyond blue colorant (IV-3) conduct [IV] coloring agent of blue dyes, carry out as described above and modulate blue-colored constituent.
Example 4
[formation of colored pattern]
It is formed with the SiO preventing sodium ion dissolution from the teeth outwards2On the soda-lime glass substrate of film, the red colored constituent using spin coater and being coated with in example 3 gained.Secondly, the hot plate of 90 DEG C carries out the preliminary drying of 2 minutes, forms the film that pre-baked thickness is 2.5 μm.After those substrates are cooled to room temperature, use high-pressure mercury-vapor lamp, be situated between every photomask with 1,000 (J/m2) light exposure film exposure is comprised the lonizing radiation of each wavelength of 365nm, 405nm and 436nm.Thereafter, with developer pressure 1 (kgf/cm2) (nozzle diameter is 1mm) and to those substrates spray developer solution (the 0.04wt% potassium hydroxide aqueous solutions of 23 DEG C), therefrom carry out spray development, substrate is formed the colored pattern of 200 μ m 200 μm.At 180 DEG C, carry out the after bake of 30 minutes further and form red colored pattern.
In use-case 3, the green coloring constituent of gained is as colored composition, carries out in addition as described above and forms green colored pattern.And, in use-case 3, the blue-colored constituent of gained is as colored composition, carries out in addition as described above and forms blue colored pattern.
Example 5
[evaluation of colored pattern]
Manufactured colored pattern is carried out following evaluation.
The evaluation of resistance to developability
In the formation of the colored pattern of above-mentioned colors, calculate the value of following formula:
Film Thickness Ratio=(thickness before thickness/development after development) × 100 before and after development.
The Film Thickness Ratio that the colored pattern of above-mentioned colors is all before and after development is more than 95%, it is known that have good resistance to developability.
The evaluation of thermostability
The colored pattern of above-mentioned colors is added heating 30 minutes further at 180 DEG C.And obtain the color changes delta Eab added before and after heating*.The colored pattern of above-mentioned colors is all Δ Eab*Less than 3, it is known that have good thermostability.
The evaluation of solvent resistance
About above-mentioned colored pattern, with in the N-Methyl pyrrolidone that substrate together impregnated in 60 DEG C 30 minutes.Thereafter, observing the assorted colored pattern on substrate, results verification remains colored pattern all after impregnating, and the N-Methyl pyrrolidone after dipping is completely not painted.The known above-mentioned equal solvent resistance of any colored pattern is good.
<formation of protecting film and evaluation>
Example 6
[synthesis of [A] compound]
Loading 2 in there is the flask of condensing tube and blender, double; two (2,4-methyl pentane nitrile) 7 weight portions of 2 '-azo and diethylene glycol ethylmethyl ether 200 weight portion.Secondly methacrylic acid 16 weight portion, methacrylic acid three ring [5.2.1.0 are loaded2,6] decane-8-base ester 16 weight portion, methyl methacrylate 38 weight portion, styrene 10 weight portion, glycidyl methacrylate 20 weight portion, after carrying out nitrogen displacement, one side gently stirring one side makes the temperature of solution rise to 70 DEG C, this temperature is kept 4 hours and is polymerized, obtain the solution (solid concentration=34.4wt%, Mw=8,000, Mw/Mn=2.3) containing copolymer (A-1) therefrom.It addition, solid concentration indicates that the ratio that the weight of copolymer is shared in the gross weight of copolymer solution.
Example 7
[modulation of radiation-sensitive resin composition]
nullRelative to copolymer (A-1) 100 weight portion of gained in the example 6 as [A] compound，Mix dipentaerythritol acrylate (B-1) 100 weight portion as [B] polymerizable compound、Ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime) (IrgacureOXE02 as [C] polymerization initiator、Ciba company limited) (C-1) 5 weight portion、And as the 4 of [D] compound，4 '-diamino diphenyl sulfone (D-1)，Mix γ-glycidoxypropyltrimewasxysilane 5 weight portion as [J-1] then auxiliary agent further、[J-2] surfactant (FTX-218、Neos company) 0.5 weight portion、4-methoxyphenol 0.5 weight portion as [J-3] preserving stabilizer，After being separately added into propylene glycol methyl ether acetate in the way of solid concentration becomes 30wt%，The microfilter utilizing aperture to be 0.5 μm is filtered，Modulate radiation-sensitive resin composition therefrom.
