CN102955188B - 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 PDF

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Publication number
CN102955188B
CN102955188B CN201210295610.XA CN201210295610A CN102955188B CN 102955188 B CN102955188 B CN 102955188B CN 201210295610 A CN201210295610 A CN 201210295610A CN 102955188 B CN102955188 B CN 102955188B
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compound
colored
acid
carbon number
group
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CN102955188A (en
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铃木康伸
本田晃久
奥田务
一户大吾
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JSR Corp
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JSR Corp
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    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • 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
    • 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
    • G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/075—Silicon-containing compounds

Abstract

The invention provides the manufacture method of a kind of colored filter of high reliability of hardening at subcritical temerature, liquid crystal display cells and colored filter, and use this colored filter and liquid crystal display cells is provided.Use colored pattern (6), diaphragm (8) and distance piece (9) and manufacture colored filter (10), described colored pattern (6) is containing diketopyrrolopyrroles pigment, zinc halide phthalocyanine pigment, any number of in triarylmethane class dye well azo dyes, described diaphragm (8) is obtained by the 1st radiation-sensitive resin composition comprising siloxane polymer, distance piece (9) by comprise alkali soluble resins and following formula (1) or following formula (2) compound person at least arbitrarily the 2nd radiation-sensitive resin composition and obtain.Use colored filter (10) and form liquid crystal display cells (1).

Description

The manufacture method of colored filter, liquid crystal display cells and colored filter
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 such as clamps liquid crystal and forms in a pair substrate such as glass substrate.
Liquid crystal display cells can have LCD alignment alignment film on the surface of the substrate of clamping liquid crystal.Previously, waited by distribution and between the substrate of liquid crystal display cells, configure the spherical or bar-shaped distance piece formed by glass, aluminium oxide or resin, the thickness of liquid crystal had remained the setting of 1 μm ~ about 10 μm.Liquid crystal display cells plays the function as fine optical gate (shutter) to the light radiated from the light source such as backlight or outer light.And, liquid crystal display cells make light partial through or shading and showing, there is the feature that slim, light weight etc. is excellent.
Liquid crystal display cells is the display element being used as counter centered by Charactes Display etc. or clock in exploitation originally.Thereafter, owing to becoming the lattice display that can carry out in large picture, therefore purposes is extended in display element of notebook computer etc.
And liquid crystal display cells overcomes the problems such as high-precision refinement, colorize and visual angle expansion, purposes is expanded to further in the display applications of PC (PC).Recently, achieve wider visual angle, the high-speed response of liquid crystal and the raising etc. of display quality, thus be used as large-scale slim TV display element.
Can realize one of technology of the development of this kind of liquid crystal display cells is the colorize technology that can realize colored display as above.
Liquid crystal display cells can not develop the color with himself usually, thus is difficult to carry out colour display.Therefore, develop the technology utilizing colored filter, become and can realize colored display.
In addition, in the colour display of organic electroluminescent (Electroluminescence, the EL) element using the colorize technology of colored filter also to can be used on to use white light-emitting layer or Electronic Paper etc.In addition, if utilize colored filter, then become and can carry out charge coupled cell (ChargeCoupledDevice, CCD) colour phhotograpy of the solid-state imager such as imageing sensor, complementary metal oxide semiconductor (CMOS) (ComplementaryMetalOxideSemiconductor, CMOS) imageing sensor.
Colored filter comprises the transparency carriers such as glass and red, green and blue etc. slight pigmentation pattern.Colored pattern adopts the regular shapes such as clathrate and arranges on the transparent substrate.
The manufacture method of colored filter such as there will be a known method as described below.On the transparent substrate or be formed on the transparency carrier of light shield layer of desired pattern, the colored composition of the suitable illuminated line responded to is coated with.Colored composition can be used in colorant the painted radiation-sensitive composition of pigment-dispersing type of the pigment comprising red, green, blue etc.Secondly, after making dried coating film, be situated between every mask to dry coating irradiation radioactive ray (hereinafter referred to as " exposure "), implement development treatment.Then, carry out the sclerosis under the high temperature more than 200 DEG C such as such as 230 DEG C, obtain fixing colored pattern (such as with reference 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 contribute to this kind of performance and improves.In order to the high-precision refinement of the high-contrast or solid-state imager that realize display element, effectively use dyestuff as colorant (such as with reference to patent documentation 3 ~ patent documentation 5).In colored filter, dyestuff is used also to receive publicity as the technology of colorant.In the previous colored composition comprising dyestuff, mainly adopt method for curing polyfunctional acrylic ester, alkoxy methyl melamine resin etc. and polymerization initiator combined.
But, there is following problem using the colored composition comprising dyestuff in the colored pattern formed: comprise the colored pattern of the colored composition of pigment Comparatively speaking with use, reliability, particularly poor heat resistance.Therefore, in order to be formed in the cure step of colored pattern, heating is at lower temperatures required.
And, in the manufacture of colored filter, when after formation colored pattern, become the ITO (IndiumTinOxide: the indium oxide doped with tin) of electrode in film forming before, diaphragm can be formed on colored pattern.This diaphragm is to protect colored pattern, realizes the ITO of excellent characteristic on the other hand and is formed.Herein, in order to form diaphragm, required cure step usually.Heating in cure step becomes and causes the use being in diaphragm lower floor to comprise the colored composition of dyestuff and the deterioration of the colored pattern formed.Therefore, the low temperature of the cure step forming diaphragm is required.
In addition, in colored filter, nearest exploitation prevailing arranges the technology (such as with reference to patent documentation 6) of column spacer.On colored filter, the upright column spacer arranged can use and the interval between a pair substrate of clamping liquid crystal can be remained the such as photoresist of setting etc. and be formed.The distance piece of column can realize the control of the thickness of liquid crystal clamped between substrate accurately.Therefore, become the technology of the spherical or bar-shaped distance piece configured between aforesaid substrate replaced in prior art, the homogeneity of the characteristic in liquid crystal display cells face can be made to improve.
When colored filter arranges column spacer, this distance piece be formed in colored filter as on the ITO of transparency electrode.That is, after substrate forms colored pattern, form ito film thereon, utilize such as photoetching technique etc. and form column spacer on ITO.Now, in order to form distance piece, required cure step usually.Heating in the cure step of this distance piece causes the colored pattern deterioration of the colored filter being in its lower floor.Particularly when being formed colored pattern by the colored composition containing dyestuff, this deterioration becomes large problem.Therefore, for the cure step of column spacer, be 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 mentioned above, the problem of poor heat resistance is there is in the colored filter formed using the previous colored composition comprising dyestuff.
Therefore require to be manufactured the colored filter that contain colored pattern, diaphragm and column spacer by the cure step of low temperature.In this case, in previous colored filter, there is following phenomenon: in resistance to developability or be applied in liquid crystal display cells time the reliability such as voltage retention in cannot realize sufficient performance, thus become problem.The reason of this kind of problem can be enumerated: the sclerous reaction of the colored composition of hardening at subcritical temerature or diaphragm or distance piece is insufficient.Therefore, require to develop the colored composition using and can comprise dyestuff, the colored filter that the reliability formed by hardening at subcritical temerature is high.
In addition, in the manufacture of previous colored filter, carried out the formation of colored pattern formation, diaphragm formation, column spacer (following, if record, referred to as distance piece without special) by the elevated temperature heating stage more than 200 DEG C.The film forming of LCD alignment alignment film is also undertaken by the elevated temperature heating stage more than 200 DEG C.But, recently, consider from energy-conservation viewpoint, pursue the low temperature of the heating steps in this kind of manufacturing step gradually.That is, pursue the manufacturing step low temperature by making to comprise cure step gradually and realize energy-conservation.
According to above situation; the colored filter that strong expectation is following: there is the colored composition forming colored pattern by hardening at subcritical temerature; the diaphragm formed by hardening at subcritical temerature and the distance piece formed by hardening at subcritical temerature; and the excellence such as resistance to developability, thermotolerance, solvent resistance, voltage retention, the higher image quality of liquid crystal display cells and the colored filter of high brightness can be realized.
Summary of the invention
The present invention forms in view of problem as above.That is; the object of the present invention is to provide colored filter and manufacture method thereof, described colored filter comprises: use the colored composition and the colored pattern, the diaphragm formed by hardening at subcritical temerature and the distance piece formed by hardening at subcritical temerature that are formed by hardening at subcritical temerature that can comprise dyestuff.
And; other objects of the present invention are to provide the liquid crystal display cells using colored filter to form, and described colored filter comprises: use the colored composition that can comprise dyestuff and the colored pattern, the diaphragm 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 characterized in that contain colored pattern, diaphragm,
Described colored pattern contains at least a kind of colorant being selected from the group be made up of diketopyrrolopyrroles pigment, zinc halide phthalocyanine pigment, triarylmethane class dye well azo dyes;
Described diaphragm is formed by the 1st radiation-sensitive resin composition containing, for example lower composition:
[A] siloxane polymer,
[B] radical polymerization initiator and
[C] organic solvent.
In the 1st aspect of the present invention, preferably comprise distance piece further, described distance piece is formed by the 2nd radiation-sensitive resin composition containing, for example lower composition:
[α] alkali soluble resins,
[β] have ethene unsaturated link polymerizable compound,
[γ] radioactivity-sensitive polymerization initiator and
[δ] is selected from least a kind of compound of the group that the compound represented by following formula (1) and the compound represented by following formula (2) are formed;
[changing 1]
[changing 2]
In formula (1), R 1~ R 6be independently hydrogen atom, electron-withdrawing group or amino; Wherein, R 1~ R 6in at least 1 be electron-withdrawing group, and R 1~ R 6in at least 1 be amino; And all or part of alkyl that can be also 1 ~ 6 by carbon number of the hydrogen atom of above-mentioned amino replaces;
In formula (2), R 7~ R 16be independently hydrogen atom, electron-withdrawing group or amino; Wherein, R 7~ R 16in at least 1 be amino; And all or part of alkyl that can be also 1 ~ 6 by carbon number of the hydrogen atom of above-mentioned amino replaces; A is singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number are 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.
In the 1st aspect of the present invention, preferred colored pattern is formed by the colored composition containing, for example lower composition:
[I] alkali soluble resins,
[II] have ethene unsaturated link polymerizable compound,
[III] radioactivity-sensitive polymerization initiator and
[IV] described colorant.
In the 1st aspect of the present invention, preferred colored composition is selected from least a kind of compound of the group that the compound represented by above-mentioned formula (1), the compound represented by above-mentioned formula (2), tertiary amine compound, amine salt, phosphonium salt, amidine salt, amide compound, mercaptan compound, block isocyanate compound and the compound containing imidazole ring are formed further containing [V].
In the 1st aspect of the present invention, [I] alkali soluble resins contained in preferred colored composition is the multipolymer comprising following structural unit: the structural unit that (I-1) is formed by the unsaturated compound containing epoxy radicals by least a kind that is selected from the group be made up of unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides structural unit formed, (I-2).
In the 1st aspect of the present invention, preferably contained in the 1st radiation-sensitive resin composition [A] siloxane polymer is the hydrolytic condensate of hydrolysable silanes compound, and this hydrolysable silanes compound comprises:
(a1) the hydrolysable silanes compound represented by following formula (A-1), with
(a2) the hydrolysable silanes compound represented by following formula (A-2);
[changing 3]
[changing 4]
In formula (A-1), R 1to be carbon number be 1 ~ 6 alkyl; R 2it is the organic group comprising free-radical reactive functional group; P is the integer of 1 ~ 3; Wherein, R is worked as 1and R 2when becoming multiple situations, multiple R 1and R 2independently;
In formula (A-2), R 3to be carbon number be 1 ~ 6 alkyl; R 4hydrogen atom, the carbon number alkyl that is 1 ~ 20, carbon number be 1 ~ 20 fluorinated alkyl, phenyl, naphthyl, epoxy radicals, amino or isocyanate group; N is the integer of 0 ~ 20; Q is the integer of 0 ~ 3; Wherein, R is worked as 3and R 4when becoming multiple situations, multiple R 3and R 4independently.
In the 1st aspect of the present invention, preferably the 1st radiation-sensitive resin composition is further containing [D] ethene unsaturated compound except [A] siloxane polymer.
In the 1st aspect of the present invention, preferably the 1st radiation-sensitive resin composition is further containing [E] radioactivity-sensitive acid agent or radioactivity-sensitive generated base alkaline agent.
In the 1st aspect of the present invention, preferably contained in the 2nd radiation-sensitive resin composition [α] alkali soluble resins is the multipolymer comprising following structural unit: the structural unit that (α-1) is formed by the unsaturated compound containing epoxy radicals by least a kind that is selected from the group be made up of unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides structural unit formed, (α-2).
In the 1st aspect of the present invention, preferred colored pattern is the colored pattern formed under the hardening temperature below 200 DEG C.
In the 1st aspect of the present invention, preferred diaphragm is the diaphragm formed under the hardening temperature below 200 DEG C.
In the 1st aspect of the present invention, preferred interval part is the distance piece formed under the hardening temperature below 200 DEG C.
In the 1st aspect of the present invention, preferred colored pattern is the colored pattern formed under the hardening temperature lower than the hardening temperature of diaphragm.
In the 1st aspect of the present invention, preferred colored pattern is the colored pattern formed under the hardening temperature lower than the hardening temperature of distance piece.
In the 1st aspect of the present invention, preferred diaphragm is the diaphragm formed under the hardening temperature lower than the hardening temperature of distance piece.
In the 1st aspect of the present invention, preferably comprise alignment film, described alignment film be use the crystal aligning agent and comprising comprising the radioactivity-sensitive polymkeric substance with light regiospecific base do not have light regiospecific base polyimide crystal aligning agent in the alignment film of any number of gained.
In the 1st aspect of the present invention, preferred alignment film uses the alignment film comprising the crystal aligning agent gained of the radioactivity-sensitive polymkeric substance with light regiospecific base.
2nd aspect of the present invention relates to a kind of liquid crystal display cells, it is characterized in that the colored filter comprising the 1st aspect of the present invention.
3rd aspect of the present invention relates to a kind of manufacture method of colored filter, it is characterized in that comprising the steps:
[1] on substrate, form the step of the film of colored composition, described colored composition contains at least a kind of colorant being selected from the group be made up of diketopyrrolopyrroles pigment, zinc halide phthalocyanine pigment, triarylmethane class dye well azo dyes;
[2] on the film of colored composition, form the step of colored pattern;
[3] below 200 DEG C to the step that the film being formed with colored pattern hardens;
[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 composition:
[A] siloxane polymer,
[B] radical polymerization initiator and
[C] organic solvent;
[5] to the step of irradiating radioactive ray at least partially of the film of the 1st radiation-sensitive resin composition;
[6] to the step that the film having irradiated radioactive ray in step [5] develops;
[7] below 200 DEG C, make the step of the film sclerosis of developing in step [6];
[8] on the substrate of the film through sclerosis with step [7], form the step of the 2nd radiation-sensitive resin composition film, described 2nd radiation-sensitive resin composition is containing, for example lower composition:
[α] alkali soluble resins,
[β] have ethene unsaturated link polymerizable compound,
[γ] radioactivity-sensitive polymerization initiator and
[δ] is selected from least a kind of compound of the group that the compound represented by following formula (1) and the compound represented by following formula (2) are formed;
[9] to the step of irradiating radioactive ray at least partially of the film of the 2nd radiation-sensitive resin composition;
[10] to the step that the film having irradiated radioactive ray in step [9] develops; And
[11] below 200 DEG C, the film developed in step [10] is made to harden and form the step of distance piece;
[changing 5]
[changing 6]
In formula (1), R 1~ R 6be independently hydrogen atom, electron-withdrawing group or amino; Wherein, R 1~ R 6in at least 1 be electron-withdrawing group, and R 1~ R 6in at least 1 be amino; And all or part of alkyl that can be also 1 ~ 6 by carbon number of the hydrogen atom of above-mentioned amino replaces;
In formula (2), R 7~ R 16be independently hydrogen atom, electron-withdrawing group or amino; Wherein, R 7~ R 16in at least 1 be amino; And all or part of alkyl that can be also 1 ~ 6 by carbon number of the hydrogen atom of above-mentioned amino replaces; A is singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number are 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.
In the 3rd aspect of the present invention, preferred colored composition has polymerizable compound, [III] radioactivity-sensitive polymerization initiator of ethene unsaturated link further containing [I] alkali soluble resins, [II].
In the 3rd aspect of the present invention, the hardening temperature of preferred steps [3] is the temperature lower than the hardening temperature of step [7].
In the 3rd aspect of the present invention, the hardening temperature of preferred steps [3] is the temperature lower than the hardening temperature of step [11].
In the 3rd aspect of the present invention, the hardening temperature of preferred steps [7] is the temperature lower than the hardening temperature of step [11].
In the 3rd aspect of the present invention, after step [11], preferably comprise the step that [12] form alignment film below 200 DEG C.
In the 3rd aspect of the present invention, preferred steps [12] be use the crystal aligning agent and comprising comprising the radioactivity-sensitive polymkeric substance with light regiospecific base do not have light regiospecific base polyimide crystal aligning agent in any one and form alignment film.
The effect of invention
There is provided a kind of manufacture by hardening at subcritical temerature according to the present invention and there is colored filter and the manufacture method thereof of high reliability.
And, provide according to the present invention to manufacture by hardening at subcritical temerature and to have the colored filter of high reliability a kind of comprising, the liquid crystal display cells of colored display can be carried out.
Accompanying drawing explanation
Fig. 1 is the mode sectional drawing of the colored filter of this example.
Fig. 2 is the mode sectional drawing of the color liquid crystal display device of the colored filter comprising this example.
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: diaphragm
9: distance piece
10: colored filter
12: alignment film
13: liquid crystal
14: Polarizer
16: encapsulant
17: backlight light
Embodiment
Below example of the present invention is illustrated.
In addition, in the present invention, " radioactive ray " that irradiate when exposing are the concepts comprising luminous ray, ultraviolet, far ultraviolet, X ray, charged particle beam etc.
< liquid crystal display cells >
The liquid crystal display cells of this example is the color liquid crystal display device of the colored filter comprising this example.
Below, the structure of the liquid crystal display cells of this example is illustrated.
The liquid crystal display cells of this example can be such as make to be configured with thin film transistor (TFT) (ThinFilmTransistor; The structure of driving substrate TFT), every the liquid crystal layer subtend of being situated between with other substrates of colored filter forming this example.Or, liquid crystal display cells can also be make to be formed the colored pattern of described later example or diaphragm or distance piece on the driving substrate being configured with thin film transistor (TFT) (TFT) and form substrate, be formed with ITO (IndiumTinOxide; Indium oxide doped with tin) substrate of electrode is situated between every liquid crystal layer the structure of subtend.The structure of the latter has following advantage: 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 example.
Colored filter 10 shown in Fig. 1 is examples for the colored filter of this example.There is following structure: on transparent substrate 5, be configured with redness (R), the colored pattern 6 of green (G) and blue (B), black matrix" 7, the diaphragm 8 be located on colored pattern 6, the ITO electrode 4 be located on diaphragm 8, the upright distance piece 9 arranged in ITO electrode 4.
In addition, the color of colored pattern 6 does not limit above-mentioned RGB3 look, can also select other colors or adds yellow (Y) further and make the colored pattern of 4 looks.
As described later, in the colored filter 10 of this example, colored pattern 6 is formed containing suitable colorant.Specifically, the colored composition containing preferred colorant is coated on after substrate carries out patterning, makes it harden and be formed.Diaphragm 8 is after carrying out patterning, make it harden and be formed at coating radiation-sensitive resin composition similarly.Distance piece 9 is after carrying out patterning, make it harden and be formed at coating radiation-sensitive resin composition similarly.In addition; in the following description; for convenience's sake, the radiation-sensitive resin composition in order to form diaphragm 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 have following feature: as described later; all can be made into radiation-sensitive resin composition, and by less than 200 DEG C hardening at subcritical temerature and form colored pattern 6 and diaphragm 8 and distance piece 9 respectively.
Therefore, in the colored filter 10 of this example, become and can be formed colored pattern 6 and diaphragm 8 and distance piece 9 respectively by the hardening at subcritical temerature of less than 200 DEG C, and can hardening at subcritical temerature be utilized and manufacture.
And, in colored filter 10, after formation colored pattern 6, form diaphragm 8.Diaphragm 8 by less than 200 DEG C hardening at subcritical temerature and formed, under the state therefore becoming the high-temperature heating without the need to being exposed to colored pattern 6 after its formation to be formed diaphragm.Similarly, in colored filter 10, after formation colored pattern 6, formation diaphragm 8, form distance piece 9.Distance piece 9 can be formed, under the state therefore becoming the high-temperature heating without the need to being exposed to colored pattern 6 after its formation to be formed distance piece 9 by the hardening at subcritical temerature of less than 200 DEG C.Therefore, in colored filter 10, even if although use color characteristics excellence in the formation of colored pattern 6 to there is the dyestuff of problem as colorant in thermotolerance, also step deterioration can be reduced.That is, dyestuff can being selected as the colorant of colored composition, the colored pattern 6 of color characteristics excellence can be formed by using the colored composition of dyestuff.
In addition, as mentioned above, colored composition, the 1st radiation-sensitive resin composition and the 2nd radiation-sensitive resin composition are all resin combinations of radioactivity-sensitive, respectively in order to manufacture colored filter 10.Therefore, when manufacturing colored filter 10, can consider to be formed hardening temperature when diaphragm 8 and adjustment form colored pattern 6 on colored pattern 6.That is, on the substrate 5, utilize the hardening temperature Comparatively speaking lower with optimum hardening temperature when forming separately colored pattern 6 and form colored pattern 6.Thereafter, the heating undertaken colored pattern 6 by carrying out sclerosis heating to the diaphragm 8 that colored pattern 6 is formed.Similarly, when manufacturing colored filter 10, can consider to be formed the hardening temperature formed after colored pattern 6 when distance piece 9 and adjustment form colored pattern 6.That is, on the substrate 5, utilize the hardening temperature Comparatively speaking lower with optimum hardening temperature when only to form colored pattern 6 and form colored pattern 6.And, after formation ITO electrode 4, can also heat colored pattern 6 by being uprightly arranged on the sclerosis heating of the distance piece 9 in ITO electrode 4.
Such as, be respectively less than 200 DEG C at colored pattern 6 and the optimum hardening temperature of diaphragm 8, when being specifically 180 DEG C, colored pattern 6 can be formed on the substrate 5 in advance by the hardening temperature lower than 180 DEG C.Such as, colored pattern 6 can be pre-formed by the hardening temperature of 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 diaphragm 8 therefrom.And the colored pattern 6 become being in its lower floor heats, and can obtain the colored pattern 6 of desired state.In addition, on the substrate 5, be pre-formed colored pattern 6 with the hardening temperature of such as 150 DEG C, form distance piece 9 with the hardening temperature of optimum 180 DEG C by the 2nd radiation-sensitive resin composition thereafter.Its result, becomes and heats the colored pattern 6 of the lower floor being in distance piece 9, can obtain the colored pattern 6 of desired state.In the above circumstances, become the colorant that dyestuff can be selected as colored composition, utilize the colored pattern 6 formed by using the colored composition of dyestuff, the colored filter 10 of color characteristics excellence can be provided.
And, when manufacturing colored filter 10, can consider to form distance piece 9 after forming colored pattern 6 and diaphragm 8 and the hardening temperature that adjusts when forming colored pattern 6 and form diaphragm 8 time hardening temperature.That is, on the substrate 5, utilize the hardening temperature Comparatively speaking lower with optimum hardening temperature when only to form colored pattern 6 and form colored pattern 6.Secondly, utilize the hardening temperature Comparatively speaking lower with optimum hardening temperature when only forming diaphragm 8 and form diaphragm 8.And, after formation ITO electrode 4, also can also heat colored pattern 6 and diaphragm 8 by being uprightly arranged on the sclerosis heating of the distance piece 9 in ITO electrode 4.
Such as, be respectively less than 200 DEG C in colored pattern 6 and diaphragm 8 and the optimum hardening temperature of distance piece 9, when being specifically 180 DEG C, can by the hardening temperature lower than 180 DEG C formation colored pattern 6 on the substrate 5 in advance.Such as, colored pattern 6 can be pre-formed by the hardening temperature of 150 DEG C.Secondly, this colored pattern 6 forms the film of the 1st radiation-sensitive resin composition, such as, can be pre-formed by the hardening temperature of 150 DEG C.Secondly, after diaphragm 8 is formed ITO electrode 4, ITO electrode 4 forms the film of the 2nd radiation-sensitive resin composition.Secondly, patterning is carried out to this film, hardens with optimum 180 DEG C, form distance piece 9 therefrom.Its result, the colored pattern 6 and diaphragm 8 become being in lower floor heats, and can obtain colored pattern 6 and the diaphragm 8 of desired state.In such cases, become the colorant that dyestuff can be selected as colored composition, utilize the colored pattern 6 formed by using the colored composition of dyestuff, the colored filter 10 of color characteristics excellence can be provided.
In addition, in the colored filter 10 of this example, after formation distance piece 9, LCD alignment alignment film (at Fig. 1 and not shown) can be set as described later like that.Alignment film can use the crystal aligning agent that comprises the radioactivity-sensitive polymkeric substance with light regiospecific base or comprise do not have light regiospecific base polyimide crystal aligning agent and obtain.In this case, become and can form alignment film under the heating-up temperature below 200 DEG C.
Secondly, the liquid crystal display cells of this example of the colored filter of this example of application is illustrated.
Fig. 2 is the mode sectional drawing of the color liquid crystal display device of the colored filter comprising this example.
Liquid crystal display cells 1 shown in Fig. 2 is an example of the liquid crystal display cells of this example, is the display element of twisted nematic (TwistedNematic, TN) the type liquid crystal mode that TFT drives.This color liquid crystal display device has above-mentioned driving substrate, is situated between every TN liquid crystal layer and the structure of subtend with the substrate of the colored filter forming above-mentioned example.
As shown in Figure 2, in the side connected with liquid crystal 13 of transparent substrate 2, the transparent pixel electrode 3 comprising ITO and TFT (not shown) are arranged for clathrate and form driving substrate.
And, in the side connected with liquid crystal 13 of transparent substrate 5, be configured with the above-mentioned colored pattern 6 etc. manufactured by hardening at subcritical temerature, form colored filter 10.More specifically be configured with colored filter 10; described colored filter 10 includes on the substrate 5: with the redness set by the position of pixel electrode 3 subtend, green and blue colored pattern 6; black matrix" 7; diaphragm 8 set on colored pattern 6; ITO electrode 4 set on diaphragm 8; the distance piece 9 that ITO electrode 4 is uprightly arranged, alignment film 12.ITO electrode 4 forms public electrode in liquid crystal display cells 1.