Example 8
[formation of protecting film]
After utilizing rotator to coat on alkali-free glass substrate by the radiation-sensitive resin composition solution modulated in example 7, the hot plate of 100 DEG C carries out the preliminary drying of 2 minutes and forms the film that thickness is 4.0 μm.Secondly, high-pressure mercury-vapor lamp is used to make light exposure be 700J/m2And the film of gained is carried out lonizing radiation irradiation.Secondly, in an oven, carry out after bake when the firm time of the hardening temperatures of 180 DEG C and 30 minutes and form protecting film.
Example 9
[evaluation of protecting film]
The evaluation of storage stability
By the radiation-sensitive resin composition solution of the example 7 after just modulating, form protecting film by the forming method of example 8, measure thickness (being called " just the thickness after modulation " in following formula).And, after utilizing the forming method of example 7 to be modulated, at 25 DEG C, preserve radiation-sensitive resin composition solution 5 days, similarly measure the thickness (being called " thickness after 5 days " in following formula) of the protecting film formed after 5 days.Thickness increment rate (%) is calculated according to following formula.
Thickness increment rate (%)=(thickness after the thickness after 5 days-just modulation)/(just the thickness after modulation) × 100
Thickness increment rate is less than 3%, thus judging that storage stability is good.
Sunproof evaluation
About the protecting film of the forming method gained utilizing example 8, carry out 800,000J/m with UV irradiation unit (UVX-02516S1JS01, UshioInc.) with the illumination of 130mW further2Irradiation, check film minimizing amount.Film minimizing amount is less than 2%, thus judging that light resistance is good.
The evaluation of thermostability
Protecting film about the forming method gained utilizing example 8; further in an oven, heating 20 minutes at 230 DEG C, measure the thickness before and after its heating with contact pin type determining film thickness machine (AlphaStepIQ, US business's KLA-Tencor (KLA-TENCOR) company).And calculate residual film ratio (thickness after process/thickness × 100 before treatment), using this residual film ratio as thermostability.Residual film ratio is 99%, thus judging that thermostability is good.
The evaluation of chemical-resistant
Protecting film about the forming method gained utilizing example 8; in dipping 15 minutes of heating to alignment film stripper CHEMICLEAN (registered trade mark) TS-204 (chemical conversion industrial group of Sanyo) of 60 DEG C; after being washed, further in an oven, at 120 DEG C dry 15 minutes.Measure the thickness before and after this process with contact pin type determining film thickness machine (AlphaStepIQ, US business KLA-Tencor company), calculate residual film ratio (thickness after process/thickness × 100 before treatment), using this residual film ratio as chemical-resistant.Residual film ratio is 99%, thus judging that chemical-resistant is good.
<formation of distance piece and evaluation>
Example 10
[formation of distance piece]
As the example forming distance piece, the example only forming distance piece on substrate is illustrated.In order to form the radiation-sensitive resin composition used in the formation of protecting film modulated in use-case 7 in the radiation-sensitive resin composition of distance piece.
On alkali-free glass substrate, use the radiation-sensitive resin composition solution that spin coater and being coated with in example 7 is modulated.Secondly, the hot plate of 100 DEG C carries out the preliminary drying of 2 minutes, is consequently formed the film that thickness is 6.0 μm.Secondly, use high-pressure mercury-vapor lamp and with 700J/m2Light exposure the film of gained is carried out lonizing radiation irradiation.Thereafter, with developer pressure 1 (kgf/cm2) (nozzle diameter is 1mm) and to this substrate spray developer solution (the 0.04wt% potassium hydroxide aqueous solutions of 23 DEG C), therefrom carry out spray development, substrate is formed the pattern of distance piece.Secondly, carry out after bake with the firm time of the hardening temperature of 180 DEG C and 30 minutes in an oven, on substrate, form distance piece therefrom.And, confirm to form distance piece with desired position and shape (resolution) on substrate.
Example 11
[evaluation of distance piece]
About the distance piece of gained in example 10, use scanning electron-microscopic observation section shape.The distance piece formed is all pattern edge is along wedge shape, well.
Secondly, on the distance piece formed on substrate in example 10, it is coated with printer with liquid crystal orienting film and is coated with AL3046 (JSRCorporation manufacture), at 180 DEG C, carry out 1 hour dry, form the film of the alignment film that dry film thickness is 0.05 μm and as liquid crystal orienting film.Utilize the strigil of roller with the cloth being wound with nylon, the rotating speed at roller be 500rpm, platform translational speed this film is carried out friction treatment when being 1cm/sec.Now, in distance piece, do not produce to cut down or peel off.
<manufacture of colored filter>
Example 12
Assorted colored composition (red colored constituent, green coloring constituent and blue-colored constituent) illustrated in use-case 3 and manufacture colored filter.First, utilize slit die coating machine to be coated with red colored constituent on the glass substrate be formed with black matrix pattern, carry out the preliminary drying of 2 minutes and form film on hot plate, at 90 DEG C.Thereafter, it is situated between every predetermined pattern mask, uses exposure machine CanonPLA501F (Canon Inc.) to irradiate and count as 1,000J/m with the conversion of i line2The ghi line of light exposure (wavelength is strength ratio=2.7 of 436nm, 405nm, 365nm: 2.5: 4.8), 0.05% potassium hydroxide aqueous solution is used to develop, the flushing of 60 seconds is carried out in ultra-pure water, then further in an oven, carry out the heat treated of 30 minutes at 180 DEG C, form the red striped design (pattern width is 100 μm) that thickness is 2.0 μm.
Secondly, similarly it is operated, uses green coloring constituent to form the striped design of green.Use blue-colored constituent to form the striped design of blueness further, form red, green and indigo plant 3 color striated colored filters (width of fringe is 100 μm).Above-mentioned the formed redness formed when after bake temperature is 180 DEG C, 30 minutes, green, 3 blue chromatic colorant patterns do not produce to harden insufficient caused pattern defect, on substrate the problem such as peeling, the striped design of 3 colors can be formed.
Secondly, on 3 color striped design of gained, it is coated with radiation-sensitive resin composition illustrated in example 7 by slit die coating machine.Secondly, carry out the preliminary drying of 5 minutes and form film on hot plate, at 90 DEG C, further in an oven, carry out the heat treated of 60 minutes at 180 DEG C, form the protecting film that thickness is 2.0 μm from the upper surface of 3 color striped design.Carry out as described above and manufacture the colored filter that is formed with protecting film on colored pattern.
The substrate being formed with protecting film on colored pattern about gained; use contact determining film thickness device α-Step (KLA-Tencor Japanese firm) and measure concavo-convex (flatness) on protecting film surface that (measured length is 2; 000 μm, measurement range be 2,000 μm square, measure and count n=5).That is, the streak line short-axis direction that makes mensuration direction be red, green, blue direction and red-red, green-green, blue-blue these 2 directions of whole-colored streak line long axis direction, all directions are measured with n=5 (the n number of total is 10).Obtain the meansigma methods of the highest portion of each mensuration and 10 times hung down from (nm) of lowest part.Meansigma methods now is 220nm.Even if after forming protecting film, colored pattern does not also shrink, expands, protecting film surface no concave-convex, it is shown that good flatness.
Secondly, about the substrate being formed with protecting film on colored pattern of gained, use sputtering method to form ito film on protecting film, thus forming ITO electrode.
Secondly, in ITO electrode, the radiation-sensitive resin composition modulated it is coated with in example 7 with slit die coating machine.Secondly, the hot plate of 100 DEG C carries out the preliminary drying of 2 minutes, form the film that thickness is 6.0 μm therefrom.Secondly, use high-pressure mercury-vapor lamp with 700J/m2Light exposure and the film of gained is carried out lonizing radiation irradiation.Thereafter, with developer pressure 1 (kgf/cm2) (nozzle diameter is 1mm) and to this substrate spray developer solution (the 0.04wt% potassium hydroxide aqueous solutions of 23 DEG C), therefrom carry out spray development, substrate is formed the pattern of distance piece.Secondly, after bake is carried out with the firm time of the hardening temperature of 180 DEG C and 30 minutes in an oven.Distance piece is formed therefrom in ITO electrode.Distance piece forms being formed in the region that region is corresponding with black matrix" in ITO electrode.