Be provided with the alignment film 12 same with substrate 5 on a substrate 2.By carrying out the orientation process such as such as friction treatment to each alignment film 12 in the case of necessary, the homogeneous orientation of liquid crystal 13 clamped between substrate 2, substrate 5 can be realized.
In substrate 2 with substrate 5, be configured with Polarizer 14 respectively 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 from back light unit (not shown) to the backlight light that liquid crystal 13 irradiates.Back light unit such as can use combination to have the back light unit of the structure of the fluorescent tubes such as cold cathode fluorescent tube (CCFL:ColdCathodeFluorescentLamp) and scatter plate.And can also use with White LED is the back light unit of light source.White LED include, for example: use 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 is obtained the White LED of white light by colour mixture, by blue led, red LED, green-emitting phosphor is combined and is obtained the White LED of white light by colour mixture, by blue led, red light-emitting phosphor, green-emitting phosphor body is combined and is obtained the White LED of white light by colour mixture, pass through blue led, the colour mixture of YAG class fluorophor and obtain the White LED of white light, by blue led, orange luminescence fluorophor, green-emitting phosphor body is combined and is obtained the White LED of white light by colour mixture, by ultraviolet LED, red light-emitting phosphor, green-emitting phosphor body, blue-light-emitting fluorescent material is combined and is obtained the White LED etc. of white light by colour mixture.
In the color liquid crystal display device of this example, except above-mentioned TN type, STN Super TN (SuperTwistedNematic can also be set to, STN) type, coplanar conversion (In-PlanesSwitching, IPS) type, vertical orientation (VerticalAlignment, VA) liquid crystal mode such as type or optical compensation birefringence (OpticallyCompensatedBirefringence, OCB) type.In this case, LCD alignment alignment film selects optimum alignment film in each liquid crystal mode, such as, use the alignment film of vertical orientation type when VA type.
Secondly, the colored filter of this example of the main composition key element of the liquid crystal display cells as this example is described in more detail.
The colored filter of this example contains colored pattern as described above, the diaphragm be located on this colored pattern.ITO electrode on diaphragm can comprise the upright distance piece arranged, be color characteristics excellence and the colored filter manufactured by hardening at subcritical temerature.
Colored pattern can use colored composition and be formed on suitable substrate, and diaphragm is use the 1st radiation-sensitive resin composition and is formed on this colored pattern.Distance piece can use the 2nd radiation-sensitive resin composition and be formed in the ITO electrode on diaphragm.That is the colored filter of this example can use colored composition, the 1st radiation-sensitive resin composition and the 2nd radiation-sensitive resin composition and manufacture.
Following, first the colored pattern of the colored filter of this example is illustrated, particularly the colored composition of this example used in the formation of colored pattern is illustrated.
< colored composition >
The colored composition used in the manufacture of the colored filter of this example contains [I] alkali soluble resins, [II] polymerizable compound, [III] polymerization initiator and [IV] colorant.And, [V] compound can be contained further.And, only otherwise undermine effect of the present invention, then can also contain other any compositions.Below, each composition contained in colored composition is illustrated.
< [I] alkali soluble resins >
[I] if alkali soluble resins has the resin that thus carboxyl has alkali-developable, is then not particularly limited.And, preferably comprise the multipolymer of at least a kind of structural unit being selected from the group be made up of the structural unit with (methyl) acryloxy and the structural unit with epoxy radicals.[I] alkali soluble resins has above-mentioned specific structure unit, therefore can be formed and have the excellent indurative cured film of Surface hardened layer and deep.
[I] alkali soluble resins synthesizes by making following structural unit copolymerization, thus obtains the multipolymer comprising those structural units: the structural unit that the structural unit that (I-1) was formed by least a kind (being also called below " (I-1) compound ") being selected from the group be made up of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides, (I-2) are formed by the unsaturated compound (being also called below " (I-2) compound ") containing epoxy radicals.
[I] alkali soluble resins such as can by a solvent, (I-1) compound of making under the existence of polymerization initiator imparting contain the structural unit of carboxyl and (I-2) the compound copolymerization of the structural unit given containing epoxy radicals and manufacture.And, (I-3) can also be added further and give the hydroxyl unsaturated compound (being also called below " (I-3) compound ") of the structural unit containing hydroxyl and make multipolymer.In addition, in the manufacture of [I] alkali soluble resins, can also together add (I-4) compound (imparting is derived from the unsaturated compound of the structural unit beyond the structural unit of above-mentioned (I-1) compound, (I-2) compound and (I-3) compound) further with above-mentioned (I-1) compound, (I-2) compound and (I-3) compound and make multipolymer.Below, each compound is described in detail.
[(I-1) compound]
(I-1) compound can enumerate unsaturated monocarboxylic, unsaturated dicarboxylic, the acid anhydrides of unsaturated dicarboxylic, list [(methyl) acryloxyalkyl] ester of polybasic carboxylic acid, list (methyl) acrylate at two ends with the polymkeric substance of carboxyl and hydroxyl, the unsaturated polycyclic compound with carboxyl and acid anhydrides etc. thereof.
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 acid anhydrides of unsaturated dicarboxylic include, for example as above-mentioned dicarboxylic acid and the acid anhydrides etc. of illustrative compound;
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 at two ends with the polymkeric substance of carboxyl and hydroxyl include, for example ω-carboxy-polycaprolactone list (methyl) acrylate etc.;
Unsaturated polycyclic compound and the acid anhydrides 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" acid anhydrides 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 also can be used in combination by two or more.
As the usage ratio of (I-1) compound, based on the total of (I-1) compound and (I-2) compound (being optionally arbitrary (I-3) compound and (I-4) compound), be preferably 5 quality % ~ 30 quality %, be more preferably 10 quality % ~ 25 quality %.By making the usage ratio of (I-1) compound be 5 quality % ~ 30 quality %, the dissolubility optimization for alkaline aqueous solution of [I] alkali soluble resins can be made, thus obtain the colored composition of the sexy luminosity excellence of radioactive ray.
[(I-2) compound]
(I-2) compound has the free-radical polymerised unsaturated compound containing epoxy radicals.Epoxy radicals can enumerate Oxyranyle (1,2-epoxy construction), epoxypropane 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 of copolyreaction and colored pattern etc. improve, preferable methyl glycidyl acrylate, 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 epoxypropane base include, for example: 3-(acryloyloxymethyl) epoxypropane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-3-ethyl epoxypropane, 3-(acryloyloxymethyl)-2-benzyl ring Ethylene Oxide, 3-(2-acryloyl-oxyethyl) epoxypropane, 3-(2-acryloyl-oxyethyl)-2-ethyl epoxypropane, 3-(2-acryloyl-oxyethyl)-3-ethyl epoxypropane, the acrylate such as 3-(2-acryloyl-oxyethyl)-2-benzyl ring Ethylene Oxide, 3-(methacryloxymethyl) epoxypropane, 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryloxymethyl)-3-ethyl epoxypropane, 3-(methacryloxymethyl)-2-benzyl ring Ethylene Oxide, 3-(2-methacryloxyethyl) epoxypropane, 3-(2-methacryloxyethyl)-2-ethyl epoxypropane, 3-(2-methacryloxyethyl)-3-ethyl epoxypropane, 3-(2-methacryloxyethyl)-2-benzyl ring Ethylene Oxide, 3-(2-methacryloxyethyl)-2, the methacrylates etc. such as 2-difluoro epoxypropane.
Preferred (methyl) glycidyl acrylate in those (I-2) compounds.Those (I-2) compounds can be used alone also can be used in combination by two or more.
As the usage ratio of (I-2) compound, based on the total of (I-1) compound and (I-2) compound (being optionally arbitrary (I-3) compound and (I-4) compound), be preferably 5 quality % ~ 60 quality %, be more preferably 10 quality % ~ 50 quality %.By making the usage ratio of (I-2) compound be 5 quality % ~ 60 quality %, the cured film with excellent hardening etc. can be formed.
[(I-3) compound]
(I-3) first compound can enumerate (methyl) acrylate with hydroxyl, (methyl) acrylate, the hydroxy styrenes with phenolic hydroxyl group.
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 own ester of acrylic acid-6-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 own ester of methacrylic acid-6-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 also can be used in combination by two or more.
As the usage ratio of (I-3) compound, based on the total of (I-1) compound, (I-2) compound and (I-3) compound (being optionally arbitrary (I-4) compound), be preferably 1 quality % ~ 30 quality %, be more preferably 5 quality % ~ 25 quality %.
[(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 aromatics, conjugated diolefine, has the unsaturated compound and other unsaturated compounds etc. of tetrahydrofuran skeleton, furans skeleton, oxinane skeleton, pyrans skeleton etc.
Methacrylic acid chain-like alkyl ester include, for example methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, methacrylic acid secondary 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 [5.2.1.0 2,6] decane-8-base ester, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base oxygen base ethyl ester, isobornyl methacrylate etc.
Acrylic acid chain-like alkyl ester include, for example methyl acrylate, 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 [5.2.1.0 2,6] decane-8-base ester, acrylic acid three ring [5.2.1.0 2,6] 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 diethyl 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 dicyclo [2.2.1] hept-2-ene", 5-ethoxy 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 aromatics include, for example styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene etc.
Conjugated diolefine include, for example 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.
Unsaturated compound containing tetrahydrofuran skeleton include, for example (methyl) acrylic acid tetrahydrofuran methyl ester, 2-methacryloxy-propionic acid tetrahydrofuran methyl ester, 3-(methyl) acryloxy tetrahydrofuran-2-ketone etc.
Unsaturated compound containing furans skeleton include, for example 2-methyl-5-(3-furyl)-1-penten-3-one, (methyl) acrylic acid furfuryl group ester, 1-furans-2-butyl-3-alkene-2-ketone, 1-furans-2-butyl-3-methoxyl-3-alkene-2-ketone, 6-(2-furyl)-2-methyl isophthalic acid-hexene-3-one, 6-furans-2-base-oneself-1-alkene-3-ketone, acrylic acid-2-furans-2-base-1-methyl-ethyl ester, 6-(2-furyl)-6-methyl isophthalic acid-teracrylic acid-one etc.
Unsaturated compound containing oxinane skeleton include, for example methacrylic acid (oxinane-2-base) methyl esters, 2,6-dimethyl-8-(oxinane-2-base oxygen base)-Xin-1-alkene-3-ketone, 2-methacrylic acid oxinane-2-base ester, 1-(oxinane-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 vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate etc.
In those (I-4) compounds, preferable methyl acrylic acid chain-like alkyl ester, methacrylic acid cyclic alkyl ester, aryl methacrylate, maleimide compound, tetrahydrofuran skeleton, furans skeleton, oxinane skeleton, pyrans skeleton, unsaturated aromatics, acrylic acid cyclic alkyl ester.Consider from copolyreaction and for the deliquescent aspect of alkaline aqueous solution, more preferably styrene, methyl methacrylate, Tert-butyl Methacrylate, the positive Lauryl Ester of methacrylic acid, benzyl methacrylate, methacrylic acid three ring [5.2.1.0 in those compounds 2,6] decane-8-base ester, to methoxy styrene, acrylic acid-2-methyl cyclohexyl, N-phenylmaleimide, N-N-cyclohexylmaleimide, (methyl) acrylic acid tetrahydrofuran methyl ester, polyglycol (n=2 ~ 10) single (methyl) acrylate, 3-(methyl) acryloxy tetrahydrofuran-2-ketone.Those (I-4) compounds can be used alone also can be used in combination by two or more.
As the usage ratio of (I-4) compound, based on the total of (I-1) compound, (I-2) compound and (I-4) compound (and arbitrary (I-3) compound), be preferably 10 quality % ~ 80 quality %.
The synthetic method 1> of < [I] alkali soluble resins
[I] alkali soluble resins is such as by a solvent, under the existence of polymerization initiator, make (arbitrary (I-3) compound and (I-4) compound) copolymerization of above-mentioned (I-1) compound and (I-2) compound and manufacture.By this synthetic method, the multipolymer of the structural unit at least comprised containing epoxy radicals can be synthesized.
Include, for example alcohol, glycol ethers, ethylene glycol alkylether acetates, 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.
Usually the compound being known as radical polymerization initiator 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 two-(2,4-methyl pentane nitrile), 2,2 '-azo is two-azo-compound such as (4-methoxyl-2,4-methyl pentane nitrile).
In the polyreaction in order to manufacture [I] alkali soluble resins, in order to adjust molecular weight, molecular weight adjusting agent can be used.Molecular weight adjusting agent 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, mercaptoacetic acid; The xanthate classes 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, is more preferably 5,000 ~ 20,000.By making the Mw of [I] alkali soluble resins be above-mentioned scope, the light sensitivity of colored composition and developability can be made to improve.In addition, the Mw of the polymkeric substance in this instructions and number average molecular weight (Mn) measure by utilizing the gel permeation chromatography of following condition (GPC).
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: tetrahydrofuran
Tubing string temperature: 40 DEG C
Flow velocity: 1.0mL/min
Sample solution concentration: 1.0 quality %
Sample injection rate IR: 100 μ L
Detecting device: differential refractometer
Standard substance: monodisperse polystyrene
The synthetic method 2> of < [I] alkali soluble resins
And [I] alkali soluble resins such as can allow to use the multipolymer (being also called below " specific copolymer ") of more than a kind of above-mentioned (I-1) compound and synthesis and above-mentioned (I-2) compound to carry out reacting and synthesizing.Utilize this synthetic method, the multipolymer at least comprising the structural unit with (methyl) acryloxy can be synthesized.
The structural unit with (methyl) acryloxy contained by [I] alkali soluble resins is as shown in following formula (3).This structural unit is derived from the carboxyl in the specific copolymer of (I-1) compound and the epoxy reaction of (I-2) compound, forms ester bond and obtain.
[changing 7]
In above-mentioned formula (3), R 20and R 21be independently hydrogen atom or methyl.C is the integer of 1 ~ 6.R 22following formula (4-1) or the divalent base represented by formula (4-2).
[changing 8]
In above-mentioned formula (4-1), R 23for hydrogen atom or methyl.In above-mentioned formula (4-1) and formula (4-2), * represents the position with oxygen atom bond.
About the structural unit represented by above-mentioned formula (3), such as making the compound such as glycidyl methacrylate, methacrylic acid-2-methylglycidyl esters as (I-2) compound with when having the situation of copolymer reaction of carboxyl, the R in formula (3) 22become formula (4-1).On the other hand, make the compound such as methacrylic acid-3,4-epoxycyclohexanecarboxylate as (I-2) compound with when having the situation of copolymer reaction of carboxyl, the R in formula (3) 22become formula (4-2).
When synthesizing specific copolymer, also can use the compound beyond (I-1) compound, such as above-mentioned (I-3) compound, (I-4) compound etc. are as copolymer composition.Consider from the aspect of copolyreaction, those compounds are preferably methyl methacrylate, n-BMA, benzyl methacrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, styrene, to methoxy styrene, methacrylic acid tetrahydrofuran-2-base ester, 1,3-butadiene.
The copolymerization process of specific copolymer include, for example and uses radical polymerization initiator in a solvent, makes (I-1) compound and (I-3) compound etc. optionally carry out the method for being polymerized.Radical polymerization initiator can be enumerated and the identical person of radical polymerization initiator illustrated in the project of above-mentioned [I] alkali soluble resins.As the use amount of radical polymerization initiator, for polymerizable unsaturated compound 100 quality %, be generally 0.1 quality % ~ 50 quality %, be preferably 0.1 quality % ~ 20 quality %.Specific copolymer directly can be supplied in the manufacture of [I] alkali soluble resins in polymeric reaction solution, also after being temporarily separated in solution by multipolymer, can be supplied in the manufacture of [I] alkali soluble resins.
The Mw of specific copolymer is preferably 2, and 000 ~ 100,000, be more preferably 5,000 ~ 50,000.Be 2 by making Mw, more than 000, the sufficient development latitude of colored composition can be obtained, and the reduction of the residual film ratio of formed film (ratio that pattern-like film is suitably remaining) can be prevented, keep the shape or thermotolerance etc. of the pattern of gained further well.On the other hand, by making Mw be 100, less than 000, the light sensitivity of height can be kept, obtain good pattern form.And the molecular weight distribution (Mw/Mn) of specific copolymer is preferably less than 5.0, is 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 comprising the specific copolymer of the Mw/Mn with above-mentioned particular range has the developability of height, in development step, the residual ground of development can not be produced and easily form predetermined pattern shape.
The containing ratio being derived from the structural unit of (I-1) compound of [I] alkali soluble resins is preferably 5 quality % ~ 60 quality %, is more preferably 7 quality % ~ 50 quality %, is particularly preferably 8 quality % ~ 40 quality %.
The containing ratio being derived from the structural unit of the compound such as (I-3) compound, (I-4) compound beyond (I-1) compound of [I] alkali soluble resins is preferably 10 quality % ~ 90 quality %, more preferably 20 quality % ~ 80 quality %.
In the reaction of specific copolymer with (I-2) compound, if necessary under the existence of suitable catalyzer, preferably in the copolymer solution comprising polymerization inhibitor, drop into the unsaturated compound with epoxy radicals, under heating, carry out the stirring of the schedule time.Above-mentioned catalyzer include, for example tetrabutyl ammonium bromide etc.Above-mentioned polymerization inhibitor include, for example p methoxy phenol etc.Temperature of reaction is preferably 70 DEG C ~ 100 DEG C.Reaction 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 multipolymer, be preferably 5 quality % ~ 99 quality %, be more preferably 10 quality % ~ 97 quality %.By making the usage ratio of (I-2) compound be above-mentioned scope, can make to improve further with the reactivity of multipolymer, the hardening etc. of cured film.(I-2) compound can be used alone or two or more is used in combination.
< [II] polymerizable compound >
[II] polymerizable compound contained in the colored composition used in manufacture to the colored filter of this example is illustrated.
[II] polymerizable compound is the polymerizable compound with ethene unsaturated link.
Can be used as [II] polymerizable compound and the compound used 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, polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, two phenoxetol 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, pentaerythrite three (methyl) acrylate, pentaerythrite 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 there is straight chain alkylen and alicyclic structure and the compound with more than 2 isocyanate group with there is in molecule more than 1 hydroxyl and the compound with 3 ~ 5 (methyl) acryloxies reacts and the polyurethane of gained (methyl) acrylate compounds etc.
The commercially available product of spendable [II] polymerizable compound include, for example:
ARONIX (registered trademark) 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 trademark) TO-756, ARONIXTO-1450, ARONIXTO-1382 (being manufactured by East Asia Synesis Company above), KAYARAD (registered trademark) DPHA, KAYARADDPCA-20, KAYARADDPCA-30, KAYARADDPCA-60, KAYARADDPCA-120, KAYARADMAX-3510 (being made by Japanese chemical drug Inc. above), Viscoat295, Viscoat300, Viscoat360, ViscoatGPT, Viscoat3PA, Viscoat400 (being manufactured by Osaka Organic Chemical Industry company above), as Newfrontier (registered trademark) R-1150 (the first industrial pharmaceutical company) of urethane acrylate compounds, KAYARAD (registered trademark) DPHA, KAYARAD (registered trademark) DPHA-40H, UX-5000 (being made by Japanese chemical drug Inc. above), UN-9000H (Gen Shang industrial group), ARONIX (registered trademark) M-5300, ARONIXM-5600, ARONIXM-5700, ARONIXM-210, ARONIXM-220, ARONIXM-240, ARONIXM-270, ARONIXM-6200, ARONIXM-305, ARONIXM-309, ARONIXM-310, ARONIXM-315 (being manufactured by East Asia Synesis Company above), KAYARAD (registered trademark) HDDA, KAYARAD (registered trademark) HX-220, KAYARADHX-620, KAYARADR-526, KAYARADR-167, KAYARADR-604, KAYARADR-684, KAYARADR-551, KAYARADR-712, KAYARADUX-2201, KAYARADUX-2301, KAYARADUX-3204, KAYARADUX-3301, KAYARADUX-4101, KAYARADUX-6101, KAYARADUX-7101, KAYARADUX-8101, KAYARADUX-0937, KAYARADMU-2100, KAYARADMU-4001 (being made by Japanese chemical drug Inc. above), ArtresinUN-9000PEP, ArtresinUN-9200A, ArtresinUN-7600, ArtresinUN-333, ArtresinUN-1003, ArtresinUN-1255, ArtresinUN-6060PTM, ArtresinUN-6060P, ArtresinSH-500B (being manufactured by Gen Shang industrial group above), Viscoat260, Viscoat312, Viscoat335HP (being manufactured by Osaka Organic Chemical Industry company above) etc.
[II] polymerizable compound can be used alone or two or more is used in combination.As the usage ratio of [II] polymerizable compound in colored composition, for [I] alkali soluble resins 100 mass parts, be preferably 10 mass parts ~ 700 mass parts, be more preferably 20 mass parts ~ 600 mass parts.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 thermotolerance, solvent resistance, voltage retention under low exposure.
< [III] polymerization initiator >
[III] polymerization initiator contained in the colored composition used in manufacture to the colored filter of this example is illustrated.
[III] polymerization initiator is radioactivity-sensitive polymerization initiator, is the composition responded to radioactive ray and generate 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 also can be used in combination by two or more.
O-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-acetic acid esters, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-ethane-1-ketoxime-O-benzoic ether, 1-[9-normal-butyl-6-(2-ethylamino benzonitrile acyl group)-9H-carbazole-3-base]-ethane-1-ketoxime-O-benzoic ether, 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) methoxybenzoyl base }-9H-carbazole-3-base]-1-(O-acetyl oxime) etc.
1 is preferably in those compounds, 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 methoxybenzoyl base)-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) methoxybenzoyl base }-9H-carbazole-3-base]-1-(O-acetyl oxime).
Acetophenone compound include, for example alpha-amido ketonic compound, alpha-hydroxyacetone compounds.
Alpha-amido ketonic 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 alpha-amido ketonic 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 preferred 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-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-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
As the usage ratio of [III] polymerization initiator, for [I] alkali soluble resins 100 mass parts, be preferably 1 mass parts ~ 40 mass parts, be more preferably 5 mass parts ~ 30 mass parts.By making the usage ratio of [III] polymerization initiator be 1 mass parts ~ 40 mass parts, even if colored composition also can form the colored pattern and colored filter with high solvent resistance etc. when low exposure.
< [IV] colorant >
As mentioned above, high excitation, brightness, contrast etc. are strongly required to colored pattern and colored filter.Therefore, [IV] colorant contained in the colored composition used in the manufacture as the colored filter of this example, becomes the colorant must selecting to be suitable for realizing this kind of characteristic.[IV] coloring agents as any one of pigment, dye well natural colouring matter can be used, if but consider colored pattern and the high excitation required by colored filter or brightness etc., then preferably select pigment and dyestuff.And particularly preferably select dyestuff.
The dyestuff used about can be used as [IV] colorant, include, for example oil-soluble dyes, acid dyes or derivatives thereof, direct dyes, mordant dyes etc.As dyestuff, as long as dissolve in organic solvent, then known dyestuff can be used.
C.I. oil-soluble dyes include, for example:
C.I. solvent yellow 4 (omits the record of " C.I. solvent yellow " below and only records 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 dyes include, for example:
C.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；
C.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. dyestuff such as acid black 24 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;
C.I. direct indigo plant 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.
The pigment used about can be used as [IV] colorant, can use any one of organic pigment, inorganic pigment.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;
C.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] colorant 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 class, oxa anthracenes, phthalocyanines, benzo pyran, indigo class, diketopyrrolopyrroles etc. can be enumerated.The colorant of triarylmethane class, barbiturates azo, pyrazoles azo, anilino-azo, Pyrazolotriazole azo, pyridone azo, phthalocyanines, Anthraquinones, anthrapyridones and diketopyrrolopyrroles is preferably selected in those colorants.
Triarylmethane based colorant as the example of preferred [IV] colorant is in colorant that is blue, purple.
Colorant in blueness, purple belongs to the pigment such as C.I. alizarol saphirol, C.I. pigment violet, C.I. the basic-dyeable fibre such as alkali blue, C.I. alkalescence purple, C.I. the oil-soluble dyes such as solvent blue, C.I. solvent violet, C.I. the acid dyes such as acid blue, C.I. acid violet, C.I. disperse blue, C.I. disperse violet isodispersity dyestuff etc., the colorants such as edible coloring agent such as the edible indigo plant of C.I., the edible purple of C.I..
In addition, the salt forming dye with gegenion, those acid dyess (also comprising direct dyes), basic-dyeable fibre being carried out to modification is belonged to.
Triphenyl methane based colorant as the example of triarylmethane based colorant is the NH owing to being positioned at for the position of contraposition for the carbon of center 2or OH base is oxidized and become quinone structure, thus carry out the colorant that develops the color.And, be mainly basic-dyeable fibre, but imported sulfonic dyestuff and become acid dyes.
According to NH 2, OH base number and be divided into following 3 types, wherein triaminotriphenyl methylmethane class dyestuff form demonstrate good blue in be preferred form.
A) diamido 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 preferably using.And, wherein particularly preferably as the Bisphenylnaphthylmethane dyes of basic-dyeable fibre.
Triarylmethane based colorant can use the dye well pigment of following 5 kinds of forms.
1) basic-dyeable fibre (triarylmethane class basic-dyeable fibre) of triarylmethane class dyestuff
2) salt-forming compound of the salt-forming compound of triarylmethane class basic-dyeable fibre and organic sulfonic acid, triarylmethane class basic-dyeable fibre and aromatic hydroxy-carboxylic
3) acid dyes 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, wherein preferably use the salt-forming compound of the basic-dyeable fibre of triarylmethane class dyestuff, triarylmethane class basic-dyeable fibre and organic sulfonic acid, triarylmethane class basic-dyeable fibre and the salt-forming compound of aromatic hydroxy-carboxylic, the metallic lakes pigment of triarylmethane class dyestuff.
Triarylmethane class dyestuff has following dichroism: in 400nm ~ 430nm, have high transmissivity.But, even if having good dichroism, also thermotolerance extreme difference in the same manner as general dyestuff.When using in the color liquid crystal display device requiring high reliability, previously, characteristic was also insufficient.Therefore, preferably use in the colored filter of this example.And, can also alkalize to dyestuff as previously improving the problem points of triarylmethane class dyestuff, became salinization, oil-soluble, utilize the modification of resin and use.Or Dye lake can also be made pigment.