Manufacture the colored filter of this example as mentioned above.The colored filter of this manufactured example has the color characteristics of excellence.
Example 13
[there is the manufacture of the colored filter of light alignment film]
In this example, the colored filter of gained in use-case 12, use the crystal aligning agent comprising the radioactivity-sensitive polymer with light regiospecific base to form light alignment film.
First, colored filter at example 12 is formed on the substrate of distance piece, utilizes rotator to be coated with as crystal aligning agent A-1 described in the example 6 of the International Publication (WO) 2009/025386 of the crystal aligning agent comprising the radioactivity-sensitive polymer with light regiospecific base.Secondly, after the hot plate of 80 DEG C carries out the preliminary drying of 1 minute, carry out the heating of 1 hour and form the film that thickness is 80nm in the baking oven that inside has been carried out nitrogen displacement, at 180 DEG C.Secondly, use Hg-Xe lamp and Glan-Taylor prism, from the direction tilting 40 ° for the direction being perpendicular to substrate surface, this film coated surface is irradiated 200J/m2The polarisation ultraviolet of the open-wire line comprising 313nm, manufacture the colored filter with light alignment film.
Example 14
[there is the manufacture of the colored filter of vertical orientation film]
In this example, the colored filter of gained in use-case 12, use the crystal aligning agent comprising the polyimides not having light regiospecific base to form vertical orientation film.
First, the colored filter at example 12 is formed on the substrate of distance piece, utilizes rotator to be coated with the vertical orientation film formation AL60101 (JSRCorporation manufacture) as the crystal aligning agent comprising the polyimides not having light regiospecific base.Secondly, after the hot plate of 80 DEG C carries out the preliminary drying of 1 minute, carry out the heating of 1 hour and form the film that thickness is 80nm in the baking oven that inside has been carried out nitrogen displacement, at 180 DEG C, manufacture the colored filter with vertical orientation film.
<colored filter application in liquid crystal display cells>
Example 15
[manufacture of color liquid crystal display device]
The colored filter with light alignment film of gained in use-case 13 and manufacture liquid crystal display cells.Manufactured color liquid crystal display device has the structure identical with the color liquid crystal display device shown in above-mentioned Fig. 2.The color liquid crystal display device of this example demonstrates the homogeneity of the height in the gap between the substrate of clamping liquid crystal.And demonstrate electrical characteristic and display characteristic and the unfailing performance of excellence.
[industrial applicability]
The colored filter of the present invention may utilize hardening at subcritical temerature and manufactures, and has high reliability and color characteristics is excellent.Therefore, the colored filter of the present invention may be used as the flexible liquid crystal display colored filter of resin substrate or requires the large-scale liquid crystal display television colored filter of high image quality and use aptly.
Claims (21)
1. a colored filter, it is characterised in that comprise colored pattern, protecting film and distance piece,
Described colored pattern contains at least one coloring agent of the group selecting free triarylmethane class dyestuff and azo dyes to constitute；
Described protecting film is formed by the 1st radiation-sensitive resin composition containing, for example lower compound:
[A] have epoxy radicals compound,
[B] have ethylene unsaturated bond polymerizable compound,
[C] radioactivity-sensitive polymerization initiator and
At least one compound of the group that the compound represented by [D] the free following formula of choosing (1) and the compound represented by following formula (2) are constituted,
It is polymer that [A] contained in described 1st radiation-sensitive resin composition has the compound of epoxy radicals,
[A] contained in described 1st radiation-sensitive resin composition has the compound of epoxy radicals and has carboxyl；
Described distance piece is formed by the 2nd radiation-sensitive resin composition containing, for example lower compound:
[E] alkali soluble resins,
[F] have ethylene unsaturated bond polymerizable compound,
[G] radioactivity-sensitive polymerization initiator and
At least one compound of the group that the compound represented by [H] the free following formula of choosing (1) and the compound represented by following formula (2) are constituted；
[changing 1]
[changing 2]
In formula (1), R1～R6It is each independently hydrogen atom, electron-withdrawing group or amino；Wherein, R1～R6In at least 1 be electron-withdrawing group, and R1～R6In at least 1 be amino；And, all or part of of the hydrogen atom of above-mentioned amino can also be replaced by the alkyl that carbon number is 1～6；
In formula (2), R7～R16It is each independently hydrogen atom, electron-withdrawing group or amino；Wherein, R7～R16In at least 1 be amino；And, all or part of of the hydrogen atom of above-mentioned amino can also be replaced by the alkyl that carbon number is 1～6；A is singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number is the alkylene of 2～6；Wherein, all or part of of the hydrogen atom of above-mentioned methylene and alkylene can also be replaced by cyano group, halogen atom or fluoroalkyl.
2. colored filter according to claim 1, it is characterised in that:
Described colored pattern is formed by the colored composition containing, for example lower compound:
[I] alkali soluble resins,
[II] have ethylene unsaturated bond polymerizable compound,
[III] radioactivity-sensitive polymerization initiator and
[IV] described coloring agent.
3. colored filter according to claim 2, it is characterised in that:
Described colored composition contains at least one compound of the group that [V] choosing freely compound represented by above-mentioned formula (1), the compound represented by above-mentioned formula (2), tertiary amine compound, amine salt, salt, amidine salt, amide compound, mercaptan compound, block isocyanate compound and the compound containing imidazole ring are constituted further.
4. the colored filter according to Claims 2 or 3, it is characterised in that:
[I] alkali soluble resins contained in described colored composition is the copolymer comprising following construction unit: the construction unit that construction unit that (I-1) is formed by least one of the group selecting free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute, (I-2) are formed by the unsaturated compound containing epoxy radicals.
5. colored filter according to any one of claim 1 to 3, it is characterised in that:
[E] alkali soluble resins contained in described 2nd radiation-sensitive resin composition is the copolymer comprising following construction unit: the construction unit that construction unit that (E-1) is formed by least one of the group selecting free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides to constitute, (E-2) are formed by the unsaturated compound containing epoxy radicals.
6. colored filter according to any one of claim 1 to 3, it is characterised in that:
Described colored pattern is the colored pattern formed under the hardening temperature below 200 DEG C.
7. colored filter according to any one of claim 1 to 3, it is characterised in that:
Described protecting film is the protecting film formed under the hardening temperature below 200 DEG C.
8. colored filter according to any one of claim 1 to 3, it is characterised in that:
Described distance piece is the distance piece formed under the hardening temperature below 200 DEG C.
9. colored filter according to any one of claim 1 to 3, it is characterised in that:
Described colored pattern is the colored pattern formed under than the less hardening temperature of the hardening temperature of described protecting film.
10. colored filter according to any one of claim 1 to 3, it is characterised in that:
Described colored pattern is the colored pattern formed under than the less hardening temperature of the hardening temperature of described distance piece.
11. colored filter according to any one of claim 1 to 3, it is characterised in that:
Described protecting film is the protecting film formed under than the less hardening temperature of the hardening temperature of described distance piece.
12. colored filter according to any one of claim 1 to 3, it is characterised in that:
It comprises alignment film, and described alignment film is the alignment film using the crystal aligning agent comprising the radioactivity-sensitive polymer with light regiospecific base and any number of gained in the crystal aligning agent comprising the polyimides not having light regiospecific base.
13. colored filter according to claim 12, it is characterised in that:
Described alignment film is the alignment film using the crystal aligning agent gained comprising the radioactivity-sensitive polymer with light regiospecific base.
14. a liquid crystal display cells, it is characterised in that comprise the colored filter according to any one of claim 1 to 13.