Basic-dyeable fibre, the oil-soluble dyes of triarylmethane class dyestuff mix preferably by with the resin or rosin ester of the acidic group had as carboxyl, Abietyl modified maleic acid resin (Abietyl modified fumaric resin also synonym) and improve tolerance.Those have the resin of acidic group, rosin ester, Abietyl modified maleic acid resin acid number be preferably 20 ~ 200.Herein, acid number is the value utilizing the method for JISK-0070 and measure.
Triarylmethane class basic-dyeable fibre can enumerate C.I. alkali blue 1,5,7,26, C.I. alkaline purple 1,3 etc.Wherein preferably use C.I. Blue 7.
Secondly, the salt-forming compound of triarylmethane class basic-dyeable fibre and organic sulfonic acid is illustrated.Triarylmethane class basic-dyeable fibre and organic sulfonic acid by making both be dissolved in aqueous solution, alcoholic solution is medium, thus react and obtain 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.
Have in naphthalene class sulfonated bodies: bond has 1 sulfonic naphthalene list sulfonic acid, bond has 2 sulfonic naphthalenedisulfonic acids, bond has 3 sulfonic naphthalene trisulfonic acids.Be specifically 1-naphthalene sulfonic aicd, 2-naphthalene sulfonic acids, 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 acid, 1,3,7-naphthalene trisulfonic acid etc.
And naphthalene class sulfonated bodies also comprises naphthylamine sulfonic acid except above-mentioned naphthalene sulfonic acids.And have: bond has 1 sulfonic naphthylamines list sulfonic acid, bond has 2 sulfonic naphthylamine disulfonic acids, bond has 3 sulfonic naphthylamines trisulfonic acids.Be 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.
Also have in aphthols sulfonated bodies: bond has 1 sulfonic naphthols list sulfonic acid, bond has 2 sulfonic naphthol disulfonic acids, bond has 3 sulfonic naphthol trisulfonic acids.Be 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.
In addition, comprising the salt-forming compound of Victoria pure blue BO (C.I. Blue 7) and naphthalenedisulfonic acid, comprising Victoria pure blue BO (C.I. Blue 7) with the salt-forming compound of naphthol disulfonic acid is preferred dyestuff.
Two sulfonated bodies of naphthalene class, two sulfonated bodies of aphthols and triarylmethane class basic-dyeable fibre are reacted, and when making the situation of [IV] colorant of this example, two sulfonated bodies of 1 mole are salify 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 gegenion composition, is therefore the preferred component becoming the colour developing not undermining dyestuff as colorant.That is, preferably use and there are at least 2 sulfonic organic sulfonic acids.
And the salt-forming compound of triarylmethane class basic-dyeable fibre and organic sulfonic acid, (aromatic hydroxy-carboxylic) synthesizes by previously known method.Concrete gimmick is disclosed in Japanese Patent Laid-Open 2003-215850 publication etc.
And, can aromatic hydroxy-carboxylic be used and obtain salt-forming compound in the same manner as above-mentioned organic sulfonic acid.As preferred aromatic hydroxy-carboxylic, wherein preferably use 3,5-di-tert-butyl salicylic acid, 3-hydroxy-2-naphthoic acid, 3-phenylo salicylic acid.When using the situation of aromatic hydroxy-carboxylic, obtain the amino (-NHC in triarylmethane class dyestuff 2h 5) part and the salt-forming compound of carboxylic acid (-COOH) the part bond of aromatic hydroxy-carboxylic.And hydroxyl (-OH) is with salt-forming reaction and irrelevant class ground is remaining.
In addition, comprising Victoria pure blue BO (C.I. Blue 7) with the salt-forming compound of 3,5-di-tert-butyl salicylic acids is preferred dyestuffs.
The acid dyes of triarylmethane class dyestuff preferably uses edible blue No. 101 (C.I. Blue VRS), acid ethereal blues (C.I. acid blue 3), the blue I (C.I. acid blue 5) in color lake, the blue II (C.I. Acid Blue 7) in color lake, 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 synthesizes by previously known method.
If enumerate an example, then, after being dissolved in the water by triarylmethane acid dye, add quaternary ammonium compound, one side is carried out stirring one side and is carried out into salinization process.Herein, the sulfonic group (-SO in triarylmethane acid dye is obtained 3h) part and the ammonium (NH of quaternary ammonium compound 4 +) salt-forming compound of part bond.Quaternary ammonium compound preferably uses triethyl benzyl ammonia chloride etc.
In this example, triarylmethane mordant pigment can be used as triarylmethane based colorant.
The color lake of carrying out in pigmentation utilizes precipitation agent and obtains insoluble salt by the dyestuff of solubility, be have chemically to react, and dye component is adsorbed in the state on precipitation agent particle.
Triaminotriphenyl methylmethane class dyestuff improves weatherability, thermotolerance by carrying out color lake, becomes stable good colorant.
Precipitation agent in order to carry out color lake to triarylmethane class dyestuff can be enumerated barium chloride, lime chloride, ammonium sulfate, aluminum chloride, aluminium acetate, lead acetate, tannic acid, catarrh promise (Katanol), be called 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, use the mordant pigment of compound heteropoly acid due to distinct and colouring power large, photostability significantly improves, and is therefore preferred pigment.
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.
Preferred triarylmethane class pigment is represented particularly following.
C.I. pigment blue 1.
With phosphotungstomolybdic acid, color lake is carried out to C.I. alkali blue 26, C.I. Blue 7.
C.I. pigment violet 3.
With phosphotungstomolybdic acid, color lake is carried out to C.I. alkaline purple 1.
C.I. pigment violet 39.
With phosphotungstomolybdic acid, color lake is carried out to C.I. alkaline purple 3 (crystal violet).
Wherein preferably use C.I. pigment blue 1.
Secondly, as the barbiturates azo dyes of the example of preferred [IV] colorant and pyridone azo, such as there is following structure.But the barbiturates azo dyes used in this example and pyridone azo are not limited to those structures.
[changing 9]
In formula (101), T 1and T 2separately represent oxygen atom or sulphur atom.
R 101~ R 104separately represent hydrogen atom, also can have substituent carbon number be 1 ~ 10 aliphatic alkyl, also can have substituent carbon number be 6 ~ 20 aryl, also can to have substituent carbon number be the aralkyl of 7 ~ 20 or also can have the acyl group that substituent carbon number is 2 ~ 10.
R 105~ R 112separately represent hydrogen atom, carbon number be 1 ~ 10 aliphatic alkyl, carbon number be 1 ~ 8 alkoxy, carboxyl, sulfo group, sulfamoyl or N position-replacement sulfamoyl.Hydrogen atom contained in above-mentioned aliphatic alkyl also can be replaced by halogen atom.
If be described in more detail, then in formula (101), R 101~ R 104in carbon number be 1 ~ 10 aliphatic alkyl can be any one of straight-chain, branch-like or ring-type.Carbon number is that the carbon number of the aliphatic alkyl of 1 ~ 10 is preferably 2 ~ 8, is more preferably 3 ~ 6.Carbon number be 1 ~ 10 aliphatic alkyl include, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, ethylhexyl (2-ethylhexyl etc.), cyclopentyl, cyclohexyl and cyclohexylalkyl etc.
And, carbon number be hydrogen atom contained in the aliphatic alkyl of 1 ~ 10 also can by hydroxyl, carbon number be 1 ~ 8 (preferred carbon number be 1 ~ 4) alkoxy or carbon number be 1 ~ 8 (preferred carbon number be 1 ~ 4) thio alkoxy replace.The aliphatic alkyl be 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.
R 101~ R 104in carbon number be 6 ~ 20 aryl can be unsubstituted, also can have aliphatic alkyl, alkoxy, carboxyl, sulfo group or the substituting group such as the base comprising ester bond.The carbon number of described aryl comprises substituent carbon number and counts, and is preferably 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-(COOC 2h 5) Ph base (Ph basis representation phenyl) etc.) etc.
R 101~ R 104in carbon number be the moieties of the aralkyl of 7 ~ 20 can be straight-chain, branch-like or ring-type any one.The carbon number of aralkyl comprises substituent carbon number and counts, and is preferably 7 ~ 10.Carbon number be 7 ~ 20 aralkyl can enumerate benzyl and phenethyl etc.
R 101~ R 104in carbon number be 2 ~ 10 acyl group can be unsubstituted, also can the substituting group such as bond aliphatic alkyl or alkoxy.The carbon number of acyl group comprises substituent carbon number and counts, and its number is preferably 2 ~ 10.Acyl group include, for example acetyl group, benzoyl, methoxybenzoyl base (to methoxybenzoyl base etc.) etc.
R 105~ R 112in carbon number be 1 ~ 10 aliphatic alkyl can enumerate and R 101~ R 104when identical base.R 105~ R 112aliphatic alkyl in contained hydrogen atom also can be replaced by halogen atom, halogen atom preferably enumerates fluorine atom.The concrete example of the aliphatic alkyl replaced by halogen atom can enumerate trifluoromethyl etc.
R 105~ R 112in carbon number be that the carbon number of the alkoxy of 1 ~ 8 is preferably 1 ~ 4.Alkoxy include, for example methoxyl, ethoxy, isopropoxy, positive propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy etc.
R 105~ R 112in N position-replacement sulfamoyl be such as preferably N position-monosubstituted sulfamoyl, with-SO 2nHR 140and represent.
-SO 2nHR 140in contained R 140represent also can have substituent carbon number be 1 ~ 10 aliphatic alkyl, also can have substituent carbon number be 6 ~ 20 aryl, also can to have substituent carbon number be the aralkyl of 7 ~ 20 or also can have the acyl group that substituent carbon number is 2 ~ 10.
R 140in carbon number be 1 ~ 10 aliphatic alkyl can be any one of straight-chain, branch-like or ring-type.The carbon number of aliphatic alkyl does not comprise substituent carbon number, and its number is preferably 6 ~ 10.
R 140in carbon number be 1 ~ 10 aliphatic alkyl include, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, 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.), cyclopentyl, cyclohexyl, methylcyclohexyl (2-methylcyclohexyl etc.) and cyclohexylalkyl etc.
-SO 2nHR 140in contained R 140in carbon number be 1 ~ 10 aliphatic alkyl can be also 1 ~ 8 by carbon number (be preferably carbon number be 1 ~ 4) alkoxy replaces, include, for example propoxypropyl (3-(isopropoxy) propyl group etc.) etc.
R 140in carbon number be 6 ~ 20 aryl can be unsubstituted, also can have the substituting group such as aliphatic alkyl or hydroxyl.The carbon number of described aryl comprises substituent carbon number and counts, and is preferably 6 ~ 10.Aryl include, for example phenyl, hydroxy phenyl (4-hydroxy phenyl etc.), trifluoromethyl (4-trifluoromethyl etc.) etc.
R 140in carbon number be the moieties of the aralkyl of 7 ~ 20 can be straight-chain or branch-like any one.The carbon number of aralkyl is generally 7 ~ 20, is preferably 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.).
R 140in carbon number be 2 ~ 10 acyl group can be unsubstituted, hydrogen atom contained in acyl group also can be replaced by aliphatic alkyl or alkoxy.The carbon number of acyl group comprises substituent carbon number and counts, and its number is preferably 6 ~ 10.Acyl group include, for example acetyl group, benzoyl, adjacent toluyl groups, a toluyl groups, to toluyl groups and methoxybenzoyl base (to methoxybenzoyl base etc.) etc.
Pyridone azo as the example of preferred [IV] colorant such as has following structure.
[changing 10]
In formula (102), Z represents halogen atom, also the aliphatic alkyl that substituent carbon number is 1 ~ 12 can be had, carbon number is the alkoxy of 1 ~ 8, there is 1 or 2 select free hydroxyl, carboxyl, carbamyl, sulfo group, at least a kind of substituent phenyl of the group that sulfamoyl and N position-replacement sulfamoyl are formed, or having 1 ~ 3 is selected from by halogen atom, also the aliphatic alkyl that substituent carbon number is 1 ~ 12 can be had, carbon number is the alkoxy of 1 ~ 8, hydroxyl, carboxyl, carbamyl, sulfo group, at least a kind of substituent naphthyl of the group that sulfamoyl and N position-replacement sulfamoyl are formed.
R 121represent hydrogen atom, the carbon number of straight-chain, branch-like or ring-type is aliphatic alkyl, carboxyl or the trifluoromethyl of 1 ~ 10.
R 122represent hydrogen atom, cyano group, carbamyl, N position-replacement carbamyl, sulfamoyl or sulfo group.
R 123represent hydrogen atom, also the straight-chain that substituent carbon number is 1 ~ 10 can be had, the aliphatic alkyl of branch-like or ring-type, also the aryl that substituent carbon number is 6 ~ 30 can be had, also the aralkyl that substituent carbon number is 7 ~ 20 can be had, also the heterocyclic radical that substituent carbon number is 3 ~ 20 can be had, carbamyl, N position-replacement carbamyl, also the alkoxy carbonyl that substituent carbon number is 2 ~ 20 can be had, also the aryloxycarbonyl that substituent carbon number is 7 ~ 30 can be had, also the acyl group that substituent carbon number is 2 ~ 20 can be had, also can to have substituent carbon number be the aliphaticsulfonyl of 1 ~ 30 or also can have the aryl sulfonyl that substituent carbon number is 6 ~ 30.
If be described in more detail, then in formula (102), the carbon number in Z be 1 ~ 12 aliphatic alkyl can be any one of straight-chain, branch's chain or ring-type.The carbon number of aliphatic alkyl comprises all substituent carbon numbers, and its number is preferably 1 ~ 12, is more preferably 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 alkoxy or the carboxyl substituted of 1 ~ 8 by carbon number.There is substituent aliphatic alkyl and can enumerate alkoxy propyl group (3-(2 '-ethyl hexyl oxy) propyl group etc.) and 8-(carboxyl) octyl group etc.
Carbon number in Z be 1 ~ 8 alkoxy include, for example methoxyl, ethoxy, 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-SO 2n (R 141) R 142and represent.R 141and R 142separately represent hydrogen atom, also can have substituent carbon number be 1 ~ 16 aliphatic alkyl, also can have substituent carbon number be 6 ~ 20 aryl, also can to have substituent carbon number be the aralkyl of 7 ~ 20 or also can have acyl group (wherein, the R that substituent carbon number is 2 ~ 15 141and R 142be not hydrogen atom) simultaneously.
Carbon number be 1 ~ 16 aliphatic alkyl can be any one of straight-chain, branch-like or ring-type, the carbon number of aliphatic alkyl is preferably 6 ~ 16.
R 141and R 142in carbon number be 1 ~ 16 aliphatic alkyl can be any one of straight-chain, branch's chain or ring-type.The carbon number of aliphatic alkyl does not comprise substituent carbon number, and its number is preferably 1 ~ 16, is more preferably 6 ~ 10.Aliphatic alkyl include, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, methyl butyl (1,1,3,3-tetramethyl butyl etc.), methylhexyl (1,5-dimethylhexanyl etc.), ethylhexyl (2-ethylhexyl etc.), cyclopentyl, cyclohexyl, methylcyclohexyl (2-methylcyclohexyl etc.) and cyclohexylalkyl etc.Hydrogen atom contained in aliphatic alkyl also can be alkoxy or the carboxyl substituted of 1 ~ 8 by carbon number.There is substituent aliphatic alkyl and can enumerate propoxypropyl (3-(isopropoxy) propyl group etc.), 2-(carboxyl) ethyl, 3-(carboxyl) ethyl and 4-carboxy ethyl etc.
R 141and R 142in carbon number be 6 ~ 20 aryl also can have the substituting group such as aliphatic alkyl or hydroxyl.The carbon number of aryl comprises substituent carbon number and counts, and is preferably 6 ~ 20, is more preferably 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.
R 141and R 142in carbon number be the moieties of the aralkyl of 7 ~ 20 can be straight-chain or branch-like any one.The carbon number of aralkyl is preferably 7 ~ 20, is more preferably 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.).
R 141and R 142in carbon number be 2 ~ 15 acyl group can be unsubstituted, also can have the substituting groups such as aliphatic alkyl, alkoxy or carboxyl.The carbon number of acyl group comprises substituent carbon number and counts, and its number is preferably 2 ~ 15, is more preferably 6 ~ 10.Acyl group include, for example acetyl group, benzoyl, methoxybenzoyl base (to methoxybenzoyl base etc.), carboxyacetyl, 2-carboxypropanoyl, 3-carboxypropanoyl, 2-carboxybutanoyl, 3-carboxybutanoyl and 4-carboxybutanoyl etc.
R 121represent hydrogen atom, the carbon number of straight-chain, branch-like or ring-type is the aliphatic alkyl of 1 ~ 10, carboxyl or trifluoromethyl.
R 121in carbon number be that the carbon number of the aliphatic alkyl of 1 ~ 10 does not comprise substituent carbon number.Its carbon number is preferably 2 ~ 8, is more preferably 3 ~ 6.Aliphatic alkyl can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, cyclopentyl and cyclohexyl etc.
R 122represent hydrogen atom, cyano group, carbamyl or N position-replacement carbamyl, sulfamoyl or sulfo group.
R 122in N position-replacement carbamyl can enumerate-CON (R 143) R 144.R 143and R 144independently represent hydrogen atom, also can have substituent carbon number be 1 ~ 10 aliphatic alkyl, also can have substituent carbon number be 6 ~ 20 aryl, also can to have substituent carbon number be the aralkyl of 7 ~ 20 or also can have the acyl group that substituent carbon number is 2 ~ 10.
R 143and R 144aliphatic alkyl, aryl, the explanation of aralkyl and acyl group and concrete example and aforesaid R 141and R 142identical.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.
R 123represent hydrogen atom, also the straight-chain that substituent carbon number is 1 ~ 10 can be had, the aliphatic alkyl of branch-like or ring-type, also the aryl that substituent carbon number is 6 ~ 30 can be had, also the aralkyl that substituent carbon number is 7 ~ 20 can be had, also the heterocyclic radical that substituent carbon number is 3 ~ 20 can be had, carbamyl, N position-replacement carbamyl, also the alkoxy carbonyl that substituent carbon number is 2 ~ 20 can be had, also the aryloxycarbonyl that substituent carbon number is 7 ~ 30 can be had, also the acyl group that substituent carbon number is 2 ~ 20 can be had, also can to have substituent carbon number be the aliphaticsulfonyl of 1 ~ 30 or also can have the aryl sulfonyl that substituent carbon number is 6 ~ 30.
R 123in aliphatic alkyl can enumerate and above-mentioned R 121in the identical base of aliphatic alkyl.
As R 123in aryl, carbon number is preferably 6 ~ 30, is more preferably 6 ~ 20, is more preferably 6 ~ 16.The concrete example of aryl can enumerate phenyl, 4-nitrobenzophenone, 2-nitrobenzophenone, 2-chlorphenyl, 2,4-dichlorophenyls, 2,4-3,5-dimethylphenyls, 2-aminomethyl phenyl, 4-methoxyphenyl, 2-methoxyphenyl and 2-methoxycarbonyl-4-nitrobenzophenone etc.
R 123in aralkyl can be any one 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.).
R 123in carbon number be 3 ~ 20 heterocyclic radical saturable also can be unsaturated, carbon number is preferably 3 ~ 20, is more preferably 5 ~ 15.The concrete example of heterocyclic radical can enumerate pyrazolyl, 1,2,4-triazolyl, isothiazolyl, benzisothiazole base, thiazolyl, benzothiazolyl, oxazolyl and 1,2,4-thiadiazolyl group etc.And, also can have substituting group further.
R 123in N position-replacement carbamyl with about R 122and described N position-replacement carbamyl is identical.
R 123in alkoxy carbonyl can be unsubstituted and also can have substituting group, also can be ring-type.The carbon number of alkoxy carbonyl is preferably 2 ~ 20, is more preferably 2 ~ 16, is more preferably 2 ~ 10 further.Alkoxy carbonyl can enumerate methoxycarbonyl, ethoxy carbonyl and butoxy carbonyl etc.
R 123in aryloxycarbonyl can be unsubstituted and also can have substituting group, carbon number is preferably 7 ~ 30, is more preferably 7 ~ 20, is more preferably 7 ~ 16 further.Aryloxycarbonyl can enumerate phenyloxycarbonyl and 4-methylphenoxy carbonyl etc.
R 123in acyl group can be aliphatic Oxo and also can be aryl carbonyl, and can be saturated or undersaturated any one, also can be ring-type, also can have substituting group further.Carbon number is preferably 2 ~ 20, is more preferably 2 ~ 15, is more preferably 2 ~ 10 further.Acyl group can enumerate acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, pivaloyl group, benzoyl etc.
R 123in aliphaticsulfonyl saturable also can be unsaturated, also can be ring-type.Carbon number is preferably 1 ~ 30, is more preferably 1 ~ 20, is more preferably 1 ~ 16 further.Aliphaticsulfonyl can enumerate mesyl, fourth sulfonyl, methoxy methyl sulfonyl, methoxyl ethylsulfonyl and ethoxy ethylsulfonyl etc.
R 123in aryl sulfonyl also can have substituting group, carbon number is preferably 6 ~ 30, is more preferably 6 ~ 20, is more preferably 6 ~ 18 further.Aryl sulfonyl can enumerate benzenesulfonyl and tosyl etc.
Secondly, as the diketopyrrolopyrroles of the example of preferred [IV] colorant and phthalocyanines, such as there is following structure.But the diketopyrrolopyrroles used in this example and phthalocyanine-based colorant are not limited in those.
[changing 11]
In formula (103), Y represents oxygen atom or sulphur atom.R 131with R 132can identical also can be different, represent hydrogen atom, alkyl, naphthenic base, thiazolinyl, alkynyl, aryl, aralkyl, carbamyl, alkylcarbamoyl group, aromatic yl ammonia methanoyl or alkoxy carbonyl.R 133, R 134can identical also can be different, represent alkyl, naphthenic base, aralkyl or carbocyclic ring or hetero ring type aromatic residue.
If be described in more detail, then in formula (103), R 131, R 132, R 133and R 134in alkyl can branch also can not branch, preferably have and be preferably 1 ~ 18, be more preferably 1 ~ 12, be more preferably the carbon atom of 1 ~ 6 further.Specifically can enumerate methyl, ethyl, isopropyl, sec-butyl, the tert-butyl group, tertiary pentyl, octyl group, decyl, dodecyl or octadecyl etc.
R 131, R 132, R 133and R 134in naphthenic base preferably have and be preferably 3 ~ 8, be more preferably the carbon atom of 3 ~ 6, specifically can enumerate cyclopentyl, cyclohexyl etc.R 131, R 132in thiazolinyl preferably have and be preferably 2 ~ 8, be more preferably the carbon atom of 2 ~ 6, specifically can enumerate vinyl, allyl etc.R 131, R 132in alkynyl preferably have and be preferably 2 ~ 8, be more preferably the carbon atom of 2 ~ 6, specifically can enumerate ethinyl etc.R 131, R 132in aryl preferably have and be preferably the carbon atom of 6 ~ 10, specifically can enumerate phenyl, naphthyl etc.R 131, R 132in the alkyl of alkylcarbamoyl group can enumerate the alkyl identical with abovementioned alkyl.R 131, R 132in the aryl of aromatic yl ammonia methanoyl can enumerate the aryl identical with above-mentioned aryl.R 131, R 132in the alkoxy of alkoxy carbonyl can enumerate the alkoxy that carbon number is 1 ~ 4, specifically can enumerate methoxyl, ethoxy, butoxy etc.
In formula (103), R 131, R 132, R 133and R 134when representing aralkyl, particularly preferably containing monocycle ~ three-ring type, the aromatic yl residue being more preferably monocyclic or two ring types.Specifically include, for example benzyl and phenylethyl.In formula (103), work as R 133and R 134when 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), R 133and R 134when 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, triazinyl, furyl, pyrrole radicals, thienyl, quinolyl, cumarin base, benzofuranyl, benzimidazolyl or benzoxazolyl etc.
In formula (103), R 131, R 132be preferably hydrogen atom.And, R 133, R 134be independently preferably alkyl, dialkyl amido, the alkylhalide group of 1 ~ 4 for carbon number 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] colorant, such as, there is following structure.
[changing 12]
In formula (104), X 1~ X 16separately represent hydrogen atom, chlorine atom or bromine atoms.
More specifically, in formula (104), X 1~ X 16it is 0 ~ 6 that represented substituent number is preferably chlorine atom, and bromine atoms is 10 ~ 16, and chlorine atom and bromine atoms and be 10 ~ 16; Be more preferably that chlorine atom is 0 ~ 3, bromine atoms is 13 ~ 16, and chlorine atom and bromine atoms and be 13 ~ 16; Be more preferably that chlorine atom is 1 ~ 3, bromine atoms is 13 ~ 15 further, and chlorine atom and bromine atoms and be 14 ~ 16.
Secondly, about the inorganic pigment that can use in [IV] colorant, include, for example titanium dioxide, barium sulphate, 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] colorant contained in colored composition is illustrated.
As the content of [IV] colorant, for [I] alkali soluble resins 100 mass parts, be preferably 1 mass parts ~ 400 mass parts, be more preferably 5 mass parts ~ 350 mass parts.By making the content of [IV] colorant be above-mentioned scope, balance the alkali-developable of colored composition, the thermotolerance of pixel, solvent resistance and as the high brightness of colored pattern and colored filter or high-contrast can be reached well using high level.
< [V] compound >
The colored composition used in the manufacture of the colored filter of this example can contain [V] compound.[V] compound is the compound of the function played as rigidizer.Therefore, [V] rigidizer is sometimes referred to as.
[V] compound is at least a kind of compound being selected from the group that the compound represented by following formula (1), the compound represented by following formula (2), tertiary amine compound, amine salt, phosphonium salt, amidine salt, amide compound, mercaptan compound, block isocyanate compound and the compound containing imidazole ring are formed.Colored composition is by realizing the hardening at subcritical temerature of colored pattern containing [V] compound being selected from this specific compound group.And, the storage stability of colored composition also can be made to improve.Below, each compound is described in detail.
[changing 13]
[changing 14]
[formula (1) and the compound represented by formula (2)]
[V] compound is preferably selected from least a kind of compound of the group that the compound represented by above-mentioned formula (1) and formula (2) is formed.As [V] compound, by selecting to have the amino hardening at subcritical temerature realizing colored pattern with the above-mentioned specific compound of short of electricity subbase.And, the storage stability of colored composition also can be made to improve.Can further improve the voltage retention of the liquid crystal display cells of the colored filter using gained.
In above-mentioned formula (1), R 1~ R 6be independently hydrogen atom, electron-withdrawing group or amino.Wherein, R 1~ R 6in at least 1 be electron-withdrawing group, and R 1~ R 6in at least 1 be amino, all or part of alkyl that can be also 1 ~ 6 by carbon number of the hydrogen atom of above-mentioned amino replaces.