15. the manufacture method of a colored filter, it is characterised in that comprise the steps:
[1] forming the step of the film of colored composition on substrate, described colored composition contains at least one coloring agent of the group selecting free triarylmethane class dyestuff and azo dyes to constitute；
[2] on the film of described colored composition, form the step of colored pattern；
[3] step below 200 DEG C, the film being formed with described colored pattern hardened；
[4] on substrate, form the step of film of the 1st radiation-sensitive resin composition, described 1st radiation-sensitive resin composition containing, for example under compound:
[A] have epoxy radicals compound,
[B] have ethylene unsaturated bond polymerizable compound,
[C] radioactivity-sensitive polymerization initiator and
At least one compound of the group that the compound represented by [D] the free following formula of choosing (1) and the compound represented by following formula (2) are constituted,
It is polymer that [A] contained in described 1st radiation-sensitive resin composition has the compound of epoxy radicals,
[A] contained in described 1st radiation-sensitive resin composition has the compound of epoxy radicals and has carboxyl；
[5] at least some of step irradiating lonizing radiation to the film of described 1st radiation-sensitive resin composition；
[6] step that the described film having irradiated lonizing radiation in step [5] is developed；
[7] below 200 DEG C, make the step of the described film hardening developed in step [6]；
[8] forming the step of the 2nd radiation-sensitive resin composition film on the substrate of hardened described film with step [7], described 2nd radiation-sensitive resin composition is containing, for example lower compound:
[E] alkali soluble resins,
[F] have ethylene unsaturated bond polymerizable compound,
[G] radioactivity-sensitive polymerization initiator and
At least one compound of the group that the compound represented by [H] the free following formula of choosing (1) and the compound represented by following formula (2) are constituted；
[9] at least some of step irradiating lonizing radiation to the film of described 2nd radiation-sensitive resin composition；
[10] step that the described film having irradiated lonizing radiation in step [9] is developed；And
[11] the described film developed in step [10] hardening is made to form the step of distance piece below 200 DEG C；
[changing 3]
[changing 4]
In formula (1), R1～R6It is each independently hydrogen atom, electron-withdrawing group or amino；Wherein, R1～R6In at least 1 be electron-withdrawing group, and R1～R6In at least 1 be amino；And, all or part of of the hydrogen atom of above-mentioned amino can also be replaced by the alkyl that carbon number is 1～6；
In formula (2), R7～R16It is each independently hydrogen atom, electron-withdrawing group or amino；Wherein, R7～R16In at least 1 be amino；And, all or part of of the hydrogen atom of above-mentioned amino can also be replaced by the alkyl that carbon number is 1～6；A is singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number is the alkylene of 2～6；Wherein, all or part of of the hydrogen atom of above-mentioned methylene and alkylene can also be replaced by cyano group, halogen atom or fluoroalkyl.
16. the manufacture method of colored filter according to claim 15, it is characterised in that:
Described colored composition contains [I] alkali soluble resins further, [II] has the polymerizable compound of ethylene unsaturated bond, [III] radioactivity-sensitive polymerization initiator.
17. the manufacture method of the colored filter according to claim 15 or 16, it is characterised in that:
The hardening temperature of step [3] is the hardening temperature lower temperature than step [7].
18. the manufacture method of the colored filter according to claim 15 or 16, it is characterised in that:
The hardening temperature of step [3] is the hardening temperature lower temperature than step [11].
19. the manufacture method of the colored filter according to claim 15 or 16, it is characterised in that:
The hardening temperature of step [7] is the hardening temperature lower temperature than step [11].
20. the manufacture method of the colored filter according to claim 15 or 16, it is characterised in that:
[12] step at 200 DEG C of alignment films formed below is comprised after step [11].
21. the manufacture method of colored filter according to claim 20, it is characterised in that:
Step [12] be use comprise the radioactivity-sensitive polymer with light regiospecific base crystal aligning agent and comprise the polyimides not having light regiospecific base crystal aligning agent in any number of and form described alignment film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-112878 | 2011-05-19 | ||
| JP2011112878A JP5786451B2 (en) | 2011-05-19 | 2011-05-19 | Color filter, liquid crystal display element, and method of manufacturing color filter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102789020A CN102789020A (en) | 2012-11-21 |
| CN102789020B true CN102789020B (en) | 2016-07-06 |
Family
ID=47154467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210154317.1A Active CN102789020B (en) | 2011-05-19 | 2012-05-17 | The manufacture method of colored filter, liquid crystal display cells and colored filter |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5786451B2 (en) |
| KR (1) | KR101892491B1 (en) |
| CN (1) | CN102789020B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012255963A (en) * | 2011-06-10 | 2012-12-27 | Sumitomo Chemical Co Ltd | Colored photosensitive resin composition |
| JP5884325B2 (en) * | 2011-07-15 | 2016-03-15 | Jsr株式会社 | Color filter, liquid crystal display element, and method of manufacturing color filter |
| JP5826135B2 (en) * | 2012-08-23 | 2015-12-02 | 富士フイルム株式会社 | Colored radiation-sensitive composition and color filter using the same |
| US11044802B2 (en) | 2017-02-16 | 2021-06-22 | Azotek Co., Ltd. | Circuit board |
| US11225563B2 (en) | 2017-02-16 | 2022-01-18 | Azotek Co., Ltd. | Circuit board structure and composite for forming insulating substrates |
| US10813213B2 (en) | 2017-02-16 | 2020-10-20 | Azotek Co., Ltd. | High-frequency composite substrate and insulating structure thereof |
| US10743423B2 (en) * | 2017-09-15 | 2020-08-11 | Azotek Co., Ltd. | Manufacturing method of composite substrate |
| JP2021179451A (en) * | 2018-07-23 | 2021-11-18 | Jsr株式会社 | Color filter, liquid crystal display element and manufacturing method for color filter |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1512269A (en) * | 2002-12-26 | 2004-07-14 | Jsr株式会社 | Radioactive ray sensitive composition, black array, color filter and color liquid crystal display device |
| CN101458452A (en) * | 2007-12-14 | 2009-06-17 | Jsr株式会社 | X-ray sensitive resin composition, barrier body and protection film of liquid crystal display member and their forming methods |
| CN101498894A (en) * | 2008-01-28 | 2009-08-05 | 富士胶片株式会社 | Photosensitive resin composition, optical spacer, protecting film, coloring pattern, display device and substrate thereof |
| CN101526740A (en) * | 2008-03-03 | 2009-09-09 | 东进世美肯株式会社 | Low-temperature curable photosensitive resin composition |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2891418B2 (en) | 1988-11-26 | 1999-05-17 | 凸版印刷株式会社 | Color filter and manufacturing method thereof |
| JPH0812292B2 (en) | 1989-07-20 | 1996-02-07 | 凸版印刷株式会社 | Heat resistant color filter and manufacturing method thereof |
| JP4257758B2 (en) * | 1999-02-25 | 2009-04-22 | 大日本印刷株式会社 | Photosensitive resin composition and color filter |
| DE60020762T2 (en) * | 1999-02-25 | 2006-05-04 | Dai Nippon Printing Co., Ltd. | Photosensitive resin composition, color filter and copolymer resin suitable therefor |
| JP3651874B2 (en) | 1999-05-17 | 2005-05-25 | 大日本印刷株式会社 | Color filter and liquid crystal display device |
| JP2001022065A (en) * | 1999-07-05 | 2001-01-26 | Nippon Steel Chem Co Ltd | Image forming material and image device using same |
| JP2001081416A (en) * | 1999-09-13 | 2001-03-27 | Nippon Steel Chem Co Ltd | Cured film and color filter prepared by using same |
| JP2003066604A (en) * | 2001-08-28 | 2003-03-05 | Jsr Corp | Radiation sensitive resin composition for spacer, spacer and liquid crystal display element |
| JP4315429B2 (en) | 2003-09-26 | 2009-08-19 | 日本化薬株式会社 | Negative coloring photosensitive composition |
| JP4884832B2 (en) | 2006-01-17 | 2012-02-29 | 富士フイルム株式会社 | Dye-containing negative curable composition, color filter and method for producing the same |