In above-mentioned formula (2), R 7~ R 16be independently hydrogen atom, electron-withdrawing group or amino.Wherein, R 7~ R 16in at least 1 be amino.And all or part of alkyl that can be also 1 ~ 6 by carbon number of the hydrogen atom of this amino replaces.And during the situation of [V] compound used in colored composition, the alkyl that this amino can be also 1 ~ 6 by carbon number replaces.A is singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number are 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 R 1~ R 16represented electron-withdrawing group include, for example halogen atom, cyano group, nitro, trifluoromethyl, carboxyl, acyl group, alkyl sulphonyl, alkyloxysulfonyl, dicyanoethenyl, tricyano vinyl, sulfonyl etc.Nitro, trifluoromethyl, alkyloxysulfonyl is preferably in those bases.The methylene that base represented by A is preferably sulfonyl, also can be replaced by fluoroalkyl.
As the compound represented by above-mentioned formula (1) and formula (2),
Be preferably two (4-aminophenyl) HFC-236fa of 2,2-, two (4-aminophenyl) succinonitrile of 2,3-, 4,4 '-diaminobenzophenone, 4,4 '-diaminobenzoic acid phenyl ester, 4,4 '-diamino diphenyl sulfone, Isosorbide-5-Nitrae-diamido-2-chlorobenzene, Isosorbide-5-Nitrae-diamido-2-bromobenzene, Isosorbide-5-Nitrae-diamido-2-iodobenzene, Isosorbide-5-Nitrae-diamido-2-nitrobenzene, Isosorbide-5-Nitrae-diamido-2-trifluoromethylbenzene, 2,5-diamido 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) biphenylamine, 3-amino phenyl sulfonyl acetoacetic ester, 3,5-bis trifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline, is more preferably two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-diamino diphenyl sulfone, 2,2 '-bis-(trifluoromethyl) biphenylamine, 3-amino phenyl sulfonyl acetoacetic ester, 3,5-bis trifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline.
Above-mentioned formula (1) and the compound represented by formula (2) can be used alone or two or more is used in combination.Proportional as containing of the compound represented by above-mentioned formula (1) and formula (2), for [I] alkali soluble resins 100 mass parts, be preferably 0.1 mass parts ~ 20 mass parts, be more preferably 0.2 mass parts ~ 10 mass parts.By make the compound represented by above-mentioned formula (1) and formula (2) containing proportional for above-mentioned scope, storage stability and the hardening at subcritical temerature of colored composition can be taken into account with higher level.
[tertiary amine compound]
If make reactive high general primary amine or secondary amine compound and epoxy compound coexist, then in the preservation of constituent solution, carry out sclerous reaction due to the nucleophilic attack to epoxy radicals of amine, thus have the possibility that harm is the quality of goods.But when using tertiary amine, because reactivity is lower or coexist with epoxy compound in composition portion, storage stability becomes good.
Tertiary amine compound can use at least a kind that is selected from the group that the compound represented by following formula (5) is formed.
[changing 15]
In above-mentioned formula (5), R 24~ R 26the alkyl, the carbon number that are independently 1 ~ 20 for carbon number be 6 ~ 18 aryl or carbon number be the aralkyl of 7 ~ 30.Wherein, R 24and R 25also can bond mutually, together form ring texture with the nitrogen-atoms of those bonds.Part or all of the hydrogen atom of abovementioned alkyl, aryl and aralkyl also can be substituted.
Above-mentioned R 24~ R 26represented above-mentioned carbon number be 1 ~ 20 alkyl include, for example the methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, lauryl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc. of straight-chain or branch-like.
Above-mentioned R 24~ R 26represented carbon number be 6 ~ 18 aryl include, for example phenyl, naphthyl etc.
Above-mentioned R 24~ R 26represented carbon number be 7 ~ 30 aralkyl include, for example benzyl, phenethyl etc.
Tertiary 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-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, preferred trioctylphosphine amine, N, N-diethylaniline, 2-dimethylaminomethyl phenol etc.Tertiary amine compound can be used alone or two or more is used in combination.Proportional as containing of the tertiary amine compound in colored composition, for [I] alkali soluble resins 100 mass parts, be preferably 0.1 mass parts ~ 10 mass parts, be more preferably 0.5 mass parts ~ 5 mass parts.By make tertiary amine compound containing proportional for above-mentioned particular range, storage stability and the hardening at subcritical temerature of colored composition can be taken into account with higher level.
[amine salt is Ji phosphonium salt]
Amine salt is Ji phosphonium salt can use at least a kind that is selected from the group that the compound represented by following formula (6) is formed.
[changing 16]
In above-mentioned formula (6), A 1for nitrogen-atoms or phosphorus atoms.R 27~ R 30the alkyl, the carbon number that are independently 1 ~ 20 for hydrogen atom, 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 substituted.Q -it is 1 valency negative ion.
Above-mentioned R 27~ R 30represented carbon number be 1 ~ 20 alkyl include, for example the methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, lauryl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc. of straight-chain or branch-like.
Above-mentioned R 27~ R 30represented carbon number be 6 ~ 18 aryl include, for example phenyl, naphthyl etc.
Above-mentioned R 27~ R 30represented carbon number be 7 ~ 30 aralkyl include, for example benzyl, phenethyl etc.
Above-mentioned Q -1 represented valency negative ion 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, sulfuretted hydrogen radical ion, thiocyanate ion, Carboxylic Acid Ions, azochlorosulfonate acid ion, phenoxy group ion, tetrafluoro boric acid salt ion, four aryl boric acid salt ions, hexafluoro-antimonic acid salt ion etc.
Work as A 1during situation for nitrogen-atoms, that is ammonium salt include, for example tetramethyl ammonium chloride, tetrabutylammonium chloride, dodecyl benzyl dimethyl ammonium chloride, octyltrimethylammonium chloride, decyl trimethyl ammonium chloride, DTAC, tetradecyl trimethyl ammonium chloride, CTAB, stearyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammoinium chloride, benzalkonium chloride, benzalkonium bromide, DDAC, VARISOFT TA100.
Work as A 1during situation for phosphorus atoms, Yi and phosphonium salt include, for example tetraphenylphosphoniphenolate tetraphenyl borate salts, tetraphenylphosphoniphenolate four (p-methylphenyl) borate, tetraphenylphosphoniphenolate four (to ethylphenyl) borate, tetraphenylphosphoniphenolate four (p-methoxyphenyl) borate, tetraphenylphosphoniphenolate four (to ethoxyl phenenyl) borate, tetraphenylphosphoniphenolate four (to tert .-butoxyphenyl) borate, tetraphenylphosphoniphenolate four (tolyl) borate, tetraphenylphosphoniphenolate four (m-methoxyphenyl) borate, three (p-methylphenyl) Ben Ji Phosphonium four (p-methylphenyl) borates, four (p-methylphenyl) Phosphonium four (p-methylphenyl) borates, three (p-methoxyphenyl) Ben Ji Phosphonium four (p-methylphenyl) borates, tetraphenylphosphoniphenolate thiocyanate, Ding base triphenyl phosphonium thiocyanate, Jia base triphenyl phosphonium thiocyanate, p-methylphenyl triphenyl phosphonium thiocyanate etc.
Those amine salt are Ji preferred tetramethyl ammonium chloride, Ding base triphenyl phosphonium thiocyanate in phosphonium salt.Amine salt is Ji phosphonium salt can be used alone or two or more is used in combination.As the amine salt in colored composition and phosphonium salt containing proportional, for [I] alkali soluble resins 100 mass parts, be preferably 0.05 mass parts ~ 10 mass parts, be more preferably 0.1 mass parts ~ 5 mass parts.By make amine salt and phosphonium salt containing proportional be above-mentioned particular range, storage stability and the hardening at subcritical temerature of colored composition can be taken into account with higher level.
[amidine salt]
At least a kind of the group that amidine salt can use the salt of the compound be selected from represented by following formula (7) to form.
[changing 17]
In above-mentioned formula (7), m is the integer of 2 ~ 6.Wherein, part or all of the hydrogen atom that has of alkylene also can be replaced by organic group.And, above-mentioned alkylene refer to alkylene in tetrahydropyrimidine ring and in formula (7) with (CH 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 are amino, di-n-hexyl is 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]-undecylene-7 (DBU), 5-hydroxypropyl-1,8-diazabicyclo [5,4,0]-undecylene-7,5-dibutylamino-1,8-diazabicyclo [5,4,0]-undecylene-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 saturated fatty acid, aromatic hydroxy compound, sulfonic acid, particularly preferably as the sulfonic acid of strong acid, most preferably toluenesulfonic acid, methane-sulforic acid, octyl benzene sulfonic acid.Amidine salt is preferably the salt of the salt of the salt of the salt of DBU and toluenesulfonic acid, DBU and octyl benzene sulfonic acid, DBN and toluenesulfonic acid, DBN and octyl benzene sulfonic acid.
Amidine salt can be used alone or two or more is used in combination.Proportional as containing of the amidine salt in colored composition, for [I] alkali soluble resins 100 mass parts, be preferably 0.1 mass parts ~ 10 mass parts, be more preferably 0.5 mass parts ~ 5 mass parts.By make amidine salt containing proportional for above-mentioned particular range, storage stability and the hardening at subcritical temerature of colored composition can be taken into account with higher level.
[amide compound]
Amide compound can use at least a kind that is selected from the group be made up of the compound of the amide group had represented by following formula (8) ~ following formula (10).
[changing 18]
[changing 19]
[changing 20]
In above-mentioned formula (8), R 31and R 32independently for hydrogen atom, carbon number be 1 ~ 12 alkyl, cyclohexyl, phenyl, naphthyl, vinyl or 2-pyridine radicals.Wherein, above-mentioned carbon number is that alkyl, halogen atom, hydroxyl, carboxyl or the acetyl group that alkyl, phenyl and the naphthyl of 1 ~ 12 can be also 1 ~ 6 by carbon number replaces.
In above-mentioned formula (9), R 33and R 34be independently alkyl or cyclohexyl that hydrogen atom, carbon number are 1 ~ 12.A 2for methylene, carbon number be 2 ~ 12 alkylene, penylene, naphthylene or vinylene.Wherein, above-mentioned methylene, carbon number are that alkyl, the halogen atom that alkylene, penylene and the naphthylene of 2 ~ 12 can be also 1 ~ 6 by carbon number replaces.
In above-mentioned formula (10), R 35and R 36be independently alkyl or cyclohexyl that hydrogen atom, carbon number are 1 ~ 12.A 3for methylene, carbon number be 2 ~ 12 alkylene, penylene, naphthylene or vinylene.Wherein, above-mentioned methylene, carbon number are that alkyl, the halogen atom that alkylene, penylene and the naphthylene of 2 ~ 12 can be also 1 ~ 6 by carbon number replaces.
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, benzamide, naphthalenecarboxamide, niacinamide, Pyrazinamide etc.
The viewpoint improved from the thermotolerance, voltage retention etc. of the colored pattern of the storage stability that can make at room temperature, gained etc. is considered, preferred acetamide, N-methylacetamide, phthalamic acid in those compounds.
Above-mentioned formula (9) and the compound represented by formula (10) are the compounds in molecule with 2 amido links.Its concrete example include, for example phthalic amide, isophtalamide, adipamide, terephthalamide, malonamide, succinamide, N; N '-diacetyl-p-phenylenediamine (PPD), N; N '-diacetyl-hexane diamine, N, N '-diacetyl-dodecyl methylene diamine etc.
Consider from the viewpoint can taking into account storage stability and hardening at subcritical temerature with high level, preferred isophtalamide, adipamide, N, N '-diacetyl-p-phenylenediamine (PPD), N, N '-diacetyl-hexane diamine in those compounds.
Amide compound can be used alone or two or more is used in combination.Proportional as containing of the amide compound in colored composition, for [I] alkali soluble resins 100 mass parts, be preferably 0.1 mass parts ~ 10 mass parts, be more preferably 0.5 mass parts ~ 5 mass parts.By make amide compound containing proportional for above-mentioned particular range, storage stability and the hardening at subcritical temerature of colored composition can be taken into account with higher level.
[mercaptan compound]
Mercaptan compound is the compound in 1 molecule with more than 2 sulfydryls.Just be not particularly limited as long as mercaptan compound has more than 2 sulfydryls in 1 molecule, at least a kind that is selected from the group that the compound represented by following formula (11) is formed can be used.
[changing 21]
In formula (11), R 37for methylene, carbon number are the alkylene of 2 ~ 10.Wherein, part or all of the hydrogen atom of those bases also can be replaced by alkyl.Y 1for singly-bound ,-CO-or O-CO- *.Wherein, with key and the R of * 37bond.N is the integer of 2 ~ 10.A 4for the n valency alkyl that the carbon number also can with one or more ehter bonds is 2 ~ 70, or the base when the situation that n is 3 represented by following formula (12).
[changing 22]
In above-mentioned formula (12), R 38~ R 40independently for methylene or carbon number are the alkylene of 2 ~ 6." * Δ represents key respectively.
As the compound represented by above-mentioned formula (11), the carboxylate etc. of mercaptan carboxylic acid and polyvalent alcohol typically can be used.The mercaptan carboxylic acid forming carboxylate include, for example mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, 3-mercaptopentanoic acid etc.And the polyvalent alcohol forming carboxylate include, for example ethylene glycol, propylene glycol, trimethylolpropane, pentaerythrite, TEG, dipentaerythritol, BDO etc.
Compound represented by above-mentioned formula (11) is preferably trimethylolpropane tris (3-mercaptopropionic acid) ester, pentaerythrite four (3-mercaptopropionic acid) ester, two (3-mercaptopropionic acid) ester of TEG, dipentaerythritol six (3-mercaptopropionic acid) ester, pentaerythrite four (mercaptoacetic acid) ester, 1, two (the 3-sulfydryl butyryl acyloxy) butane of 4-, pentaerythrite four (3-mercaptobutyric acid) ester, pentaerythrite 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 23]
[changing 24]
In above-mentioned formula (13), R 41for methylene or carbon number are the alkylene of 2 ~ 20.R 42for straight chain or branch's alkylene that methylene or carbon number are 2 ~ 6.K is the integer of 1 ~ 20.
In above-mentioned formula (14), R 43~ R 46base independently represented by hydrogen atom, hydroxyl or following formula (15).Wherein, R 43~ R 46at least 1 be base represented by following formula (15).
[changing 25]
In above-mentioned formula (15), R 47for straight chain or branch's alkylene that methylene or carbon number are 2 ~ 6.
Mercaptan compound can be used alone or two or more is used in combination.Proportional as containing of the mercaptan compound in colored composition, for [I] alkali soluble resins 100 mass parts, be preferably 1 mass parts ~ 20 mass parts, be more preferably 5 mass parts ~ 15 mass parts.By make mercaptan compound containing proportional for above-mentioned particular range, storage stability and the hardening at subcritical temerature of colored composition can be taken into account with higher level.
[block isocyanate compound]
Block polyisocyanate compound makes isocyanate group react with the compound (blocking agent) containing reactive hydrogen base and become the compound of inertia at normal temperature, there is following character: if heat it, then blocking agent dissociates and regenerates isocyanate group.Colored composition contains block polyisocyanate, to carry out isocyanate-hydroxyl cross-linking reaction as effective crosslinking chemical, thus can take into account storage stability and the hardening at subcritical temerature of colored composition with high level.Block polyisocyanate compound by the polyisocyanate derivative by aliphatics or alicyclic diisocyanate with have reactive hydrogen compound (blocking agent) known reaction and obtain.
Diisocyanate 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, two (isocyanatomethyl) cyclohexane 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, include, for example:
With the oxime of butanone, the block person of forming is carried out to isocyanate group and can enumerate Duranate (registered trademark) 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, the block person of forming is carried out to isocyanate group and can enumerate Duranate (registered trademark) MF-K60X (industrial group of Asahi Chemical Industry);
The block body with the isocyanate compound of (methyl) acryloyl group can enumerate Karenz (registered trademark) MOI-BP, Karenz (registered trademark) MOI-BM (being manufactured by Showa electrician company above).In those commercially available products, show high pliability when the situation of Duranate (registered trademark) E402-B80T, MF-K60X of use, by making and the mixing class of other compounds and using, freely can control its hardness, therefore preferably using.
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 is considered, preferred fulminuric acid ester type polyisocyanate.
Blocking agent 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 methyl alcohol, ethanol, propyl alcohol, butanols, 2-Ethylhexyl Alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, phenmethylol, cyclohexanol etc.;
Phenolic compound include, for example phenol, cresols, 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, diacetone etc.;
Sulfur alcohol compound include, for example butanethiol, lauryl mercaptan etc.;
Amides compound include, for example antifebrin, acetamide, epsilon-caprolactams, δ-valerolactam, butyrolactam etc.;
Imide analog compounds include, for example succinimide, maleimide etc.;
Glyoxaline compound include, for example imidazoles, glyoxal ethyline etc.;
Pyrazole compound include, for example 3-methylpyrazole, 3,5-dimethyl pyrazoles, 3,5-ethylpyrazol etc.;
Carbamide compounds include, for example urea, thiocarbamide, ethylene-urea etc.;
Oxime compound include, for example formaldoxime, acetaldoxime, acetoxime, diacetylmonoxime, cyclohexanone-oxime etc.;
Aminated compounds include, for example diphenylamine, aniline, carbazole etc.;
Imine compound include, for example Ethylenimine, polyethyleneimine 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 is used in combination.
Proportional as containing of the block polyisocyanate compound in colored composition, for [I] alkali soluble resins 100 mass parts, be preferably 0.1 mass parts ~ 10 mass parts, be more preferably 0.5 mass parts ~ 5 mass parts.By make block polyisocyanate compound containing proportional for above-mentioned scope, storage stability and the hardening at subcritical temerature of colored composition can be taken into account with higher level.
[compound containing imidazole ring]
Compound containing imidazole ring can use at least a kind that is selected from the group that the compound represented by following formula (16) is formed.
[changing 26]
In above-mentioned formula (16), A 5, A 6, A 7and R 48independently for hydrogen atom or also can to have substituent carbon number be the straight-chain of 1 ~ 20, the alkyl of branch-like or ring-type.And, A 6with A 7also can be interconnected and form ring.
A 5, A 6, A 7and R 48represented carbon number is the straight-chain of 1 ~ 20, the alkyl of branch-like or ring-type include, for example: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, 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, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, NSC 77136 base, the carbon numbers such as n-eicosane base are the alkyl of 1 ~ 20, the carbon numbers such as cyclobutyl, cyclopentyl, cyclohexyl are the naphthenic base of 3 ~ 20, the carbon numbers such as phenyl, toluyl groups, benzyl, methyl-benzyl, xylyl, sym-trimethyl benzene base, naphthyl, anthryl are the aryl of 6 ~ 20, the carbon numbers such as norborny, three ring decyls, tetracyclododecyl group, adamantyl, methyl adamantane base, ethyl adamantyl, butyl adamantyl are the crosslinked ester ring type alkyl etc. of 6 ~ 20.
Above-mentioned alkyl also can be substituted, and this substituent concrete example 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, ethoxy, positive propoxy, isopropoxy, n-butoxy, 2-methyl propoxyl group, 1-methyl propoxyl group, tert-butoxy are the alkoxy 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 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 A 6with A 7interconnected and formed ring preferably enumerate aromatic rings, carbon number be 2 ~ 20 saturated or undersaturated nitrogen heterocyclic ring.A 6with A 7the compound containing imidazole ring during interconnected and ring that is that the formed situation that is phenyl ring can enumerate the compound represented by following formula (17).
[changing 27]
In above-mentioned formula (17), R 48and A 5with above-mentioned formula (16) synonym.R 49~ R 52be independently the straight-chain of 1 ~ 20, the alkyl of branch-like or ring-type for substituent carbon number also can be had.In addition, R 49~ R 52represented alkyl can enumerate the base same with the alkyl in above-mentioned formula (16).
Compound containing imidazole ring is preferably 2-Phenylbenzimidazole, glyoxal ethyline, 2-tolimidazole.Compound containing imidazole ring can be used alone or two or more is used in combination.Proportional as containing of the compound containing imidazole ring, for [I] alkali soluble resins 100 mass parts, be preferably 0.1 mass parts ~ 10 mass parts, be more preferably 0.5 mass parts ~ 5 mass parts.By make the compound containing imidazole ring containing proportional for above-mentioned particular range, storage stability and the hardening at subcritical temerature of colored composition can be taken into account with higher level.
Other any composition > of <
The colored composition used in the colored filter manufacture of this example, can also optionally containing other any compositions such as surfactant, preserving stabilizer, then auxiliary agent, thermotolerance promoter in the scope not undermining effect of the present invention except above-mentioned [I] alkali soluble resins, [II] polymerizable compound, [III] polymerization initiator, [IV] colorant and [V] compound (rigidizer).Those each any compositions can be used alone also can be used in combination by two or more.Below each composition is described in detail.
[surfactant]
Surfactant can improve further in order to make the film formative of colored composition.Surfactant such as can enumerate fluorine class surfactant, silicone surfactant and other surfactants.
Fluorine class surfactant preferably has the compound of fluoroalkyl and/or fluothane support at least any part of end, main chain and side chain.
The commercially available product of fluorine class surfactant include, for example Ftergent (registered trademark) FT-100, FtergentFT-110, FtergentFT-140A, FtergentFT-150, FtergentFT-250, FtergentFT-251, FtergentFT-300, FtergentFT-310, FtergentFT-400S, Ftergent (registered trademark) FTX-218, FtergentFTX-251 (being manufactured by Neos company above) etc.
The 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.
As the use amount of surfactant, for [I] alkali soluble resins 100 mass parts, be preferably below 1.0 mass parts, be more preferably below 0.7 mass parts.If the use amount of surfactant is more than 1.0 mass parts, then becomes and easily produce film inequality.
[preserving stabilizer]
Preserving stabilizer include, for example sulphur, quinones, hydroquinone type, polyoxy compounds, amine, nitro nitroso compound etc., more specifically can enumerate 4-metoxyphenol, N-nitroso--N-Phenylhydroxylamine aluminium etc.
As the use amount of preserving stabilizer, for [I] alkali soluble resins 100 mass parts, be preferably below 3.0 mass parts, be more preferably below 1.0 mass parts.If the allotment amount of preserving stabilizer is more than 3.0 mass parts, then there is light sensitivity and reduce and cause the situation of pattern form deterioration.
[then auxiliary agent]
Then auxiliary agent can improve further in order to make the adherence of the colored pattern of gained and colored filter and substrate.Then auxiliary agent preferably has the functional silanes coupling agent of carboxyl, methacryl, vinyl, isocyanate group, Oxyranyle isoreactivity functional group; include, for example trimethoxy silane yl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidoxypropyltrimewasxysilane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc.
As the use amount of then auxiliary agent, for [I] alkali soluble resins 100 mass parts, be preferably below 20 mass parts, be more preferably below 15 mass parts.If then the use amount of auxiliary agent is more than 20 mass parts, then there is the tendency becoming and easily produce development and remain.
The modulator approach > of < colored composition
The colored composition used in the manufacture of the colored filter of this example is by by [I] alkali soluble resins, [II] polymerizable compound, [III] polymerization initiator, [IV] colorant, [V] compound (rigidizer) and optionally other any uniform component mixing added and modulating.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 and can dissolve required composition and any composition equably and the solvent do not reacted 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, from the dissolubility of each composition, with the reactivity of each composition, the viewpoints such as the easiness that film is formed are considered, 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 monoethyl ether acetate, ethylene glycol propyl ether acetic acid esters, ethylene glycol mono-n-butyl ether acetic acid esters, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol list positive propyl ether acetic acid esters, diethylene glycol mono-n-butyl ether acetic acid esters, 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, tetrahydrofuran; The ketones such as butanone, cyclohexanone, 2-HEPTANONE, 3-heptanone, diacetone alcohol (4-hydroxy-4-methyl pentane-2-ketone), 4-hydroxy-4-methyl hexane-2-one;
The diacetate esters classes such as propylene-glycol diacetate, 1,3-BDO diacetate esters, 1,6-hexanediol diacetate esters, the lactic acid alkyl ester such as methyl lactate, ethyl lactate class, 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, acid n-pentyl ester, isoamyl acetate, n-butyl propionate, acetic acid-3-methoxybutyl, propionic acid-3-methyl-3-methoxybutyl, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, hydroxyl ethyl acetate, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-hydroxy-2-methyl ethyl propionate, 2-hydroxy-3-methyl methyl butyrate, other ester classes such as 2-Oxobutyric acid ethyl, toluene, dimethylbenzene etc. are aromatic hydrocarbon based,
The amide-types etc. such as 1-METHYLPYRROLIDONE, DMF, DMA.
In those solvents, from dissolubility, pigment-dispersing, the viewpoints such as coating are considered, be 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, cyclohexanone, 2-HEPTANONE, 3-heptanone, 1, 3-butylene glycol diacetate esters, 1, 6-hexanediol diacetate esters, ethyl lactate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, propionic acid-3-methyl-3-methoxy butyl acrylate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, ethyl pyruvate.Solvent can be used alone or uses two or more.
In 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-octanol, 1 nonyl alcohol, acetic acid benzyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethyleneglycol monophenylether acetic acid esters.Above-mentioned high boiling solvent can be used alone or uses two or more.
The content of solvent indefinite, consider from the viewpoint such as coating, stability of the colored composition of gained, the total concentration of each composition of the solvent of removing colored composition preferably becomes the amount of 5 quality % ~ 50 quality %, more preferably becomes the amount of 10 quality % ~ 40 quality %.When colored composition being modulated to the situation of solution state, solid concentration (composition beyond solvent shared in constituent solution) can be set as any concentration according to the value of application target or desired thickness etc.Solid concentration such as can be set as 5 quality % ~ 50 quality %.Preferred solid concentration, according to forming the formation method of film and different on substrate, is described it later.So and the constituent solution of modulation can use aperture to be, after the millipore filter etc. of about 0.5 μm filters, be supplied to use.
The colored composition of above composition and modulator approach can utilize hardening at subcritical temerature and form colored pattern.Specifically, even if under the hardening temperature under the hardening temperature below 200 DEG C, further below 180 DEG C, also can the colored pattern with good reliabilitys such as solvent resistances be obtained.And, can hardening at subcritical temerature be utilized and the colored filter of this example is provided.
Secondly, the colored filter of this example contains colored pattern, the diaphragm be located on this colored pattern.This diaphragm uses the 1st radiation-sensitive resin composition and is formed on colored pattern.
Below, the 1st radiation-sensitive resin composition of this example used in the formation to the diaphragm of the colored filter of this example is illustrated.
< the 1st radiation-sensitive resin composition >
The diaphragm of the colored filter of this example forms middle the 1st used radiation-sensitive resin composition and forms containing, for example lower compound: [A] siloxane polymer, [B] radical polymerization initiator and [C] organic solvent.In addition, can containing [D] ethene unsaturated compound as suitable compositions.And, can containing [E] acid agent or generated base alkaline agent as suitable compositions.In addition, also can containing other any compositions such as surfactants in the scope not undermining effect of the present invention.Below, each composition is described in detail.When the situation containing surfactant, can use from as the compound selecting in the surfactant cited by the surfactant that can be used in the colored composition of above-mentioned example to be suitable for.
< [A] siloxane polymer >
1st radiation-sensitive resin composition of this example contains [A] siloxane polymer.And [A] siloxane polymer contained by the 1st radiation-sensitive resin composition of this example preferably has the siloxane polymer of free-radical reactive functional group.When [A] siloxane polymer is the situation of the siloxane polymer with free-radical reactive functional group, if having the compound of free-radical reactive functional group in the main chain of polymkeric substance of compound or side chain with silicon oxygen bond, be then not particularly limited.In this case, [A] siloxane polymer hardens by free radical polymerization, curing shrinkage can be suppressed for Min..Free-radical reactive functional group include, for example the unsaturated organic groups such as vinyl, Alpha-Methyl vinyl, acryloyl group, methacryl, styryl.In those bases, self-hardening is reacted the aspect of successfully carrying out and is considered preferably have the base of acryloyl group or methacryl.
[A] siloxane polymer is preferably the hydrolytic condensate of hydrolysable silanes compound.The hydrolysable silanes compound forming [A] siloxane polymer preferably comprises the hydrolysable silanes compound of following compound: the hydrolysable silanes compound (being also called (a1) compound below) represented by (a1) following formula (A-1), the hydrolysable silanes compound (being also called (a2) compound below) represented by (a2) following formula (A-2).
[changing 28]
[changing 29]
In above-mentioned formula (A-1), R 1to be carbon number be 1 ~ 6 alkyl.R 2it is the organic group comprising free-radical reactive functional group.P is the integer of 1 ~ 3.Wherein, at R 1and R 2for when multiple, multiple R 1and R 2independently.
In above-mentioned formula (A-2), R 3to be carbon number be 1 ~ 6 alkyl.R 4hydrogen atom, the carbon number alkyl that is 1 ~ 20, carbon number be 1 ~ 20 fluorinated alkyl, phenyl, naphthyl, epoxy radicals, amino or isocyanate group.N is the integer of 0 ~ 20.Q is the integer of 0 ~ 3.Wherein, at R 3and R 4for when multiple, multiple R 3and R 4independently.
In the present invention, so-called " hydrolysable silanes compound " refers to the compound with following base: usually under the coexisting of catalyst-free, superfluous water, heat in the temperature range of room temperature (about 25 DEG C) ~ about 100 DEG C, hydrolyzable and the base generating silanol base maybe can form the base of silicone condensation thing therefrom.In the hydrolysis reaction of the hydrolysable silanes compound represented by above-mentioned formula (A-1) and above-mentioned formula (A-2), a part of water-disintegrable base with unhydrolysed state survives in generated siloxane polymer.Herein, so-called " water-disintegrable base " refers to and can carry out said hydrolyzed and the base that generates silanol base maybe can form the base of silicone condensation thing.And in the 1st radiation-sensitive resin composition, a part of hydrolysable silanes compound can also the unhydrolysed state of water-disintegrable base of part or all in its molecule, and not with other hydrolysable silanes compound condensations and with the state survives of monomer.In addition, " hydrolytic condensate " is the hydrolytic condensate of a part of silanol base condensation each other representing be hydrolyzed silane compound.Below, (a1) compound and (a2) compound are described in detail.
[(a1) compound]
In above-mentioned formula (A-1), R 1to be carbon number be 1 ~ 6 alkyl.R 2it is the organic group comprising free-radical reactive functional group.P is the integer of 1 ~ 3.Wherein, at R 1and R 2for when multiple, multiple R 1and R 2independently.
As above-mentioned R 1carbon number be 1 ~ 6 alkyl include, for example methyl, ethyl, n-pro-pyl, isopropyl, butyl etc.In those bases, consider from the viewpoint of the easiness of hydrolysis, be preferably methyl, ethyl.As above-mentioned p, the viewpoint of the condensation reaction that is certainly hydrolyzed is considered, is preferably 1 or 2, is more preferably 1.
Alkyl, carbon number that it is 1 ~ 12 that the organic group with free-radical reactive functional group can be enumerated by the carbon number of above-mentioned free-radical reactive functional group to straight chain Like, branch-like or ring-type that more than 1 hydrogen atom replaces be 6 ~ 12 aryl, carbon number be the aralkyl etc. of 7 ~ 12.At same molecular memory at multiple R 2time, those R 2independently.And, R 2represented organic group also can have heteroatoms.This kind of organic group include, for example ether, ester group, sulfide base etc.
(a1) compound when p=1 include, for example vinyltrimethoxy silane, vinyltriethoxysilane, vinyl tripropoxy silane, adjacent styryl trimethoxy silane, adjacent styryl triethoxysilane, isophthalic vinyltrimethoxy silane, isophthalic vinyltriethoxysilane, to styryl trimethoxy silane, to styryl triethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, methacryloxy trimethoxy silane, methacryloxy triethoxysilane, methacryloxy tripropoxy silane, acryloxy trimethoxy silane, acryloxy triethoxysilane, acryloxy tripropoxy silane, 2-methacryloxyethyl trimethoxy silane, 2-methacryloxyethyl triethoxysilane, 2-methacryloxyethyl tripropoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl, 3-methacryloxypropyl tripropoxy silane, 2-acryloyl-oxyethyl trimethoxy silane, 2-acryloyl-oxyethyl triethoxysilane, 2-acryloyl-oxyethyl tripropoxy silane, 3-acryloxypropyl trimethoxy silane, 3-acryloxypropyl triethoxysilane, 3-acryloxypropyl tripropoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl, 3-methacryloxypropyl tripropoxy silane, trifluoro propyl trimethoxy silane, trifluoro propyl triethoxysilane, triRuorobutyl trimethoxy silane, the trialkoxy silane compound such as 3-(trimethoxy silane base) propylsuccinic anhydride.
(a1) compound when p=2 include, for example the dialkoxysilane compounds such as vinyl methyl dimethoxysilane, vinyl methyl diethoxy silane, ethenylphenyl dimethoxysilane, ethenylphenyl diethoxy silane, allyl methyl dimethoxysilane, allyl methyl diethoxy silane, phenyl trifluoromethanesulfonate propyldimethoxy-silane.
(a1) compound when p=3 include, for example allyl dimethyl methoxylsilane, allyl dimethyl base oxethyl silane, divinylmethyl methoxy silane, divinylmethyl Ethoxysilane, 3-methacryloxypropyl dimethyl methoxy silane, 3-acryloxypropyl dimethyl methoxy silane, 3-methacryloxypropyl diphenylmethyl TMOS, 3-acryloxypropyl diphenylmethyl TMOS, 3, 3 '-dimethacryloxy propyldimethoxy-silane, 3, 3 '-two acryloxypropyl dimethoxysilane, 3, 3 ', 3 "-trimethacrylate acyl-oxygen base propylmethoxysilane, 3, 3 ', 3 "-three acryloxypropyl methoxy silane, the monoalkoxysilane compounds such as dimethyl trifluoro propyl methoxy silane.
In those (a1) compounds, from mar resistance etc. can be reached with high level and the aspect of carrying out condensation is considered, be preferably vinyltrimethoxy silane, to styryl triethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-acryloxypropyl trimethoxy silane, 3-methacryloxypropyl, 3-acryloxypropyl triethoxysilane, 3-(trimethoxy silane base) propylsuccinic anhydride.
[(a2) compound]
In above-mentioned formula (A-2), R 3to be carbon number be 1 ~ 6 alkyl.R 4for fluorinated alkyl, phenyl, naphthyl, epoxy radicals, amino or isocyanate group that hydrogen atom, the carbon number alkyl that is 1 ~ 20, carbon number are 1 ~ 20.N is the integer of 0 ~ 20.Q is the integer of 0 ~ 3.Wherein, at R 3and R 4when being respectively multiple situations, multiple R 3and R 4independently.
As above-mentioned R 3carbon number be 1 ~ 6 alkyl include, for example methyl, ethyl, n-pro-pyl, isopropyl, butyl etc.In those bases, consider from the viewpoint of the easiness of hydrolysis, be preferably methyl, ethyl.As above-mentioned q, the viewpoint of the condensation reaction that is certainly hydrolyzed is considered, is preferably 1 or 2, is more preferably 1.
At above-mentioned R 4when be above-mentioned carbon number being the situation of the alkyl of 1 ~ 20, this alkyl include, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, 3-methyl butyl, 2-methyl butyl, 1-methyl butyl, 2,2-dimethyl propyl, n-hexyl, 4-methyl amyl, 3-methyl amyl, 2-methyl amyl, 1-methyl amyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 4,4-dimethyl amyl group, 3,4-dimethyl amyl group, 2,4-dimethyl amyl group, Isosorbide-5-Nitrae-dimethyl amyl group, 3,3-dimethyl amyl group, 2,3-dimethyl amyl group, 1,3-dimethyl amyl group, 2,2-dimethyl amyl group, 1,2-dimethyl amyl group, 1,1-dimethyl amyl group, 2,3,3-trimethyl butyl, 1,3,3-trimethyl butyl, 1,2,3-trimethyl butyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methylheptyl, 2-ethylhexyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, n-heptadecane base, n-octadecane base, NSC 77136 base etc.Being preferably carbon number is the alkyl of 1 ~ 10, is more preferably the alkyl that carbon number is 1 ~ 3.
As (a2) compound when q=0, such as, can be enumerated tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes, four positive propoxy silane, tetraisopropoxysilan etc. by the silane compound that 4 water-disintegrable bases replace.
As (a2) compound when q=1, methyltrimethoxy silane is include, for example by the silane compound that 1 non-hydrolyzable base and 3 water-disintegrable bases replace, methyl triethoxysilane, methyl three isopropoxy silane, methyl three butoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three isopropoxy silane, ethyl three butoxy silane, butyl trimethoxy silane, phenyltrimethoxysila,e, naphthyl trimethoxy silane, phenyl triethoxysilane, naphthyl-triethyoxy silicane alkane, amino trimethoxy silane, amino triethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy, γ-glycidoxypropyltrimewasxysilane, 3-isocyano group propyl trimethoxy silicane, 3-isocyano group propyl-triethoxysilicane, o-tolyl trimethoxy silane, between tolyl trimethoxy silane, p-methylphenyl trimethoxy silane etc.
As (a2) compound when q=2, be include, for example dimethyldimethoxysil,ne, dimethoxydiphenylsilane, dibutyldimethoxysilane etc. by the silane compound that 2 non-hydrolyzable bases and 2 water-disintegrable bases replace.
As (a2) compound when q=3, be include, for example trimethylmethoxysilane, triphenylmethoxy silane, tributyl methoxy silane etc. by the silane compound that 3 non-hydrolyzable bases and 1 water-disintegrable base replace.
In those (a2) compounds, the silane compound preferably replaced by 4 water-disintegrable bases, the silane compound replaced by 1 non-hydrolyzable base and 3 water-disintegrable bases, more preferably by silane compound that 1 non-hydrolyzable base and 3 water-disintegrable bases replace.Particularly preferred hydrolysable silanes compound include, for example tetraethoxysilane, methyltrimethoxy silane, methyl triethoxysilane, methyl three isopropoxy silane, methyl three butoxy silane, phenyltrimethoxysila,e, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three isopropoxy silane, ethyl three butoxy silane, butyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, naphthyl trimethoxy silane, gamma-amino propyl trimethoxy silicane and γ-isocyanates propyl trimethoxy silicane.This kind of hydrolysable silanes compound can be used alone or two or more be combinationally used.
About the mixing ratio of above-mentioned (a1) compound and (a2) compound, it is desirable to (a1) compound more than 5mol%.When (a1) compound is the situation of below 5mol%, there is following tendency: exposed photosensitive degree when forming cured film is low, makes the reductions such as the mar resistance of the cured film of gained further.
[hydrolytic condensation of (a1) compound and (a2) compound]
As the condition making above-mentioned (a1) compound and the condensation of (a2) compound hydrolysis, if make the hydrolysis at least partially of (a1) compound and (a2) compound, water-disintegrable base is converted to silanol base, thus the condition producing condensation reaction is then not particularly limited, as wherein one example, can implement as described below.
The water being supplied to hydrolysis-condensation reaction preferably uses by methods such as reverse osmosis membrane processing, ion-exchange treatment, distillations and has carried out the water of purifying.By using this kind of purified water, can subsidiary reaction be suppressed, the reactivity of hydrolysis is improved.As the use amount of water, for the total amount 1 mole of the water-disintegrable base of above-mentioned (a1) compound and (a2) compound, be preferably 0.1 mole ~ 3 moles, be more preferably 0.3 mole ~ 2 moles, be particularly preferably 0.5 mole ~ 1.5 moles.By using the water of this kind of amount, the reaction velocity optimization of hydrolytic condensation can be made.
The solvent being supplied to hydrolytic condensation include, for example alcohols, ethers, glycol ethers, ethylene glycol alkylether acetates, diethylene glycol alkyl ether, propylene-glycol monoalky lether, propylene-glycol monoalky lether acetic acid esters, propylene-glycol monoalky lether propionic ester, aromatic hydrocarbon based, ketone, other ester classes etc.Those solvents can be used alone or two or more may be used and use.
Alcohols include, for example methyl alcohol, ethanol, phenmethylol, 2-phenylethanol, 3-phenyl-1-propanol etc.
Ethers include, for example tetrahydrofuran etc.
Glycol ethers include, for example glycol monoethyl ether, ethylene glycol monoethyl ether etc.Ethylene glycol alkylether acetates include, for example methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate etc.
Diethylene glycol alkyl ether include, for example diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether etc.
Propylene-glycol monoalky lether include, for example propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether etc.
Propylene-glycol monoalky lether acetic acid esters include, for example propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, propylene glycol monobutyl ether acetic acid esters etc.
Propylene-glycol monoalky lether propionic ester include, for example propylene glycol monomethyl ether propionate, dihydroxypropane single-ether propionic ester, propylene glycol monopropyl ether propionic ester, propylene glycol monobutyl ether propionic ester etc.
Aromatic hydrocarbon basedly include, for example toluene, dimethylbenzene etc.
Ketone include, for example butanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone etc.
Other ester classes include, for example methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, Butyl Glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy methyl propionate, 3-hydroxypropionate, 3-hydracrylic acid propyl ester, 3-hydracrylic acid butyl ester, 2-hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, ethyl methoxyacetate, methoxy propyl acetate, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, ethoxyacetic acid propyl ester, ethoxyacetic acid butyl ester, propoxyl group methyl acetate, propoxyl group ethyl acetate, propoxyl group propyl acetate, propoxyl group butyl acetate, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy acetic acid propyl ester, butoxy acetic acid butyl ester, 2-methoxy methyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxypropanoate, 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-propoxyl group propyl propionate, 3-propoxyl group butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, 3-butoxy butyl propionate etc.
In those solvents, preferred ethylene glycol alkylether acetates, diethylene glycol alkyl ether, propylene-glycol monoalky lether, propylene-glycol monoalky lether acetic acid esters, methoxyacetic acid butyl ester, particularly preferably diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, methoxyacetic acid butyl ester.
Hydrolysis-condensation reaction preferably carries out under the existence of following catalyzer: acid catalyst (such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acid-exchange resin, various lewis acids etc.), the base catalyst (nitrogen-containing compound such as such as ammonia, primary amine class, secondary amine class, tertiary amines, pyridine; Deacidite; The oxyhydroxide such as NaOH; The carbonate such as sal tartari; The carboxylates such as sodium acetate; Various lewis bases etc.) or alkoxide (such as alkoxide zirconium, alkoxide titanium, alkoxide aluminium etc.) etc.Such as, alkoxide aluminium can use aluminium isopropoxide.As the use amount of catalyzer, consider from the viewpoint of facilitation of hydrolysis condensation reaction, for the monomer 1 mole of hydrolysable silanes compound, be preferably less than 0.2 mole, be more preferably 0.00001 mole ~ 0.1 mole.
Temperature of reaction in hydrolytic condensation and reaction time can be suitable for setting, and such as temperature of reaction is preferably 40 DEG C ~ 200 DEG C, are more preferably 50 DEG C ~ 150 DEG C.Reaction time is preferably 30 minutes ~ 24 hours, is more preferably 1 hour ~ 12 hours.By being set to this kind of temperature of reaction and reaction time, can be hydrolyzed condensation reaction efficiently.In this hydrolytic condensation, can in reactive system, once add hydrolysable silanes compound, water and catalyzer and react with a stage, or also hydrolysable silanes compound, water and catalyzer can be divided into for several times and be added in reactive system, being hydrolyzed and condensation reaction with multiple stage.In addition, after hydrolysis-condensation reaction, by adding dewatering agent, next carries out evaporating and removes in water and the alcohol autoreaction system that generates.The dewatering agent used in this stage generally adsorbs or comprises superfluous water and consumes water separation capability completely, or removes by evaporating.
Said hydrolyzed condensation product utilize gel permeation chromatography (GelPermeationChromatograph, GPC) and the polystyrene conversion weight average molecular weight of gained (hereinafter referred to as " Mw ") be preferably 500 ~ 10,000, be more preferably 1,000 ~ 5,000.By making Mw be more than 500, the film forming of the 1st radiation-sensitive resin composition of this example can be improved.On the other hand, by making Mw be 10, less than 000, can prevent the developability of the 1st radiation-sensitive resin composition from reducing.
The polystyrene conversion number average molecular weight (hereinafter referred to as " Mn ") of GPC and gained that utilizes of said hydrolyzed condensation product is preferably 300 ~ 5,000, is more preferably 500 ~ 3,000.By making the Mn of [A] siloxane polymer be above-mentioned scope, the sclerous reaction during film sclerosis of the 1st radiation-sensitive resin composition can be improved.
The molecular weight distribution " Mw/Mn " of said hydrolyzed condensation product is preferably less than 3.0, is more preferably less than 2.6.By making the Mw/Mn of the hydrolytic condensate of (a1) compound and (a2) compound be less than 3.0, the developability of the cured film of gained can be improved.
Less and the pattern form desired by easily being formed of the 1st radiation-sensitive resin composition comprising [A] siloxane polymer generation that development is residual when developing.
< [B] radical polymerization initiator >
1st radiation-sensitive resin composition of this example contains [B] radical polymerization initiator; therefore can harden due to the free radical polymerization of [A] siloxane polymer; even low exposure also can form the cured film with sufficient mar resistance, and can low exposure and the diaphragm of this example with sufficient mar resistance is provided.In addition, [B] radical polymerization initiator is preferably the polymerization initiator (radioactivity-sensitive polymerization initiator) of radioactivity-sensitive.
[B] radical polymerization initiator can enumerate O-acyl group oxime compound, acetophenone compound, united imidazole etc.Those [B] radical polymerization initiators can be used alone or two or more is used in combination.
O-acyl group oxime compound include, for example 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-acetic acid esters, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-ethane-1-ketoxime-O-benzoic ether, 1-[9-normal-butyl-6-(2-ethylamino benzonitrile acyl group)-9H-carbazole-3-base]-ethane-1-ketoxime-O-benzoic ether, 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) methoxybenzoyl base }-9H-carbazole-3-base]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9H-carbazole-3-base]-1-(O-acetyl oxime) etc.
In those compounds; preferred O-acyl group oxime compound can enumerate 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 methoxybenzoyl base)-9H-carbazole-3-base]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-1,3-dioxolane base) methoxybenzoyl base }-9H-carbazole-3-base]-1-(O-acetyl oxime).
Acetophenone compound can enumerate alpha-amido ketonic compound, alpha-hydroxyacetone compounds.
Alpha-amido ketonic 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.
In those compounds, preferred acetophenone compound is alpha-amido ketonic compound.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 can be enumerated.
United imidazole include, for example 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (4-carboethoxyphenyl)-1,2 '-bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
In those compounds, preferred united imidazole can enumerate 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, is more preferably 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
When using united imidazole as [B] radical polymerization initiator, in order to make its sensitizing, the aliphatics or aromatics (hereinafter referred to as " amino sensitizer ") with dialkyl amido can be added.
Amino sensitizer include, for example 4,4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylamino) benzophenone etc.Preferred 4,4 '-bis-(diethylamino) benzophenone in those amino sensitizers.Above-mentioned amino sensitizer can be used alone or two or more is used in combination.
In addition, in the 1st radiation-sensitive resin composition also with united imidazole and amino sensitizer, mercaptan compound can be added as hydroperoxyl radical supplying agent.United imidazole is ftractureed by sensitizing due to amino sensitizer, thus produces imidazole radical, but also there is the situation failing directly to show high polymerization initiating power.But, add mercaptan compound by the system that coexists at united imidazole and amino sensitizer, can to the hydroperoxyl radical of imidazole radical supply from mercaptan compound.Its result, imidazole radical is converted to neutral imidazoles, and produces the high composition with Thiyl Radical of polymerization initiating power, even low radiation exposure amount also can form the higher cured film such as mar resistance thus.
Above-mentioned mercaptan compound include, for example the aromatic mercaptans compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-5-methoxybenzothiazole; The aliphatics list mercaptan compounds such as 3-mercaptopropionic acid, 3-mercapto-propionate; 2 officials such as pentaerythrite four (mercaptoacetic acid) ester, pentaerythrite four (3-mercaptopropionic acid) ester can above analiphatic sulphur alcoholic compound.Particularly preferably 2-mercaptobenzothiazole in those mercaptan compounds.
When also with united imidazole and amino sensitizer, the use amount of amino sensitizer is preferably 0.1 mass parts ~ 50 mass parts for united imidazole 100 mass parts, is more preferably 1 mass parts ~ 20 mass parts.By making the use amount of amino sensitizer be 0.1 mass parts ~ 50 mass parts, the sclerous reaction of the 1st radiation-sensitive resin composition when exposing can be improved, and the mar resistance etc. of the cured film of gained can be improved.
And, when also with united imidazole, amino sensitizer and mercaptan compound, the use amount of mercaptan compound is preferably 0.1 mass parts ~ 50 mass parts for united imidazole 100 mass parts, is more preferably 1 mass parts ~ 20 mass parts.By making the use amount of mercaptan compound be 0.1 mass parts ~ 50 mass parts, the mar resistance etc. of the cured film of gained can be improved.
As the use amount of [B] radical polymerization initiator in the 1st radiation-sensitive resin composition, for [A] siloxane polymer 100 mass parts, be preferably 0.05 mass parts ~ 30 mass parts, be more preferably 0.1 mass parts ~ 15 mass parts.Be above-mentioned scope by making the use amount of [B] radical polymerization initiator; 1st radiation-sensitive resin composition can be formed and demonstrate high radioactive ray light sensitivity; there is the cured film of high mar resistance etc. further, and the diaphragm of this example of the excellences such as mar resistance can be provided.
< [C] organic solvent >
1st radiation-sensitive resin composition of this example contains [C] organic solvent.
[C] organic solvent is preferably more than 0.1mmHg containing the vapor pressure at (C1) 20 DEG C and less than the organic solvent of 1mmHg.And the vapor pressure preferably contained at (C2) 20 DEG C is the organic solvent of more than 1mmHg below 20mmHg.By using [C] organic solvent with the vapor pressure of particular range, even if adopt jetting nozzle formula rubbing method, also can prevent crawling and become can high-speed coating.In addition, the mensuration of vapor pressure can use known method, refers to the value utilizing rising method (gas flow through methods) and mensuration in the present invention.
[C] organic solvent can be suitable for using and above-mentioned each uniform component contained in the 1st radiation-sensitive resin composition is dissolved or disperseed, and the organic solvent do not reacted with each composition.This kind [C] organic solvent include, for example alcohols, ethylene glycol monoalkyl ether class, glycol dialkyl ether class, propylene-glycol monoalky lether class, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ether class, diethylene glycol monoalkyl ether acetate class, dipropylene glycol monoalkylether class, dipropylene glycol ester class, amide-type, lactone, ketone etc.Those organic solvents can be used alone a kind, also can be used in combination by two or more.
< [D] ethene unsaturated compound >
1st radiation-sensitive resin composition of this example is preferably further containing [D] ethene unsaturated compound.[D] ethene unsaturated compound is the ethene unsaturated compound except above-mentioned [A] siloxane polymer.By making the 1st radiation-sensitive resin composition further containing [D] ethene unsaturated compound, radioactive ray light sensitivity can be made to improve and cause sublimability to reduce.Therefore, mar resistance and the transparency of the cured film formed by the 1st radiation-sensitive resin composition improve further, can provide the diaphragm of this example of mar resistance and transparency excellence.
As [D] ethene unsaturated compound, the good and viewpoint that the sclerosis film strength of gained the is improved consideration of auto polymerization, preferred simple function, 2 officials can or 3 officials can above (methyl) acrylate.By making the 1st radiation-sensitive resin composition contain those compounds, the cured film that the transparency balances with mar resistance equal altitudes can be formed.
Simple function (methyl) acrylate as [D] ethene unsaturated compound include, for example 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2-acryloyl-oxyethyl) (2-hydroxypropyl) phthalic ester, (2-methacryloxyethyl) (2-hydroxypropyl) phthalic ester, ω-carboxy-polycaprolactone mono acrylic ester etc.Commercially available product include, for example ARONIX (registered trademark) M-101, ARONIXM-111, ARONIXM-114, ARONIXM-5300 (being manufactured by East Asia Synesis Company above); KAYARAD (registered trademark) TC-110S, KAYARADTC-120S (being made by Japanese chemical drug Inc. above); Viscoat158, Viscoat2311 (being manufactured by Osaka Organic Chemical Industry company above) etc.
2 officials as [D] ethene unsaturated compound can include, for example ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol diacrylate, propylene glycol dimethacrylate fat, ethylene glycol dimethacrylate, diethylene glycol diacrylate, dimethacrylate, tetraethylene glycol diacrylate, TEG dimethylacrylate, 1 by (methyl) acrylate, 6-hexanediyl ester, 1,6-hexanediol dimethacrylate fat, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate fat etc.Commercially available product include, for example ARONIX (registered trademark) M-210, ARONIXM-240, ARONIXM-6200 (being manufactured by East Asia Synesis Company above); KAYARAD (registered trademark) HDDA, KAYARADHX-220, KAYARADR-604 (being made by Japanese chemical drug Inc. above); Viscoat260, Viscoat312, Viscoat335HP (being manufactured by Osaka Organic Chemical Industry company above); Lightacrylate1,9-NDA (chemical company of common prosperity society).
3 officials as [D] ethene unsaturated compound can include, for example trimethylolpropane triacrylate by (methyl) acrylate above, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol pentamethacrylates, dipentaerythritol acrylate, the potpourri of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate, dipentaerythritol hexamethacrylate, ethylene-oxide-modified dipentaerythritol acrylate, three (2-acryloyl-oxyethyl) phosphate, three (2-methacryloxyethyl) phosphate, isocyanuric acid modified triacrylate, isocyanuric acid EO modified triacrylate, succinate modified pentaerythritol triacrylate, succinate modified Dipentaerythritol Pentaacrylate, also can enumerate in addition and have straight chain alkylen and alicyclic structure and have more than 1 hydroxyl in the compound with more than 2 isocyanate group and molecule and have 3, the multifunctional urethane acrylate compounds etc. that the compound of 4 or 5 (methyl) acryloxies reacts and obtains.Commercially available product include, for example ARONIX (registered trademark) M-309, ARONIXM-313, ARONIXM-315, ARONIXM-400, ARONIXM-405, ARONIXM-450, ARONIXM-7100, ARONIXM-8030, ARONIXM-8060, ARONIXTO-1450 (being manufactured by East Asia Synesis Company above); KAYARAD (registered trademark) TMPTA, KAYARADDPHA, KAYARADDPCA-20, KAYARADDPCA-30, KAYARADDPCA-60, KAYARADDPCA-120, KAYARADDPEA-12 (being made by Japanese chemical drug Inc. above); Viscoat295, Viscoat300, Viscoat360, ViscoatGPT, Viscoat3PA, Viscoat400 (being manufactured by Osaka Organic Chemical Industry company above); As Newfrontier (registered trademark) R-1150 (the first industrial pharmaceutical company), KAYARAD (registered trademark) DPHA-40H (Japanese chemical drug company) etc. of the commercially available product containing multifunctional urethane acrylate compounds.
Preferred ω-carboxy-polycaprolactone mono acrylic ester in those [D] ethene unsaturated compounds, 1, 9-nonanediol dimethacrylate fat, trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, or the potpourri of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate, ethylene-oxide-modified dipentaerythritol acrylate, succinate modified pentaerythritol triacrylate, succinate modified Dipentaerythritol Pentaacrylate, commercially available product containing multifunctional urethane acrylate compounds.
Above-mentioned [D] ethene unsaturated compound can be used alone also can be used in combination by two or more.As the usage ratio of [D] ethene unsaturated compound in the 1st radiation-sensitive resin composition, for [A] siloxane polymer 100 mass parts, be preferably 5 mass parts ~ 80 mass parts, be more preferably 10 mass parts ~ 30 mass parts.By the use amount of [D] ethene unsaturated compound is set to above-mentioned scope, the mar resistance etc. of the radioactive ray light sensitivity of the 1st radiation-sensitive resin composition and the cured film of gained can be made to become better.
< [E] acid agent or generated base alkaline agent >
1st radiation-sensitive resin composition of this example can contain [E] acid agent or generated base alkaline agent.[E] acid agent or generated base alkaline agent may be defined as the compound can releasing acidic actives or basic activated material.And [E] acid agent or generated base alkaline agent are preferably [E] radioactivity-sensitive acid agent or radioactivity-sensitive generated base alkaline agent.Now, [E] radioactivity-sensitive acid agent or radioactivity-sensitive generated base alkaline agent may be defined as the compound can releasing acidic actives or basic activated material by irradiating radioactive ray.[A] siloxane polymer due to [E] acid agent or generated base alkaline agent catalyst action and harden, thus polymerism is uprised further.Its result, for the 1st radiation-sensitive resin composition, can form the cured film of the excellences such as mar resistance, and can provide the diaphragm with excellent mar resistance etc.
As in order to make [E] acid agent or generated base alkaline agent decompose, produce the kation of acidic actives or basic activated material or negative ion etc. and the radioactive ray that irradiate, visible ray, ultraviolet, infrared ray, X ray, alpha ray, β ray, gamma-rays etc. can be enumerated.In those radioactive ray, there is fixing energy level certainly, setting rate high in cured film can be reached, and the aspect consideration that irradiation unit is less expensive and small-sized, preferably use ultraviolet.
Above-mentioned radioactivity-sensitive acid agent is preferably diphenyl iodnium, triphenyl sulfonium salt, thiophane salt, is more preferably triphenyl sulfonium salt, thiophane salt.
Diphenyl iodnium include, for example diphenyl iodine tetrafluoroborate, diphenyl iodine hexafluorophosphonate, diphenyl iodine hexafluoro arsenate, diphenyl iodine fluoroform sulphonate, diphenyl iodine trifluoroacetate, diphenyl iodine tosilate, diphenyl iodine butyl three (2, 6-difluorophenyl) borate, 4-methoxyphenyl phenyl-iodide tetrafluoroborate, two (4-tert-butyl-phenyl) iodine tetrafluoroborate, two (4-tert-butyl-phenyl) iodine hexafluoro arsenate, two (4-tert-butyl-phenyl) iodine fluoroform sulphonate, two (4-tert-butyl-phenyl) iodine trifluoroacetate, two (4-tert-butyl-phenyl) iodine tosilate, two (4-tert-butyl-phenyl) iodine camsilate etc.
Triphenyl sulfonium salt include, for example triphenylsulfonium triflate sulfonate, triphenylsulfonium camsilate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium tosilate, triphenylsulfonium butyl three (2,6-difluorophenyl) borate etc.
Thiophane salt include, for example 1-(4-n-butoxy naphthalene-1-base) thiophane fluoroform sulphonate, 1-(4-n-butoxy naphthalene-1-base) the positive fourth sulfonate of thiophane nine fluorine, 1-(4-n-butoxy naphthalene-1-base) thiophane-1, 1, 2, the fluoro-2-of 2-tetra-(norbornane-2-base) esilate, 1-(4-n-butoxy naphthalene-1-base) thiophane-2-(5-tert-butoxy carbonyl oxygen base dicyclo [2.2.1] heptane-2-base)-1, 1, 2, 2-tetrafluoro esilate, 1-(4-n-butoxy naphthalene-1-base) thiophane-2-(6-tert-butoxy carbonyl oxygen base dicyclo [2.2.1] heptane-2-base)-1, 1, 2, 2-tetrafluoro esilate, 1-(4, 7-dibutoxy-1-naphthyl) thiophane fluoroform sulphonate etc.
In those radioactivity-sensitive acid agents, the viewpoint improved from the radioactive ray light sensitivity of the 1st radiation-sensitive resin composition is considered, particularly preferably triphenylsulfonium triflate sulfonate, triphenylsulfonium camsilate, 1-(4,7-dibutoxy-1-naphthyl) thiophane fluoroform sulphonate.
Above-mentioned radioactivity-sensitive generated base alkaline agent include, for example: 2-nitrobenzyl cyclohexylcarbamate, [[(2, 6-dinitrobenzyl) oxygen base] carbonyl] cyclohexylamine, N-(2-nitrobenzyloxycarbonyl) pyrrolidine, two [[(2-nitrobenzyl) oxygen base] carbonyl] hexane-1, 6-diamines, triphenylcarbinol, O-carbamyl hydroxy amide, O-carbamyl oxime, 4-(methylthio phenyl formoxyl)-1-methyl isophthalic acid-morpholino ethane, (4-morpholino benzoyl)-1-benzyl-1-dimethylaminopropanecompounds, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone, six ammonia cobalts (III) three (trityl group borate) etc.
In those radioactivity-sensitive generated base alkaline agents, the viewpoint certainly making the radioactive ray light sensitivity of the 1st radiation-sensitive resin composition improve is considered, more preferably 2-nitrobenzyl cyclohexylcarbamate, O-carbamyl hydroxy amide.
[E] acid agent or generated base alkaline agent can be used alone, also can be used in combination by two or more.As the use amount of [E] acid agent or generated base alkaline agent, for [A] siloxane polymer 100 mass parts, be preferably below 0.01 mass parts ~ 20 mass parts, be more preferably below 0.1 mass parts ~ 10 mass parts.As the 1st radiation-sensitive resin composition; by the use amount of [E] acid agent or generated base alkaline agent is set to 0.01 mass parts ~ 20 mass parts; radioactive ray light sensitivity, mar resistance, transparent isoequilibrium can form excellent cured film well, the diaphragm of this example of this kind of excellent can be provided.
The 1st radiation-sensitive resin composition formed containing above composition can utilize hardening at subcritical temerature and form diaphragm.Specifically, even if under the hardening temperature below 200 DEG C, be under the hardening temperature of less than 180 DEG C furthermore, also can obtain the diaphragm with good reliability.And, can hardening at subcritical temerature be utilized and the colored filter of this example is provided.
Secondly, the colored filter of this example has ITO electrode on diaphragm.ITO electrode uses the known methods such as sputtering method and on diaphragm, forms ito film and formed.In addition, in the colored filter of this example, also can use other transparency electrodes and replace the ITO electrode on diaphragm.This transparency electrode can use the transparent material with transmissivity high for visible ray and electric conductivity and form.Such as can use and comprise tin oxide (SnO 2) NESA film (registered trademark of PPG company of the U.S.), indium zinc oxide (IndiumZincOxide, IZO), zinc paste (ZnO) etc. and form.In this case, can on diaphragm, configure tin oxide electrode or IZO electrode etc. and replace ITO electrode.
Secondly, the colored filter of this example can comprise the distance piece in the ITO electrode that is uprightly arranged on diaphragm.This distance piece can use the 2nd radiation-sensitive resin composition and be formed.Below, the 2nd radiation-sensitive resin composition of this example used in the formation to the distance piece of the colored filter of this example 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 example contains [α] compound, [β] polymerizable compound, [γ] polymerization initiator and [δ] compound, also can contain any composition further.2nd radiation-sensitive resin composition by utilizing the exposure of radioactivity-sensitive, development and easily form the fine and pattern of exquisiteness, thus realizes hardening at subcritical temerature.And, there is storage stability and there is sufficient resolution and radioactive ray light sensitivity.Below each composition is described in detail.
< [α] compound >
As [α] compound contained in the 2nd radiation-sensitive resin composition, just consider the patterning of the distance piece of the colored filter of this example and preferred bases soluble resin.Alkali soluble resins if having the resin of alkali-developable owing to having carboxyl, is then not particularly limited.And, can containing the compound with epoxy radicals in alkali soluble resins.
The compound with epoxy radicals include, for example the compound etc. in 1 molecule with more than 2 Oxyranyles, epoxypropane base, glycidyl, 3,4-epoxycyclohexyls.
There 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 ether, 2-(3, 4-epoxycyclohexyl-5, 5-spiral shell-3, 4-epoxy) cyclohexane-Jian diox, two (3, 4-epoxycyclohexyl-methyl) adipate, two (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, 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, two (3 of ethylene glycol, 4-epoxycyclohexyl-methyl) ether, ethylene 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 ether etc.
There are more than 2 epoxypropane bases (1 in 1 molecule, 3-epoxy construction) compound include, for example Isosorbide-5-Nitrae-bis-[(3-ethyl-3-epoxypropane ylmethoxy) methyl] benzene, two { [1-ethyl (3-epoxypropane base)] methyl } ether, two (3-ethyl-3-epoxypropane ylmethyl) ether etc.
As the epoxy compound that other can contain in [α] 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 polyvalent alcohols 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 glycol of gained by addition one kind or two or more alkylene oxide on the aliphatic polyols such as ethylene glycol, propylene glycol, glycerine;
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 dibasic acid;
The ethylene oxidic ester of higher fatty acid;
Epoxidised soybean oil, epoxidation linseed wet goods.
As those commercially available product, such as: bisphenol A type epoxy resin can enumerate Epikote1001, Epikote1002, Epikote1003, Epikote1004, Epikote1007, Epikote1009, Epikote1010, Epikote828 (being manufactured by japan epoxy resin company (JapanEpoxyResinsCo., Ltd) above) etc.;
Bisphenol f type epoxy resin can enumerate Epikote807 (japan epoxy resin company) etc.;
Phenol novolak type epoxy can enumerate Epikote152, Epikote154, Epikote157S65 (being manufactured by japan epoxy resin company above), EPPN (registered trademark) 201, EPPN202 (being made by Japanese chemical drug Inc. above) etc.;
Cresol novolak type epoxy resin can enumerate EOCN (registered trademark) 102, EOCN103S, EOCN104S, EOCN1020, EOCN1025, EOCN1027 (being made by Japanese chemical drug Inc. above), Epikote180S75 (japan epoxy resin company) etc.;
Many phenol-type epoxy resins can enumerate Epikote1032H60, EpikoteXY-4000 (being manufactured by japan epoxy resin company above) etc.;
Cyclic aliphatic epoxy resin can enumerate CY-175, CY-177, CY-179, AralditeCY-182, AralditeCY-192, AralditeCY-184 (being manufactured by Ciba company limited above), ERL-4234, ERL-4299, ERL-4221, ERL-4206 (being manufactured by U.C.C company above), Shodyne509 (Showa electrician company), Epiclon200, Epiclon400 (being manufactured by large Japanese ink company above), Epikote871, Epikote872 (being manufactured by japan epoxy resin company above), ED-5661, ED-5662 (being manufactured by Celanesecoating company above) etc.,
Aliphatic polyglycidyl ether can enumerate Epolight100MF (chemical company of common prosperity society), EPIOL (registered trademark) TMP (Nof Corp.) etc.
Preferred phenol novolak type epoxy and many phenol-type epoxy resins in those.
The alkali soluble resins as [α] compound contained in 2nd radiation-sensitive resin composition can use the alkali soluble resins of the multipolymer comprising following structural unit: the structural unit that the structural unit that (α-1) is formed by least a kind ((α-1) compound) being selected from the group be made up of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides, (α-2) are formed by the unsaturated compound ((α-2) compound) containing epoxy radicals.And, the multipolymer that [I] alkali soluble resins contained in the colored composition used in the colored filter manufacture with this above-mentioned example is identical can be used.Above-mentioned (I-1) such as can be used to be selected from least a kind ((I-1) compound) of the group be made up of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides as (α-1) compound, to use (I-2) unsaturated compound containing epoxy radicals ((I-2) compound) as (α-2) compound.And the alkali soluble resins as [α] compound can use the alkali soluble resins of the multipolymer comprising following structural unit: the structural unit formed by (I-1) compound, the structural unit formed by (I-2) compound.
< [β] polymerizable compound >
[β] polymerizable compound is the polymerizable compound with ethene unsaturated link.And [β] polymerizable compound can use the compound that [II] polymerizable compound contained in the colored composition used in the colored filter manufacture with above-mentioned example is identical.
[β] polymerizable compound can be used alone or two or more is used in combination.Proportional as containing of [β] polymerizable compound in radiation-sensitive resin composition, for [α] compound 100 mass parts, be preferably 20 mass parts ~ 200 mass parts, be more preferably 40 mass parts ~ 160 mass parts.By make [β] polymerizable compound containing proportional for above-mentioned scope, even if radiation-sensitive resin composition can to form adhesion excellent and under low exposure, also have the cured film of sufficient hardness, and excellent distance piece can be provided.
< [γ] polymerization initiator >
[γ] polymerization initiator is radioactivity-sensitive polymerization initiator.[γ] polymerization initiator can use the compound that [III] polymerization initiator contained in the colored composition used in the colored filter manufacture with this above-mentioned example is identical.
[γ] polymerization initiator can be used alone or two or more is used in combination.Proportional as containing of [γ] polymerization initiator in the 2nd radiation-sensitive resin composition, for [α] compound 100 mass parts, be preferably 1 mass parts ~ 40 mass parts, be more preferably 5 mass parts ~ 30 mass parts.By make [γ] polymerization initiator containing proportional be 1 mass parts ~ 40 mass parts, even if the 2nd radiation-sensitive resin composition can be formed also have high hardness and the cured film of adhesion when low exposure, and excellent distance piece can be formed.
< [δ] compound >
The 2nd radiation-sensitive resin composition used in the formation of the distance piece of the colored filter of this example contains and has [δ] compound that is amino and electron-withdrawing group, and the sclerosis of cured film when can realize the hardening at subcritical temerature of the 2nd radiation-sensitive resin composition by this promotes.And, also can realize storage stability, the voltage retention of the liquid crystal display cells comprising colored filter (the rewarding distance piece of described colored filter tool) can be kept in addition with high level.
[δ] compound is at least a kind of compound being selected from the group that the compound represented by above-mentioned formula (1) and formula (2) is formed.About structure detailed of the compound represented by above-mentioned formula (1) and formula (2), be illustrated when [V] compound contained in above-mentioned colored composition is described.Particularly R 7~ R 16in at least 1 be amino, all or part of alkyl that can be also 1 ~ 6 by carbon number of the hydrogen atom of this amino replaces, during the situation of [δ] compound used in for the 2nd radiation-sensitive resin composition, all or part of alkylene that can be also 2 ~ 6 by carbon number of the hydrogen atom of this amino replaces.
As [δ] compound, be preferably two (4-aminophenyl) HFC-236fa of 2,2-, two (4-aminophenyl) succinonitrile of 2,3-, 4,4 '-diaminobenzophenone, 4,4 '-diaminobenzoic acid phenyl ester, 4,4 '-diamino diphenyl sulfone, Isosorbide-5-Nitrae-diamido-2-chlorobenzene, Isosorbide-5-Nitrae-diamido-2-bromobenzene, Isosorbide-5-Nitrae-diamido-2-iodobenzene, Isosorbide-5-Nitrae-diamido-2-nitrobenzene, Isosorbide-5-Nitrae-diamido-2-trifluoromethylbenzene, 2,5-diamido 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) biphenylamine, 3-amino phenyl sulfonyl acetoacetic ester, 3,5-bis trifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline, is more preferably 4,4 '-diamino diphenyl sulfone, two (4-aminophenyl) HFC-236fa of 2,2-, 2,2 '-bis-(trifluoromethyl) biphenylamine, 3-amino phenyl sulfonyl acetoacetic ester, 3,5-bis trifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline.
Proportional as containing of [δ] compound in the 2nd radiation-sensitive resin composition, for [α] compound 100 mass parts, be preferably 0.1 mass parts ~ 20 mass parts, be more preferably 0.2 mass parts ~ 10 mass parts.By make [δ] compound containing proportional be 0.1 mass parts ~ 10 mass parts, can realize the distance piece formed by the 2nd radiation-sensitive resin composition sclerosis promote.And, the storage stability of the 2nd radiation-sensitive resin composition is improved, the voltage retention of the liquid crystal display cells comprising colored filter (the rewarding distance piece of described colored filter tool) can be kept in addition with high level.
Other any composition > of <
The 2nd radiation-sensitive resin composition used in the formation of the distance piece of the colored filter of this example, also can optionally containing [ω-1] the then composition arbitrarily such as auxiliary agent, [ω-2] surfactant, [ω-3] preserving stabilizer and [ω-4] thermotolerance promoter in the scope not undermining desired effect except above-mentioned [α] compound, [β] polymerizable compound, [γ] polymerization initiator and [δ] compound.Those each any compositions can be used alone and also can be mixed with two or more.Below, described in detail in turn.
[[ω-1] then auxiliary agent]
[ω-1] then auxiliary agent can improve further in order to the adherence of the distance piece and substrate that make gained.This kind [ω-1] then auxiliary agent can use the compound identical with the then auxiliary agent in other any compositions of above-mentioned colored composition.
As the use amount of [ω-1] then auxiliary agent, for [α] compound 100 mass parts, be preferably below 20 mass parts, be more preferably below 15 mass parts.If the use amount of [ω-1] then auxiliary agent is more than 20 mass parts, then exists to become and easily produce the residual tendency of development.
[[ω-2] surfactant]
[ω-2] surfactant can improve further in order to make the film formative of the 2nd radiation-sensitive resin composition.[ω-2] surfactant such as can enumerate 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.
As the use amount of [ω-2] surfactant, for [α] compound 100 mass parts, be preferably below 1.0 mass parts, be more preferably below 0.8 mass parts.If the use amount of [ω-2] surfactant is more than 1.0 mass parts, then becomes and easily produce film inequality.
[[ω-3] preserving stabilizer]
[ω-3] preserving stabilizer can use the compound identical with the preserving stabilizer in other any compositions of above-mentioned colored composition.Include, for example sulphur, quinones, hydroquinone type, polyoxy compounds, amine, nitro nitroso compound etc., more specifically can enumerate 4-metoxyphenol, N-nitroso--N-Phenylhydroxylamine aluminium etc.
As the use amount of [ω-3] preserving stabilizer, for [α] compound 100 mass parts, be preferably below 3.0 mass parts, be more preferably below 1.0 mass parts.If the allotment amount of [J-3] preserving stabilizer is more than 3.0 mass parts, then the light sensitivity that there is the 2nd radiation-sensitive resin composition reduces and causes the situation of pattern form deterioration.
[[ω-4] thermotolerance promoter]
[ω-4] thermotolerance promoter can be set to the compound identical with the heat-resisting stabilizing agent in other any compositions of above-mentioned colored composition.
As the use amount of [ω-4] thermotolerance promoter, for [α] compound 100 mass parts, be preferably below 50 mass parts, be more preferably below 30 mass parts.If the allotment amount of [ω-4] thermotolerance promoter is more than 50 mass parts, then the light sensitivity that there is the 2nd radiation-sensitive resin composition reduces and causes the situation of pattern form deterioration.
The modulation > of < the 2nd radiation-sensitive resin composition
2nd radiation-sensitive resin composition of the distance piece that the colored filter forming this example has can be modulated in the following way: by [α] compound, [β] polymerizable compound, [γ] polymerization initiator and [δ] compound, and any composition is optionally mixed with predetermined ratio in the scope not undermining desired effect.2nd radiation-sensitive resin composition is preferably dissolved in suitable solvent and uses under solution state.
The solvent used in the modulation of the 2nd radiation-sensitive resin composition can use and can dissolve or disperse [α] compound, [β] polymerizable compound, [γ] polymerization initiator, [δ] compound and any composition equably and the solvent do not reacted with each composition.Solvent and illustrative solvent that this kind of solvent can be enumerated to use in the modulation of the colored composition of the colored filter as above-mentioned example.Solvent can be used alone or two or more is used in combination.
As the solvent of the 2nd radiation-sensitive resin composition, when also using the situation of high boiling solvent, its use amount is preferably below 50 quality % for total solvent amount, is more preferably below 40 quality %, is particularly preferably below 30 quality %.When the use amount of high boiling solvent is below 50 quality %, the thickness homogeneity of film, light sensitivity 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 according to the value of application target or desired thickness etc.Solid concentration such as can be set as 5 quality % ~ 50 quality %.As preferred solid concentration, because forming the formation method of film and different on substrate, later it is described.About like this constituent solution of modulation, aperture can be used to be, after the millipore filter etc. of about 0.5 μm filters, be supplied to use.
2nd radiation-sensitive resin composition of above composition and modulator approach can utilize hardening at subcritical temerature and form 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, can hardening at subcritical temerature be utilized and the colored filter of this example is provided.
The colored filter of this example the face of liquid crystal side as described above when forming liquid crystal display cells can arrange LCD alignment alignment film.Alignment film can use the crystal aligning agent that comprises the radioactivity-sensitive polymkeric substance with light regiospecific base or comprise do not have light regiospecific base polyimide crystal aligning agent and obtain.In this case, become and can form alignment film under the heating-up temperature below 200 DEG C.Secondly, crystal aligning agent, particularly its principal ingredient of forming alignment film are illustrated.
< crystal aligning agent >
The crystal aligning agent of the alignment film that the colored filter forming this example has is as described above containing having [L] radioactivity-sensitive polymkeric substance of light regiospecific base or not having [M] polyimide of light regiospecific base as principal ingredient.The crystal aligning agent of the alignment film that the colored filter particularly forming this example has is preferably containing [L] radioactivity-sensitive polymkeric substance 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 only otherwise undermine effect of the present invention, then crystal aligning agent can contain [N] other compositions.Below those compositions are illustrated.
[[L] radioactivity-sensitive polymkeric substance]
Forming [L] radioactivity-sensitive polymkeric substance contained in the crystal aligning agent of the alignment film of the colored filter of this example is the polymkeric substance with light regiospecific base.The light regiospecific base that this [L] radioactivity-sensitive polymkeric substance has is penetrated by illumination and gives film anisotropic functional group, in this example, particularly give film anisotropic base by producing the person at least arbitrarily of photoisomerization reaction and light dimerization reaction.
As light regiospecific base, specifically for having the base of the structure being derived from least a kind of compound being selected from the group be made up of azobenzene, stilbene, alpha-imino-'beta '-ketoester, spiro-pyrans, Luo oxazine, cinnamic acid, chalcone, stilbene azoles, benzylidene phthalimide, cumarin, dibenzenyl and anthracene.As above-mentioned smooth regiospecific base, particularly preferably there is in those base of the structure being derived from cinnamic acid.
As [L] radioactivity-sensitive polymkeric substance with light regiospecific base, be preferably above-mentioned smooth regiospecific base directly or via the polymkeric substance of concatenating group bond.This kind of polymkeric substance include, for example: on the polymkeric substance at least arbitrarily of polyamic acid and polyimide, bond has the polymkeric substance of above-mentioned smooth regiospecific base; On the polymkeric substance different from polyamic acid and polyimide, bond has the polymkeric substance of above-mentioned smooth regiospecific base.When the situation of the latter, the basic framework with the polymkeric substance of light regiospecific base include, for example poly-(methyl) acrylate, poly-(methyl) acrylamide, polyvinylether, polyolefin, polysiloxane etc.
As radioactivity-sensitive polymkeric substance, preferably with the radioactivity-sensitive polymkeric substance that polyamic acid, polyimide or polysiloxane are basic framework.Such as, and particularly preferably polysiloxane in those, obtains by method described in International Publication (WO) No. 2009/025386 instructions.
[[M] polyimide]
Forming in the crystal aligning agent of the alignment film of the colored filter of this example contained [M] polyimide is do not have a polyimide of light regiospecific base.
This kind does not have [M] polyimide of light regiospecific base by making not have the polyamic acid dehydration closed-loop of light regiospecific base and carrying out imidizate and obtain.This kind of polyamic acid such as obtains by making tetracarboxylic dianhydride and diamine reactant, can obtain as described in Japanese Patent Laid-Open 2010-97188 publication.
[M] polyimide can be the complete acid imide compound of the amic acid structure fully dehydrating closed loop had as the polyamic acid of its presoma, also can be only a part of dehydration closed-loop of amic acid structure, amic acid structure and imide ring structure and the part acid imide compound of depositing.[M] polyimide preferably its acid imide rate is more than 30%, is more preferably 50% ~ 99%, is more preferably 65% ~ 99% further.This acid imide rate represents that imide ring structure number is relative to the ratio shared by the amic acid structure number of polyimide and the total of imide ring structure number with percent.Herein, a part for imide ring also can be different imide ring, such as, can obtain as described in Japanese Patent Laid-Open 2010-97188 publication.
[[N] other compositions]
Formed the alignment film of the colored filter of this example crystal aligning agent can containing have light regiospecific base radioactivity-sensitive polymkeric substance and do not have light regiospecific base polyimide beyond [N] other compositions.[N] other compositions include, for example polymkeric substance, rigidizer, hardening catalyst, hardening accelerator, epoxy compound, functional silanes compound, surfactant, photosensitizer etc. beyond [L] the radioactivity-sensitive polymkeric substance with light regiospecific base and [M] polyimide of not having light regiospecific base.
< colored pattern, diaphragm, distance piece, colored filter and those manufacture method >
In the manufacture of the colored filter of this example, comprise the steps as main manufacturing step: in order to formed by above-mentioned colored composition colored pattern step, in order to formed by above-mentioned 1st radiation-sensitive resin composition diaphragm step, in order to be formed the step of distance piece by above-mentioned 2nd radiation-sensitive resin composition.Below, colored pattern, diaphragm, distance piece, colored filter and those manufacture method are illustrated.
Preferably the manufacture method of the colored filter of this example comprises following step [1] ~ step [11] with following order:
[1] formed on substrate the step (hereinafter sometimes referred to " [1] step ") of colored composition film,
[2] formed on colored composition film the step (hereinafter sometimes referred to " [2] step ") of colored pattern,
The step (hereinafter sometimes referred to " [3] step ") of [3] below 200 DEG C, the film being formed with colored pattern being hardened,
[4] on the substrate after [3] step formed the 1st radiation-sensitive resin composition film step (hereinafter sometimes referred to " [4] step "),
[5] to the step (hereinafter sometimes referred to " [5] step ") of irradiating radioactive ray at least partially of the 1st radiation-sensitive resin composition film on this substrate,
The step (hereinafter sometimes referred to " [6] step ") of [6] film irradiating radioactive ray being developed,
The step (hereinafter sometimes referred to " [7] step ") of [7] below 200 DEG C, the film developed being hardened,
[8] on the substrate with the film hardened in [7] step formed the 2nd radiation-sensitive resin composition film step (hereinafter sometimes referred to " [8] step "),
[9] to the step (hereinafter sometimes referred to " [9] step ") of irradiating radioactive ray at least partially of the 2nd radiation-sensitive resin composition film formed in [8] step,
The step (hereinafter sometimes referred to " [10] step ") of [10] film irradiating radioactive ray being developed,
[11] below 200 DEG C, the film developed is made to harden and form the step (hereinafter sometimes referred to " [11] step ") of distance piece.
And, when the colored filter of this example has the situation of LCD alignment alignment film, the step (hereinafter sometimes referred to " [12] step ") that [12] form alignment film can also be set after [11] step.
By the manufacture method of the colored filter of this example above; above-mentioned colored composition can be used and on substrate, form colored pattern; use above-mentioned 1st radiation-sensitive resin composition and form diaphragm, use above-mentioned 2nd radiation-sensitive resin composition and form distance piece.And, when the colored filter of this example has the situation of alignment film, above-mentioned crystal aligning agent can be used and form alignment film.Its result, can form the colored filter that thermotolerance, chemical-resistant, voltage retention etc. are good.In such cases, hardening at subcritical temerature can be realized.In above-mentioned [3] step, above-mentioned [7] step and above-mentioned [11] step, can harden under the temperature respectively below 200 DEG C.Therefore, the dyestuff that there is problem in thermotolerance can be used in and as colorant in above-mentioned colored composition.Therefore, the colored filter of color characteristics excellence can be manufactured.In addition, in above-mentioned [12] step, also can carry out the formation of alignment film under the heating-up temperature below 200 DEG C.And, consider from energy-conservation viewpoint, as mentioned above and the colored filter manufactured also becomes suitable colored filter when expecting hardening at subcritical temerature.Below, 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 light shield layer (black matrix") is formed in the mode dividing the part forming pixel.Secondly, be coated with the colored composition such as containing red [IV] colorant on the substrate, then carry out preliminary drying and solvent is evaporated, thus form film.The additive method that substrate is formed colored pattern can adopt disclose in Japanese Patent Laid-Open 7-318723 publication and Japanese Patent Laid-Open 2000-310706 publication etc. utilize ink-jetting style and obtain the method for each color pixel.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 formed dividing plate by the colored composition such as containing red stain, then carry out preliminary drying and solvent is evaporated.Secondly, optionally this film exposed and form red pattern of pixels.In addition, aforementioned barriers not only plays shade function, and the function of the colored composition playing to make the colors be ejected in partition not colour mixture, and Comparatively speaking thickness is thicker with above-mentioned black matrix".
The material of substrate include, for example the ring-opening polymerization polymer and hydride etc. thereof of the glass such as soda-lime glass or alkali-free glass, quartz, silicon, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, aromatic polyamide, polyamidoimide, polyimide, cyclic olefin.And, also optionally can implement to utilize to those substrates the pre-service that the chemicals treatment, Cement Composite Treated by Plasma, ion plating, sputtering, gas-phase reaction method, vacuum evaporation etc. of silane coupling agent etc. are suitable in advance.
As the method be coated on by colored composition on substrate, except above-mentioned ink-jetting style, also can enumerate spray-on process, rolling method, method of spin coating (spin-coating method), slit die rubbing method, bar type rubbing method etc.Preferred spin-coating method, slit die rubbing method in those methods.Preferably combine by by drying under reduced pressure and heat drying and carry out preliminary drying.When carrying out the situation of drying under reduced pressure, usually carry out in the mode arriving 50Pa ~ 200Pa.And the condition of heat drying is normally 1 minute ~ about 10 minutes at 70 DEG C ~ 110 DEG C.
Dried thickness is generally 0.6 μm ~ 8.0 μm, is preferably 1.2 μm ~ 5.0 μm.
[[2] step]
In [2] step, be situated between and every photomask, the film formed in [1] step exposed, use alkaline-based developer and developing, dissolve the unexposed portion of removing film, the arrangement that specifies can be obtained by this and be configured with the red colored pattern of red pattern of pixels.
Secondly, use each colored composition of green or blueness, repeatedly carry out above-mentioned [1] step and [2] step and sequentially form green coloring pattern and blue-colored pattern on the same substrate.Obtain the colored filter being configured with redness, green and blue three primary colors colored pattern on substrate therefrom.Wherein, in this example, 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" is formed by utilizing photoetching process that the metallic film of the chromium formed by sputter or evaporation etc. is made desired pattern, uses the colored composition containing black colorant and is formed in the same manner as the situation of the formation of above-mentioned colored pattern.
The light source of radioactive ray include, for example the LASER Light Source etc. such as lamp source or Argon ion laser, YAG laser, XeCl quasi-molecule laser, nitrogen laser such as xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, Metal halogen lamp, middle medium pressure mercury lamp, Cooper-Hewitt lamp.Optimal wavelength is in the radioactive ray of the scope of 190nm ~ 450nm.The exposure of radioactive ray is preferably 10J/m 2~ 10,000J/m 2.
Alkali compounds contained in alkaline-based developer preferably selects sodium carbonate, NaOH, potassium hydroxide, Tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecylene, 1,5-diazabicyclo-[4.3.0]-5-nonene etc.The such as water-miscible organic solvent such as methyl alcohol, ethanol or surfactant etc. can be added in right amount in alkaline-based developer.In addition, after the development using alkaline-based developer, wash in normal circumstances.The method of development treatment can be applied spray (development) method, injection (development) method, dipping (development) method, cover liquid (development) method etc.Development conditions is preferably 5 seconds ~ 300 seconds at normal temperatures.
[[3] step]
Form colored pattern in [2] step after, by carrying out hardening (being also called rear baking), colored pattern is hardened, thus the formation of colored pattern can be made to terminate.The heating condition of rear baking can be set to less than 200 DEG C.The heat time of rear baking is 10 minutes ~ 60 minutes.In this example, drying temperature even if rear is low temperature, also can obtain the colored pattern that solvent resistance etc. is good.Specifically, dry temperature even if rear and be less than 200 DEG C, be less than 180 DEG C further, also can obtain the colored filter with sufficient solvent resistance etc.The thickness of colored pattern is preferably 0.5 μm ~ 5.0 μm, is more preferably 1.0 μm ~ 3.0 μm.In addition, in order to make hardness etc. be increased in fact commercial required level, usually must for the cure step at the temperature more than 120 DEG C.And, in the scope below 180 DEG C, preferably sclerosis at a higher temperature.Therefore, hardening temperature is such as preferably 150 DEG C ~ 180 DEG C.
[[4] step]
After forming colored pattern, the film colored pattern on the substrate of colored pattern being formed the 1st radiation-sensitive resin composition is being defined at this by [3] step.
When forming the situation of film utilizing rubbing method, after the substrate defining colored pattern is coated with the 1st radiation-sensitive resin composition solution, preferably coated face is heated (preliminary drying), can film be formed thus.The solid concentration of the constituent solution used in rubbing method is preferably 5 quality % ~ 50 quality %, is more preferably 10 quality % ~ 40 quality %, is particularly preferably 15 quality % ~ 35 quality %.The coating process of the 1st radiation-sensitive resin composition solution such as can adopt the method that spray-on process, 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.Preferred spin-coating method or slot coated method in those methods.
In addition, the 1st radiation-sensitive resin composition of this example contains mentioned component and forms, and carries out high-speed coating with can there is no crawling, therefore can adopt nozzle-type rubbing method.In [4] step when using nozzle-type rubbing method, for the substrate being formed with colored pattern, one side makes nozzle and this substrate relativity move coated on one side the 1st radiation-sensitive resin composition, and it is less preferred carries out preliminary drying to coated face, forms film therefrom.Utilize nozzle-type rubbing method, the 1st radiation-sensitive resin composition can be there is no and be coated on substrate lavishly equably.
[4] the preliminary drying condition in step is different because of the kind, allotment ratio etc. of each composition, preferably 70 DEG C ~ 120 DEG C, 1 minute ~ about 15 minutes.The pre-baked thickness of film is preferably 0.5 μm ~ 10 μm, is more preferably 1.0 μm ~ about 7.0 μm.
[[5] step]
Secondly, to the radioactive ray of irradiation at least partially of the film formed in [4] step.Now, when the patterning of required film, when only a part for film being irradiated, such as, can utilize the method being situated between and irradiating every the photomask and carrying out with predetermined pattern.
The radioactive ray used in irradiation can enumerate luminous ray, ultraviolet, far ultraviolet etc.Wherein optimal wavelength is in the radioactive ray of the scope of 190nm ~ 450nm, more preferably comprises the ultraviolet radioactive ray of 365nm.
Radiation exposure amount (exposure) is the value utilizing illuminometer (OAImodel356, OpticalAssociatesInc. manufacture) and measure the intensity under the wavelength 365nm of the radioactive ray irradiated, preferred 500J/m 2~ 10,000J/m 2, more preferably 1,500J/m 2~ 7,000J/m 2.
[[6] step]
Secondly, by developing to the film after radiation exposure, removing unnecessary part (non-irradiation unit of radioactive ray is divided), forming the pattern of regulation.This step is must implement during the situation of patterning of film.
The preferred alkaline aqueous solution of the developer solution used in development.In developer solution, spendable alkali compounds include, for example the inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia; The quaternary ammonium salt such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide etc.
And, also can add the water-miscible organic solvents such as the methyl alcohol of appropriate amount, ethanol or surfactant in this kind of alkaline aqueous solution and use.Consider from the viewpoint obtaining suitable developability, the alkali concn in alkaline aqueous solution is preferably below more than 0.1 quality % 5 quality %.The method that developing method such as can utilize liquid method of covering, infusion process, (shake) infusion process, spray process etc. is suitable for.Development time is different because of the composition of the 1st radiation-sensitive resin composition, is preferably 10 seconds ~ about 180 seconds.After this kind of development treatment, such as carry out 30 seconds ~ 90 seconds flowing water cleaning after, such as by carry out with pressurized air or compressed nitrogen air-dry and formed desired by pattern.
[[7] step]
Secondly, use the heating arrangement such as hot plate, baking oven, the film of gained is heated, promote the sclerous reaction of the 1st radiation-sensitive resin composition therefrom, form diaphragm as cured film.[7] hardening temperature in step is preferably less than 200 DEG C.And, even less than 180 DEG C also can obtain the diaphragm with sufficient characteristic.Specifically be preferably 100 DEG C ~ 200 DEG C, when situation for taking into account hardening at subcritical temerature and unfailing performance with high level, be more preferably 120 DEG C ~ 180 DEG C.The heat hardening time is different because of the kind of heating arrangement, such as, can be set to 5 minutes ~ 30 minutes when carrying out heating steps on hot plate, can be set to 30 minutes ~ 90 minutes when carrying out heating steps in an oven.In addition, the substep baking etc. carrying out more than 2 times heating stepses can also be used.
1st radiation-sensitive resin composition contains mentioned component and forms, and can realize this kind sclerosis at low temperatures.And, there is sufficient resolution and radioactive ray light sensitivity.Therefore, when in order to use dyestuff and the colored pattern ideal with hardening at subcritical temerature to combine and form the situation of diaphragm, the 1st radiation-sensitive resin composition can be used as the formation material of this diaphragm aptly.
In the manufacture of the colored filter of this example, after [7] step forming diaphragm, be included in the step this diaphragm being formed transparency electrode.Transparency electrode can select ITO electrode.The method forming ITO electrode can use sputtering method form ito film and carry out.As the ITO electrode of patterning, photoetching process can be utilized in the case of necessary to carry out patterning to formed ito film and formed.
[[8] step]
Form diaphragm by [7] step, on this diaphragm, form ITO electrode thereafter, the ITO electrode then on the substrate being formed with this diaphragm is formed the film of the 2nd radiation-sensitive resin composition.
When forming the situation of film utilizing rubbing method, after the substrate defining colored pattern etc. is coated with the 2nd radiation-sensitive resin composition solution, preferably coated face is heated (preliminary drying), can film be formed thus.The solid concentration of the constituent solution used in rubbing method is preferably 5 quality % ~ 50 quality %, is more preferably 10 quality % ~ 40 quality %, is particularly preferably 15 quality % ~ 35 quality %.The coating process of the 2nd radiation-sensitive resin composition solution such as can adopt the method that spray-on process, 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.Preferred spin-coating method or slot coated method in those methods.
Above-mentioned preliminary drying condition is different because of the kind, allotment ratio etc. of each composition, preferably 70 DEG C ~ 120 DEG C, 1 minute ~ about 15 minutes.The pre-baked thickness of film is preferably 0.5 μm ~ 10 μm, is more preferably 1.0 μm ~ about 7.0 μm.
[[9] step]
Secondly, to the radioactive ray of irradiation at least partially of the film formed in [8] step.Now, in order to form distance piece in desired position, radioactive ray are irradiated to the part of film, such as, can utilize the method being situated between and irradiating every the photomask and carrying out with predetermined pattern.The radioactive ray used in irradiation can enumerate luminous ray, ultraviolet, far ultraviolet etc.Wherein optimal wavelength is in the radioactive ray of the scope of 250nm ~ 550nm, more preferably comprises the ultraviolet radioactive ray of 365nm.
Radiation exposure amount (exposure) is the value utilizing illuminometer (OAImodel356, OpticalAssociatesInc. manufacture) and measure the intensity under the wavelength 365nm of the radioactive ray irradiated, preferred 100J/m 2~ 5,000J/m 2, more preferably 200J/m 2~ 3,000J/m 2.
The distance piece of the colored filter of this example forms middle the 2nd used radiation-sensitive resin composition and has following advantage: Comparatively speaking radioactive ray light sensitivity is higher for the constituent formed with previously known distance piece.Therefore, even if be 700J/m in above-mentioned radiation exposure amount 2below, be 600J/m further 2time 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, by developing to the film after radiation exposure, removing unnecessary part, forming the pattern of the distance piece of regulation.
The developer solution used in development such as can use the inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, the aqueous solution of the alkali compounds such as the quaternary ammonium salt such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide.Also can add the water-miscible organic solvent such as methyl alcohol, ethanol of appropriate amount in the aqueous solution of above-mentioned alkali compounds and use.In 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 use.
Developing method can be any one that cover liquid method, infusion process, spray process etc., and development time is preferably 10 seconds ~ about 180 seconds at normal temperatures.After development treatment, such as, carry out the flowing water cleaning of 30 seconds ~ 90 seconds, then carry out air-dry with pressurized air or compressed nitrogen, obtain the pattern of desired distance piece therefrom.
[[11] step]
Secondly, hardened by the pattern-like film of heating arrangement to gained utilizing hot plate, baking oven etc. suitable, 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 be preferably 100 DEG C ~ 200 DEG C, when situation for taking into account hardening at subcritical temerature and unfailing performance with high level, be more preferably 150 DEG C ~ 180 DEG C.As firm time, such as, on hot plate, be preferably 5 minutes ~ 30 minutes, be preferably 30 minutes ~ 180 minutes in an oven.
2nd radiation-sensitive resin composition containing [δ] compound, therefore can realize sclerosis at low temperatures as described above as described above.And, can storage stability be realized, and there is sufficient resolution and radioactive ray light sensitivity.Therefore, when using the situation of distance piece the colored pattern ideal with hardening at subcritical temerature combines in order to use dyestuff, the 2nd radiation-sensitive resin composition can be used as the formation material of this distance piece aptly.
According to above manufacture method, colored pattern, diaphragm and distance piece can be manufactured, and the colored filter of this example can be manufactured.As mentioned above, the colored pattern of the colored filter of this example is coated by colored composition on suitable substrate and after carrying out patterning, carries out hardening and being formed.Diaphragm is at coating the 1st radiation-sensitive resin composition similarly and after carrying out patterning, carries out hardening and being formed.Distance piece is at coating the 2nd radiation-sensitive resin composition similarly and after carrying out patterning, carries out hardening and being formed.And colored composition, the 1st radiation-sensitive resin composition and the 2nd radiation-sensitive resin composition all can utilize the hardening at subcritical temerature of less than 200 DEG C and form colored pattern or diaphragm or distance piece.
Therefore, in the colored filter of this example, can hardening at subcritical temerature be utilized and manufacture.
And, in the colored filter of this example, after formation colored pattern, form diaphragm.Diaphragm can utilize the hardening at subcritical temerature of less than 200 DEG C and be formed, under the state that therefore colored pattern is not exposed to the high-temperature heating forming diaphragm after its formation.Similarly, in the colored filter of this example, after formation colored pattern, form distance piece.Distance piece can utilize the hardening at subcritical temerature of less than 200 DEG C and be formed, under the state that therefore colored pattern is not exposed to the high-temperature heating forming distance piece after its formation.Therefore, even if although use color characteristics excellence in-problem dyestuff in thermotolerance as colorant, also can lower step deterioration.
In addition, during formation colored pattern when manufacturing the colored filter of this example, the diaphragm can considering thereafter is formed or distance piece is formed and adjusts hardening temperature.That is, utilize the hardening temperature Comparatively speaking lower with the hardening temperature being most suitable for being formed separately colored pattern on substrate and form colored pattern.Thereafter, also can be heated colored pattern by the sclerosis heating of the sclerosis heating of diaphragm that colored pattern is formed or distance piece.
Such as, be respectively less than 200 DEG C in the optimum hardening temperature of colored pattern and diaphragm and distance piece, when being specifically 180 DEG C, colored pattern can be formed by the hardening temperature lower than 180 DEG C.In this case, colored pattern can be pre-formed by the hardening temperature of such as 150 DEG C.Secondly, this colored pattern is formed the film of the 1st radiation-sensitive resin composition, carries out hardening at optimum 180 DEG C and form diaphragm.Its result, the colored pattern being formed in its lower floor is also heated, and becomes the colored filter that can obtain and comprise the colored pattern of desired state and this example of diaphragm.And, such as under the hardening temperature of 150 DEG C, be pre-formed colored pattern and diaphragm respectively, can under the hardening temperature of optimum 180 DEG C, use the 2nd radiation-sensitive resin composition and form distance piece thereafter.Its result, also heats colored pattern formed before and diaphragm, thus can obtain the colored filter comprising the colored pattern of desired state and this example of diaphragm and distance piece.
[[12] step]
Secondly, in the autofrettage of the colored filter of this example, the step that [12] form alignment film can be set after [11] step as described above.And, can arrange in the colored filter of this example and there is LCD alignment ability and the alignment film that can control the orientation of liquid crystal.
Above-mentioned crystal aligning agent is used in [12] step.And; be formed on the substrate of colored pattern and diaphragm and distance piece by above-mentioned [1] step ~ [11] step, utilizing suitable coating process such as such as rolling method, spinner method, print process, ink-jet method etc. and be coated with above-mentioned crystal aligning agent.Secondly, preliminary drying is carried out to the substrate being coated with crystal aligning agent, carries out rear baking thereafter, form film therefrom.Preliminary drying condition is preferably 0.1 minute ~ 5 minutes at 40 DEG C ~ 120 DEG C.As rear baking condition, such as temperature is 120 DEG C ~ 230 DEG C, and be preferably 150 DEG C ~ 200 DEG C, be more preferably 150 DEG C ~ 180 DEG C, the time is preferably 5 minutes ~ 200 minutes, is more preferably 10 minutes ~ 100 minutes.The thickness of the film after rear baking is preferably 0.001 μm ~ 1 μm, is more preferably 0.005 μm ~ 0.5 μm.
The solid concentration of the crystal aligning agent used when being coated on substrate by crystal aligning agent (ratio that the total weight of the composition beyond the desolventizing of crystal aligning agent is shared in the general assembly (TW) of crystal aligning agent) can be considered viscosity, volatility etc. and suitablely to select, and is preferably the scope of 1 % by weight ~ 10 % by weight.
When use comprises the situation of the crystal aligning agent of [L] radioactivity-sensitive polymkeric substance with light regiospecific base, give LCD alignment ability by irradiating linear polarization or the radioactive ray of part polarisation or the radioactive ray of non-polarized to above-mentioned film.The method of the orientation process that process so is previous with friction treatment etc. is corresponding, can carry out more easily.Herein, radioactive ray such as can use ultraviolet and the luminous ray of the wavelength light comprising 150nm ~ 800nm.Particularly preferably use the ultraviolet comprising the wavelength light of 300nm ~ 400nm as radioactive ray.
When the situation that used radioactive ray are linear polarization or part polarisation, irradiate and can carry out from the direction perpendicular to real estate, also can carry out giving tilt angle from tilted direction, and also those Combination of Methods can be carried out.When irradiating the situation of radioactive ray of non-polarized, direction of illumination is tilted direction necessarily.
The exposure of radioactive ray is preferably 1J/m 2above and less than 10,000J/m 2, be more preferably 10J/m 2~ 3,000J/m 2.
Use comprise do not have the situation of crystal aligning agent of [M] polyimide of light regiospecific base time, also the film after rear baking directly can be used as alignment film.And, also can optionally to the film embodiment after rear baking as the process (friction treatment) rubbed on fixed-direction with the roller being wound with the cloth comprising the fibers such as nylon, rayon, cotton, thus give LCD alignment ability.
As mentioned above, in the method for manufacturing colored filtering substrate of this example, above-mentioned crystal aligning agent can be used 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 of the colored filter formed in above-mentioned [1] step ~ [3] step can be avoided to be formed under the state being exposed to high temperature in [12] step of alignment film.
[example]
Below, Case-based Reasoning is described in detail example of the present invention, but does not carry out limited explanation with this example to the present invention.
Formation and the evaluation > of < colored pattern
Example 1
[synthesis of [I] alkali soluble resins (IA)]
2 are loaded, two (2,4-methyl pentane nitrile) 5 mass parts of 2 '-azo and diethylene glycol ethylmethyl ether 220 mass parts in the flask with condenser pipe and stirring machine.Secondly, methacrylic acid 18 mass parts of (I-1) compound is loaded as, as methacrylic acid-2-methylglycidyl esters 14 mass parts of (I-2) compound and glycidyl methacrylate 20 mass parts, styrene 10 mass parts as (I-4) compound, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester 23 mass parts and methyl methacrylate 15 mass parts, after carrying out nitrogen displacement, one side gently stirs one side makes the temperature of solution rise to 70 DEG C, keep this temperature 5 hours and be polymerized, obtaining containing the solution as the alkali soluble resins (IA) of multipolymer therefrom.The solid concentration of the polymer solution of gained is 31.5%, and the Mw as the alkali soluble resins (IA) of multipolymer is 10,100.
Example 2
[synthesis of [I] alkali soluble resins (IB)]
AIBN4 mass parts and diethylene glycol ethylmethyl ether 300 mass parts is loaded in the flask with condenser pipe and stirring machine, methacrylic acid 23 mass parts of next is loaded as (I-1) compound, as styrene 10 mass parts of (I-4) compound, benzyl methacrylate 32 mass parts and methyl methacrylate 35 mass parts, further loading α-methylstyrenedimer 2.7 mass parts, one side gently stirs one side makes the temperature of solution rise to 80 DEG C, this temperature is kept after 4 hours, to make it rise to 100 DEG C, keep this temperature 1 hour and be polymerized, obtain the solution containing multipolymer therefrom.The solid concentration of the polymer solution of gained is 24.9%, Mw is 12,500.Secondly, tetrabutyl ammonium bromide 1.1 mass parts, 4-metoxyphenol 0.05 mass parts as polymerization inhibitor is added in comprising in the solution of multipolymer of gained, stir under air ambient, at 90 DEG C after 30 minutes, put into glycidyl methacrylate 16 mass parts as (I-2) compound and keep 90 DEG C to make it react 10 hours, obtaining the alkali soluble resins (IB) as multipolymer therefrom.The solid concentration of the polymer solution of gained is 29.0%, Mw is 14,200.
Example 3
[modulation of colored composition]
Relative to gained in example 1 (IA) 90 mass parts of the alkali soluble resins as multipolymer and mix potpourri (KAYARAD (registered trademark) DPHA-40H of ethylene-oxide-modified dipentaerythritol acrylate (II-1) as [II] polymerizable compound and polyfunctional acrylic ester compound, chemical drug company of Japan) potpourri (mixture ratio ((II-1)/(II-2))=4) 100 mass parts of (II-2), as 2-methyl isophthalic acid-(4-methylthiophene base)-2-morpholino propane-1-ketone (Irgacure907 of [III] polymerization initiator, Ciba company limited) (III-1) 25 mass parts, as red stain (IV-1) 100 mass parts comprising orchil of [IV] colorant, as the pentaerythrite four (3-mercaptopropionic acid) ester (V-1) of [V] compound and potpourri (mixture ratio ((V-1)/(V-2)=5)) 6 mass parts of 3-amino phenyl sulfonyl acetoacetic ester (V-2), as alkali soluble resins (IB) 10 mass parts of gained in the example 2 of other alkali soluble resinss.Secondly, use cyclohexanone as solvent, after the mode becoming 30wt% adds solvent, utilize aperture to be that the millipore filter of 0.5 μm filters, modulated red chromatic colorant constituent therefrom with the solid concentration of colored composition.
Except using the green colourant (IV-2) comprising green colouring material as except [IV] colorant, carrying out as described above and modulating green coloring constituent.And, except using the blue colorant (IV-3) comprising blue dyes as except [IV] colorant, carrying out as described above and modulating blue-colored constituent.
Example 4
[formation of colored pattern]
Be formed with the SiO preventing sodion stripping from the teeth outwards 2on the soda-lime glass substrate of film, use spin coater and be coated with the red colored constituent of gained in example 3.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/m 2) exposure the radioactive ray of each wavelength of 365nm, 405nm and 436nm are comprised to film exposure.Thereafter, with developer pressure 1 (kgf/cm 2) (nozzle diameter is 1mm) and to those substrates ejection developer solution (the 0.04wt% potassium hydroxide aqueous solutions of 23 DEG C), carry out spray development therefrom, the formation colored pattern of 200 μm × 200 μm on substrate.At 180 DEG C, carry out the rear baking 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 the blue-colored constituent of gained is as colored composition in use-case 3, carries out in addition as described above and form blue colored pattern.
Example 5
[evaluation of colored pattern]
Following evaluation is carried out to manufactured colored pattern.
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 the thickness/development after development) × 100 before and after development.
The colored pattern of above-mentioned colors is all the Film Thickness Ratio before and after developing is more than 95%, and known have good resistance to developability.
The evaluation of thermotolerance
At 180 DEG C, heating 30 minutes are added further to the colored pattern of above-mentioned colors.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, known have good thermotolerance.
The evaluation of solvent resistance
About above-mentioned colored pattern, to be together immersed in the 1-METHYLPYRROLIDONE of 60 DEG C 30 minutes with substrate.Thereafter, observe the colored pattern of the colors on substrate, results verification remains colored pattern all after impregnating, and 1-METHYLPYRROLIDONE after dipping is completely not painted.The equal solvent resistance of known above-mentioned any colored pattern is good.
Formation and the evaluation > of < diaphragm
Example 6
[synthesis of [A] siloxane polymer]
Propylene glycol monomethyl ether 24 mass parts is entered at the container content with stirring machine, then load methyltrimethoxy silane 54 mass parts, tetraethoxysilane 30 mass parts, 3-acryloxypropyl trimethoxy silane 16 mass parts, carry out heating until solution temperature becomes 60 DEG C.After solution temperature arrives 60 DEG C, load formic acid 0.1 mass parts, ion exchange water 19 mass parts, keep 2 hours after being heated to 75 DEG C.After being cooled to 45 DEG C, add the stirring that trimethyl orthoformate 28 mass parts is carried out as dewatering agent 1 hour.Make solution temperature become 40 DEG C further, one side keeps temperature one side to evaporate, therefrom except the methyl alcohol anhydrated and produce due to hydrolytic condensation and ethanol.Hydrolytic condensate (A-I) (solid concentration=35 quality %, Mw=1,800, Mw/Mn=2.2) is obtained by operating above.
Example 7
[modulation of the 1st radiation-sensitive resin composition]
In the example 6 as [A] siloxane polymer, the middle mixing of the solution (being equivalent to the amount of hydrolytic condensate (A-I) 100 mass parts (solid content)) comprising hydrolytic condensate (A-I) of gained is as 2-methyl-[4-(methyl mercapto) phenyl]-2-morpholino-1-propane (Irgacure907 of [B] radical polymerization initiator, BASF AG) 5 mass parts, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone (Irgacure369, BASF AG) 2 mass parts, as the dipentaerythritol acrylate of [D] ethene unsaturated compound and potpourri (the mol ratio 50/50) (trade name: DPHA of Dipentaerythritol Pentaacrylate, chemical drug Inc. of Japan makes) 5 mass parts, isocyanuric acid EO modified triacrylate (trade name: ARONIX (registered trademark) M-313, East Asia Synesis Company manufactures) 15 mass parts, the mode becoming 25 quality % using solid concentration adds the propylene glycol monomethyl ether as [C] organic solvent and makes it dissolve, modulate the 1st radiation-sensitive resin composition.
Example 8
[formation of diaphragm]
Utilize after the 1st radiation-sensitive resin composition modulated in example 7 coats on alkali-free glass substrate by spinner, 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 exposure be 2,000J/m 2and radiation exposure is carried out to the film of gained.Secondly, in an oven, dry after carrying out under the condition of the firm time of the hardening temperatures of 180 DEG C and 30 minutes and form diaphragm.
Example 9
[evaluation of diaphragm]
The evaluation of storage stability
By the 1st radiation-sensitive resin composition of the example 7 after just modulating, form diaphragm by the formation method of example 8, measure thickness (being called in following formula " thickness just after modulation ").And, utilize the formation method of example 7 and after modulating, at 25 DEG C, preserve the 1st radiation-sensitive resin composition 5 days, similarly measuring the thickness (being called in following formula " thickness after 5 days ") of the diaphragm 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)/(thickness just after modulation) × 100
Thickness increment rate is less than 3%, thus judges that storage stability is good.
Sunproof evaluation
About the diaphragm of formation method gained utilizing example 8, use UV irradiation unit (UVX-02516S1JS01, UshioInc.) further and carry out 800,000J/m with the illumination of 130mW 2irradiation, check film reduction.Film reduction is less than 2%, thus judges that photostability is good.
The evaluation of thermotolerance
About the diaphragm of formation 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 thermotolerance.Residual film ratio is 99%, thus judges that thermotolerance is good.
The evaluation of chemical-resistant
About the diaphragm of formation method gained utilizing example 8; to heat to alignment film stripper CHEMICLEAN (registered trademark) TS-204 (Sanyo changes into industrial group) of 60 DEG C dipping 15 minutes; 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's 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 judges that chemical-resistant is good.
Formation and the evaluation > of < distance piece
Example 10
[synthesis of [α] compound]
2 are loaded, two (2,4-methyl pentane nitrile) 7 mass parts of 2 '-azo and diethylene glycol ethylmethyl ether 200 mass parts in the flask with condenser pipe and stirring machine.Secondly methacrylic acid 16 mass parts, methacrylic acid three ring [5.2.1.0 is loaded 2,6] decane-8-base ester 16 mass parts, methyl methacrylate 38 mass parts, styrene 10 mass parts, glycidyl methacrylate 20 mass parts, after carrying out nitrogen displacement, one side gently stirs one side makes the temperature of solution rise to 70 DEG C, this temperature kept 4 hours and be polymerized, obtain the solution (solid concentration=34.4 quality %, Mw=8,000, Mw/Mn=2.3) containing multipolymer (α-I) therefrom.In addition, solid concentration is the ratio representing that the quality of multipolymer is shared in the gross mass of copolymer solution.
Example 11
[modulation of the 2nd radiation-sensitive resin composition]
Relative to multipolymer (α-I) 100 mass parts of gained in the example 10 as [α] compound, mix dipentaerythritol acrylate (β-I) 100 mass parts as [β] polymerizable compound, as ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime) (Irgacure (registered trademark) OXE02 of [γ] polymerization initiator, Ciba company limited) (γ-I) 5 mass parts, and as 4 of [δ] compound, 4 '-diamino diphenyl sulfone (δ-I), further mixing is as γ-glycidoxypropyltrimewasxysilane 5 mass parts of [ω-1] then auxiliary agent, as the surfactant (FTX-218 of [ω-2] surfactant, Neos company) 0.5 mass parts, as 4-metoxyphenol 0.5 mass parts of [ω-3] preserving stabilizer, after the mode becoming 30 quality % with solid concentration adds propylene glycol methyl ether acetate, aperture is utilized to be that the millipore filter of 0.5 μm filters, modulate the 2nd radiation-sensitive resin composition therefrom.
Example 12
[formation of distance piece]
As the example forming distance piece, the example that substrate is only formed distance piece is illustrated.
On alkali-free glass substrate, use spin coater and be coated with the 2nd radiation-sensitive resin composition modulated in example 11.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 thus.Secondly, high-pressure mercury-vapor lamp is used to make exposure for 700J/m 2and radiation exposure is carried out to the film of gained.Thereafter, with developer pressure 1 (kgf/cm 2) (nozzle diameter is 1mm) and to this substrate ejection developer solution (the 0.04 quality % potassium hydroxide aqueous solutions of 23 DEG C), carry out therefrom spray develop, substrate is formed the pattern of distance piece.Secondly, carry out rear baking 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 13
[evaluation of distance piece]
About the distance piece of gained in example 12, observe section shape with sweep electron microscope.
The distance piece formed is all pattern edges is along wedge shape, and is good.
Secondly, on the distance piece formed on substrate in example 12, AL3046 (JSRCorporation manufacture) is coated with liquid crystal orienting film coating printing machine, at 180 DEG C, carry out the drying of 1 hour, formed dry film thickness be the alignment film of 0.05 μm film and as liquid crystal orienting film.Utilize and there is the strigil of the roller of the cloth being wound with nylon, the rotating speed of roller be 500rpm, the translational speed of platform carries out friction treatment to this film under being the condition of 1cm/sec.Now, in distance piece, do not produce and cut down or peel off.
The manufacture > of < colored filter
Example 14
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 being formed with black matrix pattern, on hot plate, at 90 DEG C, carry out the preliminary drying of 2 minutes and form film.Thereafter, be situated between every the pattern mask of regulation, use exposure machine CanonPLA501F (Canon Inc.) and irradiate in the conversion of i line for 1,000J/m 2the ghi line of exposure (wavelength is strength ratio=2.7 of 436nm, 405nm, 365nm: 2.5: 4.8), use 0.05% potassium hydroxide aqueous solution and develop, the flushing of 60 seconds is carried out in ultrapure water, then further in an oven, carry out the heating of 30 minutes at 180 DEG C, form the striped design (pattern width is 100 μm) that thickness is the redness of 2.0 μm.
Secondly, similarly operate, use green coloring constituent and form green striped design.The blue-colored constituent of further use and form blue striped design, forms 3 look striated colored filters (width of fringe is 100 μm) that are red, green and indigo plant.
Above-mentioned formed rear baking temperature be 180 DEG C, the problem such as the redness that formed under the condition of 30 minutes, green, 3 blue chromatic colorant patterns do not produce insufficient the caused pattern defect of sclerosis, peel off on substrate, the striped design of 3 looks can be formed.
Secondly, on the striped design of 3 looks of gained, be coated with the 1st radiation-sensitive resin composition illustrated in example 7 by slit die coating machine.Secondly, on hot plate, carry out the preliminary drying of 5 minutes at 90 DEG C and form film.Use high-pressure mercury-vapor lamp with 2,000J/m 2the pre-baked film of exposure to gained carry out radiation exposure; after using alkaline aqueous solution to develop; further in an oven, carry out the heating of 60 minutes at 180 DEG C, the thickness formed from the upper surface of 3 look striped design is the diaphragm of 2.0 μm.Carry out as described above and be manufactured on substrate colored pattern being formed with diaphragm.
About the substrate being formed with diaphragm on colored pattern of gained; use contact determining film thickness device α-Step (KLA-Tencor Japanese firm) and measure concavo-convex (flatness) on diaphragm surface (measured length is 2; 000 μm, measurement range be 2,000 μm square, measure and to count n=5).That is, make mensuration direction be the streak line short-axis direction in 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 mean value of 10 times of the highest portion of each mensuration and the difference of height (nm) of lowest part.Mean value is now 200nm.Even if after formation diaphragm, colored pattern does not also shrink, expansion, and diaphragm surface no concave-convex, demonstrates good flatness.
Secondly, about the substrate being formed with diaphragm on colored pattern of gained, use sputtering method to form ito film on diaphragm, thus form ITO electrode.
Secondly, in ITO electrode, the 2nd radiation-sensitive resin composition modulated in example 11 is coated 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 thus.Secondly, use high-pressure mercury-vapor lamp and make exposure for 700J/m 2and radiation exposure is carried out to the film of gained.Thereafter, with developer pressure 1 (kgf/cm 2) (nozzle diameter is 1mm) and to this substrate ejection developer solution (the 0.04 quality % potassium hydroxide aqueous solutions of 23 DEG C), carry out therefrom spray develop, substrate is formed the pattern of distance piece.Secondly, rear baking 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 is formed in the region corresponding with black matrix" forming region in ITO electrode.
Manufacture the colored filter of this example in the above-described manner.The colored filter of this manufactured example has excellent color characteristics.
Example 15
[there is the manufacture of the colored filter of light alignment film]
In this example, the colored filter of gained in use-case 14, use comprises the crystal aligning agent of the radioactivity-sensitive polymkeric substance with light regiospecific base and forms light alignment film.
First, in the colored filter of example 14, on the substrate being formed with distance piece, utilize spinner and be coated with crystal aligning agent A-1 described in the example 6 as No. 2009/025386, the International Publication (WO) of the crystal aligning agent comprising the radioactivity-sensitive polymkeric substance with light regiospecific base.Secondly, after the hot plate of 80 DEG C carries out the preliminary drying of 1 minute, in baking oven inside having been carried out to nitrogen displacement, at 180 DEG C, carry out the heating of 1 hour and form the film that thickness is 80nm.Secondly, use Hg-Xe lamp and Glan-Taylor prism, from the direction of inclination for the direction perpendicular to substrate surface 40 °, 200J/m is irradiated to this film coated surface 2the polarisation ultraviolet comprising the open-wire line of 313nm, and manufacture there is the colored filter of light alignment film.
Example 16
[there is the manufacture of the colored filter of vertical orientation film]
In this example, the colored filter of gained in use-case 14, use comprise do not have light regiospecific base polyimide crystal aligning agent and form vertical orientation film.
First, in the colored filter of example 14, on the substrate being formed with distance piece, utilize spinner and be coated with and do not have a vertical orientation film formation AL60101 (JSRCorporation manufacture) of crystal aligning agent of polyimide of light regiospecific base as comprising.Secondly, after the hot plate of 80 DEG C carries out the preliminary drying of 1 minute, in baking oven inside having been carried out to nitrogen displacement, at 180 DEG C, carry out the heating of 1 hour and form the film that thickness is 80nm, and manufacturing the colored filter with vertical orientation film.
The application > of < colored filter in liquid crystal display cells
Example 17
[manufacture of color liquid crystal display device]
In the manufacture of liquid crystal display cells, the colored filter with light alignment film of colored filter use-case 15.Driving substrate uses the driving substrate being formed with light alignment film with the method identical with example 15 on the substrate prepared according to known method.Those are combined and is manufactured color liquid crystal display device.Manufactured color liquid crystal display device is configured with Polarizer etc., and has the structure identical with the color liquid crystal display device shown in above-mentioned Fig. 2.The liquid crystal display cells of this example demonstrates the homogeneity of the height in the gap between the substrate clamping liquid crystal.And, realize the colour display of excellent color characteristics.
Utilizability in industry
Colored filter of the present invention can utilize hardening at subcritical temerature and manufacture, and has high reliability and color characteristics is excellent.Therefore, colored filter of the present invention can be used as and uses the flexible liquid crystal display colored filter of resin substrate or require the large-scale liquid crystal display television colored filter of high image quality and use aptly.

Claims (24)

1. a colored filter, is characterized in that, contains colored pattern, diaphragm,
Described colored pattern contains at least a kind of colorant being selected from the group be made up of diketopyrrolopyrroles pigment, zinc halide phthalocyanine pigment, triarylmethane class dye well azo dyes;
Described diaphragm is formed by the 1st radiation-sensitive resin composition containing, for example lower composition:
[A] siloxane polymer,
[B] radical polymerization initiator and
[C] organic solvent,
[A] siloxane polymer contained in described 1st radiation-sensitive resin composition is the hydrolytic condensate of hydrolysable silanes compound, and this hydrolysable silanes compound comprises:
(a1) the hydrolysable silanes compound represented by following formula (A-1), with
(a2) the hydrolysable silanes compound represented by following formula (A-2);
In formula (A-1), R 1to be carbon number be 1 ~ 6 alkyl; R 2it is the organic group comprising free-radical reactive functional group; P is the integer of 1 ~ 3; Wherein, R is worked as 1and R 2when becoming multiple situations, multiple R 1and R 2independently;
In formula (A-2), R 3to be carbon number be 1 ~ 6 alkyl; R 4hydrogen atom, the carbon number alkyl that is 1 ~ 20, carbon number be 1 ~ 20 fluorinated alkyl, phenyl, naphthyl, epoxy radicals, amino or isocyanate group; N is the integer of 0 ~ 20; Q is the integer of 0 ~ 3; Wherein, R is worked as 3and R 4when becoming multiple situations, multiple R 3and R 4independently.
2. colored filter according to claim 1, is characterized in that:
Comprise distance piece further, described distance piece is formed by the 2nd radiation-sensitive resin composition containing, for example lower composition:
[α] alkali soluble resins,
[β] have ethene unsaturated link polymerizable compound,
[γ] radioactivity-sensitive polymerization initiator and
[δ] is selected from least a kind of compound of the group that the compound represented by following formula (1) and the compound represented by following formula (2) are formed;
In formula (1), R 1~ R 6be independently hydrogen atom, electron-withdrawing group or amino; Wherein, R 1~ R 6in at least 1 be electron-withdrawing group, and R 1~ R 6in at least 1 be amino; And all or part of alkyl that can be also 1 ~ 6 by carbon number of the hydrogen atom of above-mentioned amino replaces;
In formula (2), R 7~ R 16be independently hydrogen atom, electron-withdrawing group or amino; Wherein, R 7~ R 16in at least 1 be amino; And all or part of alkyl that can be also 1 ~ 6 by carbon number of the hydrogen atom of above-mentioned amino replaces; A is singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number are 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.
3. colored filter according to claim 1, is characterized in that:
Described colored pattern is formed by the colored composition containing, for example lower composition:
[I] alkali soluble resins,
[II] have ethene unsaturated link polymerizable compound,
[III] radioactivity-sensitive polymerization initiator and
[IV] described colorant.
4. colored filter according to claim 3, is characterized in that:
At least a kind of compound of the group that described colored composition selects the compound represented by free style (1), compound represented by formula (2), tertiary amine compound, amine salt, phosphonium salt, amidine salt, amide compound, mercaptan compound, block isocyanate compound and the compound containing imidazole ring to form containing [V] further
In formula (1), R 1~ R 6be independently hydrogen atom, electron-withdrawing group or amino; Wherein, R 1~ R 6in at least 1 be electron-withdrawing group, and R 1~ R 6in at least 1 be amino; And all or part of alkyl that can be also 1 ~ 6 by carbon number of the hydrogen atom of above-mentioned amino replaces;
In formula (2), R 7~ R 16be independently hydrogen atom, electron-withdrawing group or amino; Wherein, R 7~ R 16in at least 1 be amino; And all or part of alkyl that can be also 1 ~ 6 by carbon number of the hydrogen atom of above-mentioned amino replaces; A is singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number are 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.
5. colored filter according to claim 3, is characterized in that:
[I] alkali soluble resins contained in described colored composition is the multipolymer comprising following structural unit: the structural unit that (I-1) is formed by the unsaturated compound containing epoxy radicals by least a kind that is selected from the group be made up of unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides structural unit formed, (I-2).
6. colored filter according to claim 1, is characterized in that:
Described 1st radiation-sensitive resin composition is further containing [D] ethene unsaturated compound except [A] siloxane polymer.
7. colored filter according to claim 1, is characterized in that:
Described 1st radiation-sensitive resin composition is further containing [E] radioactivity-sensitive acid agent or radioactivity-sensitive generated base alkaline agent.
8. colored filter according to claim 2, is characterized in that:
[α] alkali soluble resins contained in described 2nd radiation-sensitive resin composition is the multipolymer comprising following structural unit: the structural unit that (α-1) is formed by the unsaturated compound containing epoxy radicals by least a kind that is selected from the group be made up of unsaturated carboxylic acid and the unsaturated carboxylic acid anhydrides structural unit formed, (α-2).
9. colored filter according to claim 1, is characterized in that:
Described colored pattern is the colored pattern formed under the hardening temperature below 200 DEG C.
10. colored filter according to claim 1, is characterized in that:
Described diaphragm is the diaphragm formed under the hardening temperature below 200 DEG C.
11. colored filters according to claim 2, is characterized in that:
Described distance piece is the distance piece formed under the hardening temperature below 200 DEG C.
12. colored filters according to claim 1, is characterized in that:
Described colored pattern is the colored pattern formed under the hardening temperature lower than the hardening temperature of described diaphragm.
13. colored filters according to claim 2, is characterized in that:
Described colored pattern is the colored pattern formed under the hardening temperature lower than the hardening temperature of described distance piece.
14. colored filters according to claim 2, is characterized in that:
Described diaphragm is the diaphragm formed under the hardening temperature lower than the hardening temperature of described distance piece.
15. colored filters according to any one of claim 1 to 14, is characterized in that:
Comprise alignment film, described alignment film be use the crystal aligning agent and comprising comprising the radioactivity-sensitive polymkeric substance with light regiospecific base do not have light regiospecific base polyimide crystal aligning agent in the alignment film of any number of gained.
16. colored filters according to claim 15, is characterized in that:
Described alignment film uses the alignment film comprising the crystal aligning agent gained of the radioactivity-sensitive polymkeric substance with light regiospecific base.
17. 1 kinds of liquid crystal display cells, is characterized in that the colored filter comprised according to any one of claim 1 to 16.
The manufacture method of 18. 1 kinds of colored filters, is characterized in that comprising the steps:
[1] on substrate, form the step of the film of colored composition, described colored composition contains at least a kind of colorant being selected from the group be made up of diketopyrrolopyrroles pigment, zinc halide phthalocyanine pigment, triarylmethane class dye well azo dyes;
[2] on the film of described colored composition, form the step of colored pattern;
[3] below 200 DEG C to the step that the film being formed with described colored pattern hardens;
[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 composition:
[A] siloxane polymer,
[B] radical polymerization initiator and
[C] organic solvent,
[A] siloxane polymer contained in described 1st radiation-sensitive resin composition is the hydrolytic condensate of hydrolysable silanes compound, and this hydrolysable silanes compound comprises:
(a1) the hydrolysable silanes compound represented by following formula (A-1), with
(a2) the hydrolysable silanes compound represented by following formula (A-2);
In formula (A-1), R 1to be carbon number be 1 ~ 6 alkyl; R 2it is the organic group comprising free-radical reactive functional group; P is the integer of 1 ~ 3; Wherein, R is worked as 1and R 2when becoming multiple situations, multiple R 1and R 2independently;
In formula (A-2), R 3to be carbon number be 1 ~ 6 alkyl; R 4hydrogen atom, the carbon number alkyl that is 1 ~ 20, carbon number be 1 ~ 20 fluorinated alkyl, phenyl, naphthyl, epoxy radicals, amino or isocyanate group; N is the integer of 0 ~ 20; Q is the integer of 0 ~ 3; Wherein, R is worked as 3and R 4when becoming multiple situations, multiple R 3and R 4independently;
[5] to the step of irradiating radioactive ray at least partially of the film of described 1st radiation-sensitive resin composition;
[6] to the step that the described film having irradiated radioactive ray in step [5] develops;
[7] below 200 DEG C, make the step of the described film sclerosis of developing in step [6];
[8] on the substrate of the described film through sclerosis with step [7], form the step of the 2nd radiation-sensitive resin composition film, described 2nd radiation-sensitive resin composition is containing, for example lower composition:
[α] alkali soluble resins,
[β] have ethene unsaturated link polymerizable compound,
[γ] radioactivity-sensitive polymerization initiator and
[δ] is selected from least a kind of compound of the group that the compound represented by following formula (1) and the compound represented by following formula (2) are formed;
[9] to the step of irradiating radioactive ray at least partially of the film of described 2nd radiation-sensitive resin composition;
[10] to the step that the described film having irradiated radioactive ray in step [9] develops; And
[11] below 200 DEG C, the described film developed in step [10] is made to harden and form the step of distance piece;
In formula (1), R 1~ R 6be independently hydrogen atom, electron-withdrawing group or amino; Wherein, R 1~ R 6in at least 1 be electron-withdrawing group, and R 1~ R 6in at least 1 be amino; And all or part of alkyl that can be also 1 ~ 6 by carbon number of the hydrogen atom of above-mentioned amino replaces;
In formula (2), R 7~ R 16be independently hydrogen atom, electron-withdrawing group or amino; Wherein, R 7~ R 16in at least 1 be amino; And all or part of alkyl that can be also 1 ~ 6 by carbon number of the hydrogen atom of above-mentioned amino replaces; A is singly-bound, carbonyl, carbonyl oxygen base, carbonyl methylene, sulfinyl, sulfonyl, methylene or carbon number are 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.
The manufacture method of 19. colored filters according to claim 18, is characterized in that:
Described colored composition has polymerizable compound, [III] radioactivity-sensitive polymerization initiator of ethene unsaturated link further containing [I] alkali soluble resins, [II].
The manufacture method of 20. colored filters according to claim 18 or 19, is characterized in that:
The hardening temperature of described step [3] is the temperature lower than the hardening temperature of described step [7].
The manufacture method of 21. colored filters according to claim 18 or 19, is characterized in that:
The hardening temperature of described step [3] is the temperature lower than the hardening temperature of described step [11].
The manufacture method of 22. colored filters according to claim 18 or 19, is characterized in that:
The hardening temperature of described step [7] is the temperature lower than the hardening temperature of described step [11].
The manufacture method of 23. colored filters according to claim 18 or 19, is characterized in that:
The step that [12] form alignment film below 200 DEG C is comprised after described step [11].
The manufacture method of 24. colored filters according to claim 23, is characterized in that:
Described step [12] be use the crystal aligning agent and comprising comprising the radioactivity-sensitive polymkeric substance with light regiospecific base do not have light regiospecific base polyimide crystal aligning agent in any number of and form described alignment film.
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