| JP2007316179A (en) | 2006-05-24 | 2007-12-06 | Sumitomo Chemical Co Ltd | Colored photosensitive resin composition for forming color filter to be provided in image sensor, color filter, image sensor and camera system |
| US8304031B2 (en) * | 2007-08-21 | 2012-11-06 | Jsr Corporation | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device |
| JP5262258B2 (en) * | 2008-04-11 | 2013-08-14 | 大日本印刷株式会社 | Dye color filter |
| TWI475320B (en) * | 2009-02-13 | 2015-03-01 | Sumitomo Chemical Co | Coloring photo-seinsitive resin composition and color filter |
| WO2010116551A1 (en) * | 2009-03-30 | 2010-10-14 | シャープ株式会社 | Liquid crystal display device, process for producing liquid crystal display device, composition for forming polymer layer, and composition for forming liquid crystal layer |
-
2011
- 2011-05-19 JP JP2011112878A patent/JP5786451B2/en active Active
-
2012
- 2012-05-17 KR KR1020120052453A patent/KR101892491B1/en active IP Right Grant
- 2012-05-17 CN CN201210154317.1A patent/CN102789020B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1512269A (en) * | 2002-12-26 | 2004-07-14 | Jsr株式会社 | Radioactive ray sensitive composition, black array, color filter and color liquid crystal display device |
| CN101458452A (en) * | 2007-12-14 | 2009-06-17 | Jsr株式会社 | X-ray sensitive resin composition, barrier body and protection film of liquid crystal display member and their forming methods |
| CN101498894A (en) * | 2008-01-28 | 2009-08-05 | 富士胶片株式会社 | Photosensitive resin composition, optical spacer, protecting film, coloring pattern, display device and substrate thereof |
| CN101526740A (en) * | 2008-03-03 | 2009-09-09 | 东进世美肯株式会社 | Low-temperature curable photosensitive resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20120129796A (en) | 2012-11-28 |
| KR101892491B1 (en) | 2018-08-28 |
| JP5786451B2 (en) | 2015-09-30 |
| JP2012242622A (en) | 2012-12-10 |
| CN102789020A (en) | 2012-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102879846B (en) | The manufacture method of colored filter, liquid crystal display cells and colored filter | |
| CN102789020B (en) | The manufacture method of colored filter, liquid crystal display cells and colored filter | |
| CN102955188B (en) | The manufacture method of colored filter, liquid crystal display cells and colored filter | |
| JP5708227B2 (en) | Color filter, liquid crystal display element, and method of manufacturing color filter | |
| TWI510564B (en) | Coloring composition for color filter, color filter, display element, and pigment dispersion for color filter | |
| TW201437293A (en) | Coloring composition, coloring cured film and display element | |
| TW201543149A (en) | Coloring composition, coloring cured film and display device | |
| JP5862081B2 (en) | Array substrate, liquid crystal display element, and method of manufacturing array substrate | |
| TW201538641A (en) | Coloring composition, coloring cured film and display element | |
| CN102778812A (en) | Coloring composition, colour filter and dispaly element | |
| JP5857578B2 (en) | Color filter, liquid crystal display element, and method of manufacturing color filter | |
| JP2013221980A (en) | Coloring composition, color filter and display element | |
| CN102692661B (en) | The manufacture method of colored filter, colored filter and liquid crystal display cells | |
| JP5817562B2 (en) | COLOR FILTER, COLOR FILTER MANUFACTURING METHOD, AND LIQUID CRYSTAL DISPLAY ELEMENT | |
| TWI594076B (en) | Coloring composition, color filter, and display element | |
| TW201502700A (en) | Coloring composition, coloring cured film, and display element | |
| JP5708398B2 (en) | Color filter, liquid crystal display element, and method of manufacturing color filter | |
| TW201533169A (en) | Coloring composition, coloring cured film and display device | |
| CN102890352B (en) | The manufacture method of array base palte, liquid crystal display cells and array base palte | |
| JP5786501B2 (en) | Color filter, liquid crystal display element, and method of manufacturing color filter | |
| JP5786445B2 (en) | Array substrate, liquid crystal display element, and method of manufacturing array substrate | |
| TW201510106A (en) | Coloring composition, coloring curable film and display element | |
| CN112424652A (en) | Display element and method for manufacturing display element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |