CN101113224A - Colored resin composition, color filter, and liquid crystal display - Google Patents

Colored resin composition, color filter, and liquid crystal display Download PDF

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Publication number
CN101113224A
CN101113224A CNA2007101471878A CN200710147187A CN101113224A CN 101113224 A CN101113224 A CN 101113224A CN A2007101471878 A CNA2007101471878 A CN A2007101471878A CN 200710147187 A CN200710147187 A CN 200710147187A CN 101113224 A CN101113224 A CN 101113224A
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resin composition
colored resin
acid
methyl
weight
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CN101113224B (en
Inventor
迫直树
大畑达宽
谷川景子
鸣户俊也
田野冈久永
长尾卓美
川名真
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Mitsubishi Chemical Corp
Mitsubishi Rayon Co Ltd
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Mitsubishi Kasei Corp
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A coloring resin composition which has satisfactory transparency, is less apt to leave a coloring resin composition residue remaining undissolved in the nonimage areas on a substrate, and has excellent adhesion to the substrate. It is inhibited from generating foreign matters such as dried agglomerates in application by die coating and is capable of evenly forming color pixels with a high density. The coloring resin composition comprises a colorant, a solvent, a dispersant, and a binder resin, and is characterized in that the binder resin comprises a nitrogen-free binder resin having a structure formed by causing the epoxy group of an epoxidized unsaturated compound (b) to add to each of carboxy groups of a carboxylated resin (a) and the dispersant comprises a nitrogenous dispersant, the proportion of the nitrogenous dispersant to the colorant being 0.01 to 0.5 by weight.

Description

Colored resin composition, colour filter and liquid-crystal display
The application is that application number is 200480009124.0, the applying date is on January 16th, 2004, denomination of invention is divided an application for the application of " colored resin composition, colour filter and liquid-crystal display ".
Invention field
The present invention relates to a kind of colored resin composition and its preparation method, colour filter and liquid-crystal display.More specifically, the present invention relates to a kind of colored resin composition, it has good transmitance, has pattern adhesivity good during developing, develops the back at the residual seldom resistates of image-region and have dry and hard generation of reduction during by the die head coating at the die lip end; The invention still further relates to colour filter with the pixel that forms therein with this colored resin composition; With the liquid-crystal display that this colour filter is housed.
Background technology
As the method for the colour filter that is used to produce liquid-crystal display or its analogue, known pigment dispersion usually, dyeing, galvanic deposit and printing process.Wherein, consider spectral response curve, weather resistance, pattern form and tolerance range, the most generally adopt pigment dispersion method with average good characteristic.
Pigment dispersion method generally carries out according to following program.At first, use metal optical screen film such as chromium or chromic oxide on transparent carrier such as glass substrate, to form the fast black base thing.The colored resin composition (below can be described as " color resist ") that for example wherein is dispersed with red pigment is applied to the whole surface of gained substrate by spin coating or similar approach.Through photomask exposure, developing then obtains red pixel with this substrate.In a similar way, by coating, exposure and develop formation blueness and green pixel.As a result, form three kinds of pixels.Because there is concave part in the fast black base thing place between two kinds of pixels,, there is this surperficial trend of polarization by filming with transparent resin such as Resins, epoxy or acrylic resin covering surfaces and outside forming thus.Yet, always do not form outer filming.Go up sputter or vacuum moulding machine (when when not being provided with outside, filming on pixel and fast black base thing) by filming outside, formation nesa coating such as ITO (tin indium oxide).
In recent years, also usually adopt above-mentioned colo(u)rant dispersion method to form the fast black base thing.More specifically, wherein be dispersed with the colored resin composition (can be described as below the said composition " black resist) of black pigment, then exposure and developing by coating.
Along with the marked improvement in the nearest technical renovation, needed to develop the colour filter that has than high permeability and higher concentration.The colour filter that has a high permeability for formation must improve the dispersity of coloured material.For satisfying this requirement, the nitrogenous dispersion agent with good dispersion energy becomes welcome.The colour filter that formation has high permeability and high density requires to improve the concentration of coloring material in colored resin composition, and this also requires to improve the concentration of nitrogenous dispersion agent.Yet, only use this dispersion agent can not obtain enough liquid stabilisings.Except that this problem, flavescence takes place during the heating steps that forms colour filter, therefore reduce the pixel transmission.Colored resin composition is generally by the preparation of two steps, and promptly tinting material and dispersant are with blended steps such as the step of disperseing this mixture and dispersion agent and solvent, binding agents.As the resin glue that will be mixed in the colored resin composition, known use has the resin (for example WO96-23237) that adds to the structure of the carboxy moiety acquisition that contains carboxy resin by the unsaturated compound that will contain epoxide group.The problems referred to above can not overcome fully by this photosensitive resin composition.
For liquid-crystal display, there is the trend that colour filter and structure cell between the relative substrate are narrowed down, with satisfied demand to the quick response that is suitable for the film indicating meter.This means the amount of liquid crystal that reduces every cellar area.
When the pigmentary resin composition comprises a large amount of nitrogenous dispersion agent, after forming liquid crystal cells, it takes place go in the liquid crystal through wash-outs such as ITO films, cause reducing the problem of liquid crystal voltage conservation rate.In addition, every as mentioned above structure cell area amount of liquid crystal reduces with corresponding acceleration, and this further reduces voltage retention.Voltage retention reduces and allegedly to cause display defect as showing inhomogeneous and image lasting (for example open 2000-292920 referring to the Japanese Patent spy and the Japanese Patent spy opens 2000-311228), this have for expectation highly see through, the liquid-crystal display of high density and response fast is serious problems.
Be to solve the problem of non-uniform of indicating meter, propose to be higher than the dispersion agent of the temperature-20 ℃ when forming pigmented layer as the method that is contained in the dispersion agent in the colored resin composition with having decomposition temperature.The decomposition temperature of definition is the extraction quantity of organic impurity when the colored resin composition that contains dispersion agent by heating the forms pigmented layer Heating temperature (for example opening 2000-171784 referring to the Japanese Patent spy) when becoming 100ppm in this suggestion.
Yet, in aforesaid method, use the dispersion agent of nitrogen atom to damage voltage retention sometimes and make demonstration inhomogeneous.
For forming the high density colour filter, the concentration of coloring material in colored resin composition must improve.This causes the relative quantity reduction that image is formed the component of performance such as photosensitivity and solvability contribution, the result, make colored resin composition lose image and form performance, said composition had originally or promoted undissolved colored resin composition to remain in non-imaging region after development.The resistates that do not dissolve in this non-pixel region on substrate not only causes transmitance and contrast gradient with the colour filter of this resin formation to reduce, and damages sealing property in the step subsequent step is caused disadvantageous effect because of causing ito thin film to peel off or form at liquid crystal cells.
As the measure that overcomes these problems, proposed that molecular weight is not more than 1000 organic carboxyl acid compound and added method (for example, referring to patent gazette No.3293171) in the colored resin composition.This method is effective by the residual quantity that use is used for the not dissolved substance of some colored resin compositions that the resin glue of dispersion staining pigment obtains for the back of reduce developing in non-pixel region.
The various new technologies of colour filter have been proposed to be used to form.Form in the step in various pixels,, it is evenly coated in by spin coating carries out the resist-coating step on the substrate then generally by resist is added dropwise to substrate center.Raise because the resist consumption increases with substrate size, be applied to the restriction (for example motor power) of the very big device mode on the spin coater simultaneously, therefore developed the coating technique that uses the die head coating recently, and some of them have dropped into actual use.
Resist has been used to produce floppy disk (trade mark) through the coating technique of die head coating usually, and this technology generally is fit to coating fluid such as resist are applied to medium such as polymeric film continuously.
On the other hand, in single colour filter coating, the painting erosion resistant agent interruption is carried out, and therefore repeats wetting and dry at the die lip terminal portions.When wherein having with the colored resist of high density dispersive pigment or black resist when the terminal portions of die lip is dry, because the pigment caking appears in pigment concentration remarkable increase sometimes.This caking sticks to the die lip end, when resist once more when it injects, it falls and is transferred on the substrate from the die lip end.It is not easy to remove and still remain on the substrate until final step in subsequent step.This caking becomes a reason of color filter pixel defective and damages its quality.Must avoid frequently this undesirable phenomenon taking place, because it has reduced the productivity of colour filter.
Summary of the invention
It is preferred that the inventor has found to use its total nitrogen content to keep ratio low nitrogen atom dispersion agent after heating, because the nitrogen-atoms in the nitrogen atom dispersion agent keeps than causing disadvantageous effect voltage, and use through heating easy decomposition and evaporating the dispersion agent improvement voltage retention of its nitrogen-containing functional group part.Yet when using its total nitrogen content to keep ratio after heating during low nitrogen atom dispersion agent, voltage retention sees through sometimes and developing performance is also low even improve.In some applications, use total nitrogen content higher dispersion agent after heating of its reservation to improve the overall performance of colored resin composition.
Found to add the cohesive force that the organic carboxyl acid compound of describing in the patent gazette 3293171 for example not only damages non-image areas but also infringement image-region, the border that causes developing narrows down and is tending towards causing pixel to peel off and white defective.In other words, satisfy very difficulty of not dissolved substance residual quantity reduction and preferable image adhesive power simultaneously, and keep high quality to cause productive rate to reduce inevitably.
Consider the colored resin composition desired properties, not only require above-mentioned developing performance, and require to be suitable for the good coating performance of new coating processes such as die head coating, particularly suppress to form dry and hard performance.
Based on the problems referred to above, finished the present invention.The object of the invention will be described below.
(1) provides a kind of colored resin composition, even use its total nitrogen content to keep ratio after heating during high nitrogen atom dispersion agent, said composition also can suppress to reduce and display defect because of the liquid crystal voltage conservation rate that material indirect with liquid crystal layer or that directly contact brings, and satisfies high seeing through and this concentration requirement simultaneously.
(2) provide a kind of colored resin composition, when being applied to it on substrate, the residual colored resin composition seldom of non-image areas on substrate does not dissolve resistates, said composition and substrate have good adhesive power, during the coating of die head coating, reduce the generation of foreign matter, and can evenly form the high-concentration colorful pixel as caking.
(3) provide a kind of high quality colour filter, the colored resin composition of its non-pixel region noresidue on substrate does not dissolve resistates, does not have simultaneously to be attributable to dry and hard residual foreign matter.
(4) provide the high quality liquid-crystal display that uses this filter substrate.
For overcoming the problems referred to above, the inventor has carried out broad research result, find, show that after heating high total nitrogen content keeps the nitrogen atom dispersion agent of ratio even use, also the weight ratio that can have the resin glue of ad hoc structure and keep nitrogen-atoms dispersion agent and coloring material by adding is in pre-determined range, suppress the voltage retention reduction and realize high seeing through and developing performance simultaneously, finished the present invention thus.
Find, can obtain colored resin composition by being used in combination resin glue with ad hoc structure and dispersion agent with ad hoc structure, said composition is at the not residual not dissolved substance of non-image areas of substrate, have with the good adhesion performance of substrate, during the coating that is coated with by die head, reduce foreign matter such as dry and hard generation, and can evenly form the high-concentration colorful pixel.
Found to have ad hoc structure and the common resin that in the preparation colored resin composition, is used as resin glue by use, dispersion agent as the preparation colored resin composition, this colored resin composition obtains sufficiently high liquid stabilising, the result, photosensitive colored resin combination with its preparation has good developing performance, anti-frothiness, thermostability and liquid stabilising, the pixel that so forms has higher transmittance simultaneously, has finished the present invention thus.
A theme of the present invention is a kind of colored resin composition, said composition comprises no nitrogen-atoms resin glue, and this resin has epoxide group by the unsaturated compound that will contain epoxy group(ing) (a) and adds to as the carboxy resin (b) that contains of resin glue and go up the structure that obtains; With the nitrogen atom dispersion agent, and with respect to coloring material weight ratio 0.01 or higher, comprise the nitrogen atom dispersion agent but be not more than 0.5 weight ratio.
Another theme of the present invention is a kind of colored resin composition that comprises coloring material, solvent, dispersion agent and resin glue, it is characterized in that:
This resin glue is the resin that can obtain by the following method: with 5 to 90mol% contain epoxy (methyl) acrylate (A) and 10 to 95mol% another can with free redical polymerization compound (B) copolymerization of component A copolymerization, unsaturated monoprotic acid (c) added in the gained multipolymer on contained 10 to 100mol% the epoxide group, and multi-anhydride (D) is added to 10 to the 100mol% hydroxyls that produce by addition component (C); And dispersion agent comprises at least a in the following material: amino formate dispersion agent (E), nitrogen atom graft copolymer (F) and A-B segmented copolymer and/or B-A-B segmented copolymer (G), each freedom have the block A of quaternary ammonium salt and form in the B block that does not have quaternary ammonium salt in its side chain.
Another object of the present invention is to comprise the red colored resin combination of coloring material, solvent and resin glue, it is characterized in that when the pigmentary resin composition is coated with such film thickness, being CIE becomes 0.60 and 230 ℃ of bakings 30 minutes down than the colourity x in the color system, and this falls in arbitrary scope of being represented by following equation (1) and (2) than the Y value in the color system:
Y≥200y-41.4(y＜0.34) (1)
Y≥100y-7.4(y≥0.34) (2)
(wherein Y and y represent that respectively CIE is than reflectivity in the color system and colourity);
When pattern formed with this colored resin composition, the minimum pattern width that keeps as linear image was 10 μ m or littler; With
When having area 10cm 2Non-pixel region (on obscure glass) at pressure 1kgf/cm 2Following to having flooded 0.1cc/cm 2Alcoholic acid 3 μ m or still less during the cloth 1cm that constitutes of (on average) polyester macrofiber * 1cm wiping, the spectral reflectance on the pigment attachment portion is 95% or bigger at the 500nm place.
A theme more of the present invention is to comprise the green coloring resin combination of coloring material, solvent and resin glue, it is characterized in that when the pigmentary resin composition is coated with such film thickness, being CIE becomes 0.55 and 230 ℃ of bakings 30 minutes down than the chromaticity y in the color system, and this falls in the scope by following The Representation Equation than the Y value in the color system:
Y≥240x-7.1
(wherein Y and x represent that respectively CIE is than reflectivity in the color system and colourity);
When pattern formed with this colored resin composition, the minimum pattern width that keeps as linear image was 10 μ m or littler; With
When having area 10cm 2Non-pixel region (on obscure glass) at pressure 1kgf/cm 2Following to having flooded 0.1cc/cm 2Alcoholic acid 3 μ m or still less during the cloth 1cm that constitutes of (on average) polyester macrofiber * 1cm wiping, the spectral reflectance on the pigment attachment portion is 95% or bigger at the 450nm place.
A theme more of the present invention is to comprise the blue-colored resin combination of coloring material, solvent and resin glue, it is characterized in that when the pigmentary resin composition is coated with such film thickness, being CIE becomes 0.14 and 230 ℃ of bakings 30 minutes down than the chromaticity y in the color system, and this falls in the scope by following The Representation Equation than the Y value in the color system:
Y≥20x+16.2
(wherein Y and x represent that respectively CIE is than reflectivity in the color system and colourity);
When pattern formed with this colored resin composition, the minimum pattern width that keeps as linear image was 10 μ m or littler; With
When having area 10cm 2Non-pixel region (on obscure glass) at pressure 1kgf/cm 2Following to having flooded 0.1cc/cm 2Alcoholic acid 3 μ m or still less during the cloth 1cm that constitutes of (on average) polyester macrofiber * 1cm wiping, the spectral reflectance on the pigment attachment portion is 95% or bigger at the 550nm place.
Another theme of the present invention is to comprise substrate and the colour filter of the pixel that forms on substrate, it is characterized in that the part of pixel or whole portion form with this colored resin composition.
In detail, the present invention includes the following aspects.A first aspect of the present invention provides a kind of colored resin composition, comprises coloring material, solvent, dispersion agent and resin glue, wherein:
Resin glue comprises no nitrogen-atoms resin glue, and the epoxide group that this resin has by the unsaturated compound that will contain epoxide group (b) adds to the structure that obtains on the carboxyl that contains carboxy resin (a); This dispersion agent comprises the nitrogen atom dispersion agent; With the weight ratio of nitrogen atom dispersion agent and coloring material be 0.01 or higher, but be not more than 0.5.
A second aspect of the present invention is, colored resin composition according to first aspect present invention, wherein the nitrogen atom dispersion agent comprises at least a in following: amino formate dispersion agent (E), nitrogen atom graft copolymer (F) and A-B segmented copolymer and/or B-A-B segmented copolymer (G), each freedom have the block A of quaternary ammonium salt and do not have a quaternary ammonium salt in its side chain B block is formed.
A third aspect of the present invention provides a kind of colored resin composition, comprise coloring material, solvent, dispersion agent and binding agent, wherein: this resin glue is the resin that can obtain by the following method: (methyl) acrylate (A) that contains epoxy group(ing) with 5 to 90mol% and 10 to 95mol% another can with free redical polymerization compound (B) copolymerization of component (A) copolymerization, unsaturated monoprotic acid (C) added in the gained multipolymer on contained 10 to 100mol% the epoxide group, and on 10 to the 100mol% hydroxyls that produce when adding to multi-anhydride (D) by addition said components (C); And dispersion agent comprises at least a in the following material: amino formate dispersion agent (E), nitrogen atom graft copolymer (F) and A-B segmented copolymer and/or B-A-B segmented copolymer (G), each freedom have the block A of quaternary ammonium salt and do not have a quaternary ammonium salt in its side chain B block is formed.
A fourth aspect of the present invention is, according to the colored resin composition of the second aspect present invention or the third aspect, wherein amino formate dispersion agent (E) is the dispersion resin that can have the compound (2) of one or two hydroxyl by polyisocyanate compound (1), in an one molecule and have compound (3) the reaction acquisition of reactive hydrogen and uncle's amino in an one molecule.
A fifth aspect of the present invention is that according to the colored resin composition of the second aspect present invention or the third aspect, wherein the graft copolymer of nitrogen atom (F) has the nitrogen atom repeating unit in its main chain.
A sixth aspect of the present invention is, according to any one colored resin composition in second aspect present invention, the third aspect and the 5th aspect, wherein nitrogen atom graft copolymer (F) has the repeating unit of following general formula (I) expression and/or the repeating unit of formula (II) expression
Figure A20071014718700131
(wherein, R 1Expression has the alkylidene group of 1 to 5 carbon atom, and A represents any one group of hydrogen atom or following formula (III) to (V) expression)
Figure A20071014718700141
(wherein, R 1Expression has the alkylidene group of 1 to 5 carbon atom, and A represents any one group of hydrogen atom or following formula (III) to (V) expression)
Figure A20071014718700142
(W wherein 1Expression has the alkylidene group of 2 to 10 carbon atoms, and p represents 1 to 20 integer)
Figure A20071014718700143
(Y wherein 1The expression divalent linker, W 2The alkylidene group of 2 to 10 carbon atoms of expression, Y 2The expression hydrogen atom or-CO-R 2(R 2Expression has the alkylidene group of 1 to 10 carbon atom), q represents 1 to 20 integer)
(W wherein 3The alkyl of 1 to 50 carbon atom of expression or have the hydroxyalkyl of 1 to 50 carbon atom of 1 to 5 hydroxyl).
A seventh aspect of the present invention is, according to a second aspect of the invention or the colored resin composition of the third aspect, it is characterized in that each freedom has the block A of quaternary ammonium salt and do not have A-B segmented copolymer that the B block of quaternary ammonium salt forms and/or the block A of B-A-B segmented copolymer (G) in its side chain, comprise the part-structure of following formula (1) expression:
Figure A20071014718700151
(in formula (1), R 1a, R 2aAnd R 3aRepresent hydrogen atom or can substituted ring texture or the alkyl of chain-like structure or R independently of one another 1a, R 2aAnd R 3aIn at least two mutually coupling form ring structure, R 4aExpression hydrogen atom or methyl, X represents divalent linker, Y -The expression counter anion).
A eighth aspect of the present invention is, according to any one colored resin composition in second～the 7th aspect of the present invention, wherein resin glue comprises the list with following structural formula (VI) (methyl) acrylate as component (B):
Figure A20071014718700152
(in formula (VI), R 3To R 8Represent hydrogen atom independently of one another or have the alkyl of 1 to 3 carbon atom, R 9And R 10Represent hydrogen atom independently of one another or have the alkyl or the R of 1 to 3 carbon atom 9And R 10Coupling forms ring mutually).
A ninth aspect of the present invention is, the colored resin composition of any one in the second～the eight aspect according to the present invention, and wherein composition further comprises the phosphate type dispersion agent as dispersion agent.
A tenth aspect of the present invention is that according to the colored resin composition of ninth aspect present invention, wherein the phosphate type dispersion agent has the partial structural formula of following formula (3) expression:
A eleventh aspect of the present invention is, according to any one colored resin composition in the 3rd～the tenth aspect of the present invention, wherein said composition comprises that having molecular weight is not more than 1000 organic carboxyl acid and/or organic carboxyl acid acid anhydride.
A twelveth aspect of the present invention is that according to the colored resin composition of first aspect present invention, wherein carboxylic resin (a) has hydroxyl.
A thirteenth aspect of the present invention is, according to any one colored resin composition in first～the 12 aspect of the present invention, wherein composition further comprises photopolymerizable monomer.
A fourteenth aspect of the present invention is, according to any one colored resin composition in first～the 13 aspect of the present invention, wherein composition further comprises the Photoepolymerizationinitiater initiater system component.
A fifteenth aspect of the present invention is, according to any one colored resin composition in the first, the 12 and the 14 aspect of the present invention, be added to the no nitrogen-atoms resin glue of the structure that the carboxyl of carboxylic resin (a) obtains by the epoxy group(ing) of mixing coloring material, solvent, nitrogen atom dispersion agent and having a unsaturated compound (b) by containing epoxy group(ing), with the dispersion of gained mixture with as if necessary another component is mixed acquisition with dispersion liquid.
A sixteenth aspect of the present invention provides a kind of red colored resin combination that comprises coloring material, solvent and resin glue, wherein: when the pigmentary resin composition is coated with such film thickness, be CIE than the colourity x in the color system become 0.60 and at 230 ℃ baking is after 30 minutes down, this falls into by in the scope of representing as shown in the formula (1) or (2) than the Y value in the color system:
Y≥200y-41.4(y＜0.34) (1)
Y≥100y-7.4(y≥0.34) (2)
(wherein Y and y represent that respectively CIE is than reflectivity in the color system and colourity);
When pattern formed with this pigmentary resin compound, the minimum pattern width that keeps as linear image was 10 μ m or littler; With
When having area 10cm 2Non-pixel region (on obscure glass) at pressure 1kgf/cm 2Following to having flooded 0.1cc/cm 2Alcoholic acid 3 μ m or still less during the cloth 1cm that constitutes of the polyester macrofiber of (on average) * 1cm wiping, the spectral reflectance on the pigment attachment portion is 95% or bigger at the 500nm place.
A seventeenth aspect of the present invention provides a kind of green coloring resin combination that comprises coloring material, solvent and resin glue, wherein: when the pigmentary resin composition is coated with such film thickness, being CIE becomes 0.55 and 230 ℃ of bakings after 30 minutes down than the chromaticity y in the color system, and this falls into by as shown in the formula in the scope of representing than the Y value in the color system:
Y≥240x-7.1
(wherein Y and x represent that respectively CIE is than reflectivity in the color system and colourity);
When pattern formed with this colored resin composition, the minimum pattern width that keeps as linear image was 10 μ m or littler; With
When having area 10cm 2Non-pixel region (on obscure glass) at pressure 1kgf/cm 2Following to having flooded 0.1cc/cm 2Alcoholic acid 3 μ m or still less during the cloth 1cm that constitutes of (on average) polyester macrofiber * 1cm wiping, the spectral reflectance on the pigment attachment portion is 95% or bigger at the 450nm place.
A eighteenth aspect of the present invention provides a kind of blue-colored resin combination that comprises coloring material, solvent and resin glue, wherein: when the pigmentary resin composition is coated with such film thickness, being CIE becomes 0.14 and 230 ℃ of bakings after 30 minutes down than the colourity x in the color system, and this falls into by as shown in the formula in the scope of representing than the Y value in the color system:
Y≥20x+16.2
(wherein Y and x represent that respectively CIE is than reflectivity in the color system and colourity);
When pattern formed with this colored resin composition, the minimum pattern width that keeps as linear image was 10 μ m or littler; With
When having area 10cm 2Non-pixel region (on obscure glass) at pressure 1kgf/cm 2Following to having flooded 0.1cc/cm 2Alcoholic acid 3 μ m or still less during the cloth 1cm that constitutes of (on average) polyester macrofiber * 1cm wiping, the spectral reflectance on the pigment attachment portion is 95% or bigger at the 550nm place.
A nineteenth aspect of the present invention is, according to any one colored resin composition in the 16～the tenth eight aspect of the present invention, wherein when said composition when storing 7 days down for 23 ℃, its viscosity velocity of variation with respect to initial viscosity is 10% or lower.
A twentieth aspect of the present invention is, according to any one colored resin composition in the 16～the 19 aspect of the present invention, it comprises coloring material, solvent and resin glue, wherein soak and redispersion in the solvent of this colored resin composition of formation the time when the dry film that forms by colored resin composition, the volume average particle size mv in redispersion liquid is 200nm or littler.
The of the present invention the 20 is on the one hand, according to any one colored resin composition in the 16～the 20 aspect of the present invention, it comprises coloring material, solvent and resin glue, wherein when filming of forming by colored resin composition with the liquid crystal state of contact under after the annealing, during to liquid crystal applied voltages, voltage retention is 80% or bigger by the pigmentary resin layer.
The 22 aspect of the present invention is, according to the of the present invention the 16～the 20 on the one hand in any one colored resin composition, wherein this resin glue is the resin that can obtain by the following method: (methyl) acrylate (A) that contains epoxy group(ing) with 5 to 90mol% and 10 to 95mol% another can with free redical polymerization compound (B) copolymerization of component A copolymerization, unsaturated monoprotic acid (c) added in the gained multipolymer on contained 10 to 100mol% the epoxide group, and on 10 to the 100mol% hydroxyls that produce when adding to multi-anhydride (D) by addition said components (C).
The 23 aspect of the present invention is, according to any one colored resin composition in the 16～the 22 aspect of the present invention, wherein dispersion agent comprises at least a in the following material: amino formate dispersion agent (E), nitrogen atom graft copolymer (F) and A-B segmented copolymer and/or B-A-B segmented copolymer (G), each freedom have the block A of quaternary ammonium salt and do not have a quaternary ammonium salt in its side chain B block is formed.
The 24 aspect of the present invention provides the filter substrate that the colored resin composition of any one forms in a kind of usefulness first～the 23 aspect of the present invention.
The liquid-crystal display that the 25 aspect of the present invention provides the filter substrate of a kind of usefulness the 24 aspect of the present invention to form.
The 26 aspect of the present invention provides the method for a kind of production colored resin composition (M), comprise that the resin (H) that the epoxy group(ing) that will have the unsaturated compound (b) by containing epoxy group(ing) adds to the structure that obtains on the carboxyl of carboxylic resin (a) mixes with coloring material (I), and the gained mixture disperseed with the step of preparation colored resin composition (J) with this colored resin composition (J) and resin (K) and solvent (L) blended step.
The 27 aspect of the present invention is, the method for production colored resin composition according to the twenty-sixth aspect, and the unsaturated compound (b) that wherein contains epoxy group(ing) is the alicyclic epoxy compound.
The 20 eight aspect of the present invention is, according to the of the present invention the 26 or the method for the production colored resin composition of the 27 aspect, wherein carboxylic resin (a) has hydroxyl.
The 29 aspect of the present invention is, according to the twenty-sixth aspect～the 20 eight aspect in any one the method for production colored resin composition, wherein said composition comprises that pigment derivative is as dispersing auxiliary.
The 30 aspect of the present invention provides the colored resin composition among any one the preparation method of the 26 to 29 aspect of the present invention of being used for of a kind of (J) expression.
Hentriaconta-of the present invention aspect is, according to the twenty-sixth aspect the colored resin composition of (M) expression of the preparation method's preparation of any one to the 29 aspect.
The 32 aspect of the present invention provides a kind of colored resin composition, comprise that the epoxy group(ing) with the unsaturated compound (b) by containing epoxy group(ing) adds to resin (H), coloring material (I), photopolymerizable monomer and the Photoepolymerizationinitiater initiater of the structure that obtains on the carboxyl of carboxylic resin (a), wherein the resin Composition of at least 60 weight % is an alkali soluble resin.
The 33 aspect of the present invention provides a kind of filter substrate, and wherein this substrate forms with the colored resin composition of hentriaconta-of the present invention or the 32 aspect.
The 34 aspect of the present invention provides a kind of liquid-crystal display, and wherein this indicating meter forms with the filter substrate of the 33 aspect of the present invention.
The present invention brings following effect.
1. colored resin composition of the present invention on being applied to substrate the time at the not residual undissolved material of the non-pixel region of substrate, have the adhesive power good with substrate, and can evenly form the high-concentration colorful pixel.Even when being coated with by die head, said composition also produces foreign matter such as dry and hard hardly.In addition, the pixel of using said composition to form has high transportation performance, and said composition greatly reduces the influence to the liquid crystal voltage conservation rate, and it causes developing defect as developing inhomogeneous and image persistence hardly like this.
2. colour filter of the present invention is at the colored resin composition of the non-pixel region noresidue of substrate dissolved substance not.So the pixel that forms has high permeability.Simultaneously, it has especially little influence to the voltage retention of liquid crystal, can avoid occurring developing defect like this as developing inhomogeneous and image persistence.Therefore, this colour filter has extra high quality.
3. liquid-crystal display of the present invention has extra high quality, because its uses wherein at the non-pixel region of the substrate very high-quality colour filter of the not dissolved substance of residual colored resin composition not, so the pixel that forms has high-transmittance, therefore can avoid otherwise will cause showing uneven low liquid crystal voltage conservation rate.
Embodiment
Below the present invention will be described more specifically.
[1] the formation component of colored resin composition (resist)
Colored resin composition of the present invention (resist) has coloring material, solvent, dispersion agent and the resin glue as basal component, and it can comprise the additive except that said components as if necessity.
To explain below and respectively constitute component.
[1-1] coloring material:
Term " coloring material " is meant with it the painted material of colored resin composition of the present invention.For coloring material, can use pigment or dyestuff, consider heat-resisting and photostabilization, wherein preferred pigments.
For pigment, can use various pigment such as blue pigments, veridian, red pigment, yellow ultramarine, violet pigment, orange pigments and brown.With regard to structure, can use pigment dyestuff such as azo, phthalocyanine, quinacridone, benzimidazolone, iso-dihydro-indole (indoli does not have), two  piperazines, indanthrene with perylene dye.Can also use various mineral dyes.The object lesson that can be used for pigment of the present invention will be mentioned by the pigment label below.Following term " C.I. Pigment red " or its analogue are meant color index (C.I.).
The example of red pigment comprises C.I. Pigment red 1,2,3,4,5,6,7,8,9,12,14,15,16,17,21,22,23,31,32,37,38,41,47,48,48:1,48:2,48:3,48:4,49,49:1,49:2,50:1,52:1,52:2,53,53:1,53:2,53:3,57,57:1,57:2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275 and 276.
Wherein, preferred C.I. pigment red 4 8:1,122,168,177,202,206,207,209,224,242 and 254, more preferably the C.I. Pigment red 177,209,224 and 254.
The example of blue pigments comprises C.I. pigment blue 1,1:2,9,14,15,15:1,15:2,15:3,15:4,15:6,16,17,19,25,27,28,29,33,35,36,56,56:1,60,61,61:1,62,63,66,67,68,71,72,73,74,75,76,78 and 79.
Wherein, preferred C.I. pigment Blue 15,15:1,15:2,15:3,15:4 and 15:6, more preferably C.I. pigment Blue 15: 6.
The example of veridian comprises C.I. Pigment green 1,2,4,7,8,10,13,14,15,17,18,19,26,36,45,48,50,51,54 and 55.Wherein preferred C.I. pigment Green 7 and 36.
The example of yellow ultramarine comprises C.I. Pigment Yellow 73 1,1:1,2,3,4,5,6,9,10,12,13,14,16,17,24,31,32,34,35,35:1,36,36:1,37,37:1,40,41,42,43,48,53,55,61,62,62:1,63,65,73,74,75,81,83,87,93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139,142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169,170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196,197,198,199,200,202,203,204,205,206,207 and 208.
Wherein, preferred C.I. pigment yellow 83,117,129,138,139,150,154,155,180 and 185, more preferably C.I. pigment pigment yellow 83,138,139,150 and 180.
The example of orange pigments comprises C.I. pigment orange 1,2,5,13,16,17,19,20,21,22,23,24,34,36,38,39,43,46,48,49,61,62,64,65,67,68,69,70,71,72,73,74,75,77,78 and 79.Wherein, preferred C.I. pigment orange 38 and 71.
The example of violet pigment comprises C.I. pigment violet 1,1:1,2,2:2,3,3:1,3,3:3,5,5:1,14,15,16,19,23,25,27,29,31,32,37,39,42,44,47,49 and 50.Wherein, preferred C.I. pigment purple 19 and 23, more preferably C.I. pigment Violet 23.
The example of other pigment comprises barium sulfate, lead sulfate, titanium oxide, lead and yellow-collation, rouge and chromic oxide.
Above-mentioned multiple pigment combinations can be used.Use veridian for example capable of being combined and yellow ultramarine or blue pigments and violet pigment are controlled colourity thus.Above-mentioned pigment has the common 1 μ m or lower of average particle size particle size, preferred 0.5 μ m or lower, more preferably 0.25 μ m or lower.
The dyestuff that can be used as coloring material comprises azoic dyestuff, anthraquinone dye, phthalocyanine pigment, quinonimine dye, quinoline dye, nitro-dye, carbonyl dyestuff and methine dyes.
The example of azoic dyestuff comprises the C.I. acid yellow 11, C.I. acid orange 7, C.I. Xylene Red 37, C.I. acid red 18 0, C.I. acid blue 29, C.I. directly red 28, C.I. directly red 83, C.I. direct yellow 12, C.I. direct orange 26, C.I. sun green 28, C.I. sun green 59, C.I. reactive yellow 2, C.I. reactive red 17, C.I. reactive red 120, C.I words property black 5, C.I. DISPERSE ORANGE 30 200 5, C.I. Disperse Red 58, C.I. EX-SF DISPERSE BLUE EX-SF 300 165, C.I. alkali blue 41, C.I. Basic Red 18, C.I. acid mordant red 7, C.I. acidic intermedium yellow 5 and C.I. acid mordant black 7.
The example of anthraquinone dye comprises C.I. Vat blue 4, C.I. Acid Blue 40, C.I. ACID GREEN 25, C.I. Reactive Blue 19 100, C.I. reactive blue 49, C.I. disperse red 60, C.I. Disperse Blue-56 and C.I. Disperse Blue-60.
In addition, the example of phthalocyanine pigment comprises C.I.Pad indigo plant 5, those of quinonimine dye comprise C.I. Basic Blue 3 and C.I. alkali blue 9, those of quinoline dye comprise C.I. solvent yellow 33, C.I. quinoline yellow and C.I. dispersion yellow 64 and nitro-dye those comprise C.I. turmeric yellow 1, C.I. von Muller's indicator 3 and C.I. Disperse Yellow 42.
For by using colored resin composition to form the fast black base thing of colour filter, can use the black colorant material.The black colorant material can only be the black colorant material, or is red, green and blue mixture.These coloring materials can be chosen from inorganic and pigment dyestuff and dyestuff as required.When using inorganic or during pigment dyestuff, preferably use after having the common 1 μ m of median size or littler, preferred 0.5 μ m or littler particle being separated into.
The black colorant examples of substances that can use separately comprises carbon black, acetylene black, dim, bone ash, graphite, iron oxide black, nigrosine, cyanine is black and titanium is black.
In these black colorant materials, consider shading speed and picture characteristics, preferred carbon black.Can provide following carbon black, as the sooty example.
Sooty example available from Mitsubishi Chemical Corporation comprises MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600,3050#, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B.
Can comprise Printex 3 available from the sooty example of Degussa, Printex 3OP, Printex 30, Printex 30OP, Printex 40, Printex 45, PRintex 55, Printex 60, Printex 75, Printex 80, Printex 85, Printex 90, Printex A, Printex L, Printex G, PrintexP, Printex U, Printex V, Printex G, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, SpecialBlack 4, Color Black FW1, Color Black FW2, Color Black FW2V, Color BlackFW18, Color Black FW18, Color Black FW200, Color Black S160 and ColorBlack S170.
Sooty example available from Cabot Corporation comprises Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL400R, REGAL 55R0, REGAL 660R, BLACK PEARLS480, PEARLS 130, VULCAN XC 72R and ELFTEX-8.
Sooty example available from Columbian Carbon comprises RAVEN 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22, RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, and RAVEN 500, RAVEN 780, RAVEN850, RAVEN 890H, RAVEN 1000, RAVEN 1020, RAVEN 1040, RAVEN1060U, RAVEN 1080U, RAVEN 1170, RAVEN 1190U, RAVEN 1250, RAVEN1500, RAVEN 2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN5250, RAVEN 5750 and RAVEN 7000.
For preparation has high optical density (OD) and the prima facie resin black color base of Gao Nai thing, the resin-coated carbon black of preferred especially use.
The example that can be mixed for preparing the coloring material of black colorant material comprises Victoria's ethereal blue (42595), alkaline bright yellow O (41000), Catilon Brilliant Flavin (basic 13), rhodamine 6G CP (45160), rhodamine B (45170), Safranine O K70:100 (50240), the red X of small-mouthed jar (42080), No.120/Lionol Huang (21090), the yellow GRO (21090) of Lionol, the yellow 8GF (21105) of Symuler Fast, diarylide yellow 4T-564D (21095), Symuler Fast red 4015 (12355), the red 7B4401 of Lionol (15850), the blue TGR-L (74160) of Fastgen, the blue SM (26150) of Lionol, blue ES (the pigment Blue 15: 6) of Lionol, red GD of Lionogen (Pigment red 168) and the green 2YS of Lionol (pigment green 36).Numeral color index (C.I.) in the top bracket.
The example that can be used for other pigment of blended comprises (based on the CI numeral) C.I. yellow pigment 20,24,86,93,109,110,117,125,137,138,147,148,153,154 and 166, C.I. orange pigment 36,43,51,55,59 and 61, C.I. red pigment 9,97,122,123,149,168,177,180,192,215,216,217,220,223,224,226,227,228 and 240, C.I. violet pigment 19,23,29,30,37,40 and 50, C.I. blue pigments 15,15:1,15:4,22,60 and 64, C.I. veridian 7, and C.I. brown 23,25 and 26.
The ratio of coloring material in colored resin composition is generally 1 weight % or bigger, preferred 10 weight % or bigger, common 70 weight % or littler, preferred 60 weight % or littler (based on total solids).If the weight ratio of coloring material is low excessively, then film is too thick with respect to color density, and this influences slit control unfriendly when liquid crystal cells (cell) forms.On the contrary, the weight ratio that coloring material is too high, the image that overslaugh sometimes is enough forms performance.Term used herein " total solids " is meant and desolventizes (will be described below) outer all components.
[1-2] solvent:
In colored resin composition of the present invention, solvent has and coloring material, dispersion agent, resin glue and non-essential other added components dissolved or is scattered in wherein and the function of control combination thing viscosity.
The example of solvent comprises Di Iso Propyl Ether, solvent oil, Skellysolve A, amyl ether, ethyl octylate, normal hexane, diethyl ether, different propylene, the ethyl isobutyl ether, butyl stearate, octane, Varsol#2, the Apco#18 solvent, diisobutylene, pentyl acetate, butylacetate, the Apco thinner, butyl ether, diisobutyl ketone, tetrahydrotoluene, methyl nonyl ketone, propyl ether, dodecane, Socal solvent No.1 and No.2, pentyl formate, hexyl ether, diisopropyl ketone, Solvesso#150, acetate (just-, secondary-, the tertiary butyl-) ester, hexene, Shell TS28 solvent, Butyryl Chloride, ethyl pentyl group ketone, ethyl benzoate, amyl chloride, the ethylene glycol bisthioglycolate ethyl ether, ethyl orthoformate, the methoxymethyl pentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, the methylcellulose gum acetic ester, methyl isoamyl ketone, methyl iso-butyl ketone (MIBK), propyl acetate, pentyl acetate, pentyl formate, dicyclohexyl two sweet single ethyl acetate, limonene, the methoxymethyl amylalcohol, Methyl amyl ketone, methyl isopropyl Ketone, propyl acrylate, the glycol tertiary butyl ether, methyl ethyl ketone, methylcellulose gum, ethyl cellulose, the ethyl cellulose acetic ester, Trivalin SF, pimelinketone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether, the propylene glycol monomethyl ether propylene glycol monomethyl ether, the DPGME DPGME, the DPGME acetic ester, the 3-methoxypropionic acid, the 3-ethoxy-propionic acid, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diethylene glycol dimethyl ether, the ethylene glycol ethyl ethers acid esters, ethyl carbitol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, the glycol tertiary butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether and 3-methyl-3-methoxyl group butylacetic acid ester.These solvents can be used in combination separately or with its two or more.
Although the painted colored resin composition of the present invention in content do not have particular restriction, its upper limit is generally 99 weight % or still less.It is unfavorable that quantity of solvent is filmed for formation above 99 weight %, because the quantitative change of coloring material and dispersion agent gets too little.The lower bound of considering the viscosity solvent that is suitable for being coated with is generally 75 weight % or bigger, preferred 80 weight % or bigger, more excellent 82 weight % or bigger.
[1-3] dispersion agent
Dispersion agent among the present invention is a kind of nitrogen atom dispersion agent, its total nitrogen content after 230 ℃ are heated 30 minutes down keeps ratio (total nitrogen content that the heating back keeps and the total nitrogen content weight ratio before the heating) and is generally 95 weight % or lower, preferred 90 weight % or lower, more preferably 80 weight % or lower.The weight reservation of nitrogen atom dispersion agent is preferably 95 weight % or lower, more preferably 90 weight % or lower than (ratio of the weight before weight after the heating and the heating) after 230 ℃ are heated 30 minutes down.
In the present invention, at 230 ℃ down before the heating 30 minutes, with colored resin composition under the 10mmHg decompression 60 ℃ down dry 48 hours with the evaporating solvent component.Term " before the heating " is meant " being evaporated to dry back ".Said composition was heated 30 minutes down at 230 ℃ as heating in the air circulating oven at process furnace.Nitrogen content before and after the heating is measured with elemental analyser such as CHN analyser, and weight is measured with precision balance usually.
For the dispersion agent of nitrogen atom, use tensio-active agent and macromolecule dispersing agent usually.Wherein, preferred especially macromolecule dispersing agent.For macromolecule dispersing agent, preferably introduce amino formate dispersion agent, nitrogen atom graft copolymer and by the block A that in its side chain, has quaternary ammonium salt with there be not at least a in A-B segmented copolymer that the B block of quaternary ammonium salt forms and/or the B-A-B segmented copolymer.In the present invention, be used in combination above-mentioned dispersion agent and specific resin glue (will be described below), can make the film that forms by coloured composition during developing with the substrate secure bond, and suppress that dissolved substance is not residual, keep dispersion stability simultaneously.
Dispersion agent can be used in combination separately or with its two or more.When mixing at least two kinds of nitrogen atom dispersion agents, above-mentioned reservation is than being defined as with total reservation ratio of the mixture of ratio of mixture blended nitrogen atom dispersion agent separately.
Nitrogen-atoms in the nitrogen atom dispersion agent preferably exists with amino or quaternary ammonium form.These functional groups help dispersion stable, and because of its alkalescence, they can be easily and the acidic group coordination of pigment or pigment derivative.The amine value of dispersion agent is generally 2 to 100 KOHmg/g, preferred 3 to 80 KOHmg/g.If the amine value is too low, then hypoalkalinity causes bad dispersion stability, and the voltage retention of too high acid number reduction liquid crystal is tending towards causing display defect simultaneously.Therefore, not preferred in above-mentioned extraneous amine value.
The weight ratio of nitrogen atom dispersion agent and coloring material is generally 0.01 or bigger, but is not more than 0.5, and preferred 0.02 or bigger, preferably be not more than 0.3, more preferably no more than 0.2.Too high dispersion agent weight ratio influences voltage retention unfriendly and causes display defect inhomogeneous lasting with image as showing.When this ratio is too low, insufficient demonstration dispersing property, and can not obtain high seeing through and high viscosity stability.
Preferred dispersing agent will be explained below.
[1-3-1] amino formate dispersion agent
For the amino formate dispersion agent, being preferably can be by polyisocyanate compound (1), have the compound (2) of one or more hydroxyls and have the dispersion resin that compound (3) reaction of reactive hydrogen and uncle's amino obtains in its molecule in its molecule.
(1) polyisocyanate compound,
The example of polyisocyanate compound comprises that aromatic diisocyanate is as to phenylene vulcabond, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, naphthalene-1,5-vulcabond and ditolyl vulcabond; Aliphatic vulcabond such as hexylidene diisocyanate, Methionin methyl ester vulcabond, 2,4,4-trimethylammonium hexylidene diisocyanate and dimer acid diisocyanate; Alicyclic diisocyanate such as isophorone diisocyanate, 4,4 '-methylene-bis (cyclohexyl isocyanate) and ω, ω '-vulcabond dimethyl cyclohexane; Aliphatic vulcabond such as xylylene vulcabond and the α of aliphatic vulcabond that contains aromatic nucleus as containing aromatic ring, α, α ', α '-tetramethyl-benzene dimethyl vulcabond; Triisocyanate such as Methionin ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-vulcabond-4-isocyanic ester methyloctane, 1,3,6-hexylidene triisocyanate, norbornane triisocyanate, three (isocyanate benzene methylmethane) and three (isocyanate phenyl) thiophosphatephosphorothioate; And its tripolymer, water adducts and Qi Duo alcohol adducts.
Polyisocyanates is preferably the organic diisocyanate tripolymer, most preferably the tripolymer of tolylene diisocyanate and Trimerization of Isophorone Diisocyanate body.They can be used alone or in combination.
The isocyanate trimerization style is as preparing by the following method: use catalyst for trimerization such as tertiary amine, phosphine, alkoxide, metal oxide or the carboxylate salt isocyanate groups part trimerization with above-mentioned polyisocyanates, stop this trimerization by adding catalyzer poison, with remove unreacted polyisocyanates by solvent extraction or thin film distillation, preparation contains the polyisocyanates of target isocyanuric acid ester thus.
(2) in its molecule, have-compound of individual or two hydroxyls.
The example that has the compound of one or two hydroxyl in its molecule comprises polyether glycol, polyester glycol, polycarbonate diol and polyolefin diols, with those compounds that have at its end with the alkyl alkoxylated hydroxyl of 1 to 25 carbon atom, and two or more mixture in them.
The example of polyether glycol comprises polyether glycol and polyether ester glycol, and two or more mixture.The example of polyether glycol comprises homopolymer or multipolymer such as polyoxyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxy butyleneglycol, polyoxy hexylene glycol and the polyoxy ethohexadiol of alkylene oxide, and two or more mixture.The example of polyether ester glycol comprise can be by containing ether glycol or the reactor product that obtains of the mixture of itself and other glycol and carboxylic acid or its anhydride reaction, maybe can be by the reactor product of polyester glycol and alkylene oxide reaction acquisition, as poly-(polyoxy butylidene) adipic acid ester.The most preferred example of polyether glycol comprises polyoxyethylene glycol, polypropylene glycol and polyoxy butyleneglycol, and has those compounds with the alkyl alkoxylated hydroxyl of 1 to 25 carbon atom at its end.
The example of polyester glycol comprises that dicarboxylic acid is (as Succinic Acid, pentanedioic acid, hexanodioic acid, sebacic acid, fumaric acid, toxilic acid or phthalic acid) or its acid anhydrides and glycol (as aliphatic diol ethylene glycol for example, glycol ether, triglycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 2, the 3-butyleneglycol, the 3-methyl isophthalic acid, the 5-pentane diol, neopentyl glycol, the 2-methyl isophthalic acid, the 3-propane diol, 2-methyl-2-propyl group-1, the 3-propane diol, 2-butyl-2-ethyl-1, the 3-propane diol, 1, the 5-pentane diol, 1, the 6-hexane diol, 2-methyl-2, the 4-pentane diol, 2,2,4-trimethylammonium-1, the 3-pentane diol, 2-ethyl-1, the 3-hexane diol, 2,5-dimethyl-2,5-hexane diol, 1, the 8-ethohexadiol, the 2-methyl isophthalic acid, 8-ethohexadiol or 1,9-nonanediol, the for example two methylol hexanaphthenes of alicyclic diol, aromatic diol such as xylylene glycol or two hydroxy ethoxy benzene, or N-alkyl two alkanolamines such as N methyldiethanol amine) polycondensation products, as polyethylene glycol adipate, poly adipate succinic acid ester, poly-hexanodioic acid hexylene glycol ester and poly-hexanodioic acid/ethylene glycol/propylene glycol ester; With can be by with having the polylactone two pure and mild polylactone list alcohol that the dibasic alcohol of 1 to 25 carbon atom or monohydroxy-alcohol obtain as initiator, as polycaprolactone glycol, poly-methylpent lactone and two or more mixture thereof.The most preferred example of polyester glycol comprises the polycaprolactone that polycaprolactone glycol and the alcohol with 1 to 25 carbon atom obtain as initiator, more specifically, and can be by the compound of 6-caprolactone with single pure open loop addition polymerization acquisition.
The example of polycaprolactone glycol comprises poly-(hexamethylene) carbonic ether and poly-(3-methyl isophthalic acid, 5-pentylidene) carbonic ether.
The example of polyolefin diols comprises polybutadiene diol, hydrogenated butadiene polymer two pure and mild hydrogenated polyisoprene glycol.
In an one molecule, have in the compound of 1 or 2 hydroxyl special preferred, polyethers two pure and mild polyester glycols.
The compound that has 1 or 2 hydroxyl in an one molecule has number-average molecular weight 300 to 10,000 usually, and is preferred 500 to 6,000, and more preferably 1,000 to 4,000.
(3) in an one molecule, has the compound of reactive hydrogen and uncle's amino
Reactive hydrogen, promptly directly and the hydrogen atom of Sauerstoffatom, nitrogen-atoms or sulfur atom linkage, its example is included in the hydrogen atom in functional group such as hydroxyl, amino and the thiol group.Wherein, preferred amino, the particularly hydrogen atom in the primary amino.
Although to the amino no particular restriction of uncle, its example comprises alkyl such as the dialkylamino of methyl, ethyl, sec.-propyl and normal-butyl and the group that formation has the heterocycle structure of connected dialkylamino with 1 to 4 carbon atom.Example comprises imidazole ring and triazolidine more specifically.
The example that has the compound of reactive hydrogen and uncle's amino in an one molecule comprises N, N-dimethyl-1,3-propylene diamine, N, N-diethyl-1,3-propylene diamine, N, N-dipropyl-1,3-propylene diamine, N, N-dibutyl-1,3--propylene diamine, N, N-dimethyl-ethylenediamine, N, N-diethyl ethylenediamine, N, N-dipropyl quadrol, N, N-dibutyl quadrol, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine and N, N-dibutyl-1, the 4-butanediamine.
Comprise as the nitrogenous heterocyclic example of uncle's amino and to contain 5 yuan of heterocycles of N such as pyrazoles ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzoglyoxaline ring, benzotriazole ring, benzoxazol ring, benzothiazole ring and diazosulfide ring and to contain 6 yuan of heterocycles of N such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline 99.9 ring.These nitrogenous heterocyclic preferred example comprise imidazole ring and triazole.
Object lesson with compound of imidazole ring and primary amino comprises 1-(3-aminopropyl) imidazoles, Histidine, 2-aminooimidazole and 1-(2-aminoethyl) imidazoles.Object lesson with compound of triazole ring and primary amino comprises 3-amino-1,2,4-triazole, 5-(2-amino-5-chloro-phenyl-)-3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-glycol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-phenylbenzene-1,2,3-triazole and 3-amino-1-benzyl-1H-2,4-triazole.Wherein, preferred N, N-dimethyl-1,3-propylene diamine, N, N-diethyl-1,3-propylene diamine, 1-(3-aminopropyl) imidazoles and 3-amino-1,2,4-triazole.
For these raw-material ratio of mixture that are used for dispersion resin, with 100 weight part polyisocyanate compounds and common 10 to 200 weight parts, preferred 20 to 190 weight parts, more preferably 30 to 180 weight parts have the compound of one or two hydroxyl and common 0.2 to 25 weight part, preferred 0.3 to 24 weight part have reactive hydrogen and uncle's amino in an one molecule compound blend in an one molecule.
It is common 1,000 to 200,000 that carbamate dispersion resin of the present invention has weight-average molecular weight, preferred 2,000 to 100,000, and more preferably 3,000 to 50,000, by using the gpc measurement of polystyrene standards.When molecular weight is not more than at 1,000 o'clock, dispersing property and dispersion stabilization variation, and when molecular weight be 200,000 or when bigger, solubleness reduces, and damages dispersion stabilization like this and makes reaction control difficulty.
Carbamate dispersion resin of the present invention is according to the known way preparation of preparation urethane resin.The example of the solvent that is generally used for preparing comprises ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, pimelinketone and isophorone, ester such as ethyl acetate, butylacetate and cellulose ethanoate, hydrocarbon such as benzene,toluene,xylene and hexane, some alcohol is as Pyranton, Virahol, sec-butyl alcohol and the trimethyl carbinol, muriate such as methylene dichloride and chloroform, ether such as tetrahydrofuran (THF) and Anaesthetie Ether, and non-polar solvent such as dimethyl formamide, N-Methyl pyrrolidone and methyl-sulphoxide.
As the catalyzer that is used to prepare, use the catalysts that is generally used for forming carbamate.Example comprises tin catalyst such as dibutyl tin laurate, two lauric acid dioctyl tins, two sad dibutyl tin and stannous octoates, iron catalyst such as etheric acid iron and iron protochloride, and tertiary amine catalyst such as triethylamine and triethylenediamine.
Preferably be controlled at the add-on that has the compound of reactive hydrogen and uncle's amino in the one molecule, make it fall into 1 to 100mg-KOH/g, more preferably 5 in the 95mg-KOH/g scope, based on the amine value of reaction back dispersion resin.When the amine value was lower than above-mentioned scope, dispersion stabilization was tending towards reducing, and when the amine value surpassed above-mentioned scope, developing performance was tending towards reducing.When isocyanate groups remains in the above-mentioned reacted dispersion resin, preferably destroy remaining isocyanate groups with alcohol or aminocompound, improve the time-dependent stability of dispersion resin thus.
Dispersion agent is general 10 to 300 weight % with respect to the content of the coloring material in the colored resin composition, preferred 20 to 100 weight %, preferred especially 30 to 80 weight %.When the dispersion agent components contents was too low, the adsorptive power of itself and coloring material was not enough, therefore can not prevent agglomeration.This causes thickening or gelling sometimes.On the other hand, when content is too high, film thick, and structure cell takes place during forming and controls failure at interval in liquid crystal cells after forming colour filter sometimes.Therefore not preferred at above-mentioned extraneous content.
[1-3-2] nitrogenous graft copolymer
For nitrogenous graft copolymer, preferably in its main chain, has the graft copolymer of nitrogen atom repeating unit.Wherein, preferably have the repeating unit of following general formula (I) expression and/or the graft copolymer of the repeating unit that formula (II) is represented.
Figure A20071014718700301
(wherein, R 1Expression has the alkylidene group of 1 to 5 carbon atom, and A represents that hydrogen atom or following formula (III) to (V) represent any one group).
R in following formula (I) 1Expression has chain or sub-branched alkyl such as methylene radical, ethylidene or the propylidene of 1 to 5 carbon atom, wherein preferably has the alkylidene group of 2 or 3 carbon atoms, more preferably ethylidene.A represents any one group of hydrogen atom or following formula (III) to (V), preferred formula (III) expression.
Figure A20071014718700302
In formula (II), R 1With A have with formula (I) in R 1The implication identical with A.
Figure A20071014718700303
In formula (III), W 1Expression has the chain-like structure or the sub-branched alkyl of 2 to 10 carbon atoms, wherein preferably has the alkylidene group of 4 to 7 carbon atoms, as butylidene, pentylidene and hexylidene.P represents 1 to 20 integer, preferred 5 to 10 integer.
Figure A20071014718700311
In formula (IV), Y 1The expression divalent linker, the alkylidene group of preferred 1 to 4 carbon atom such as ethylidene or propylidene, or the alkylene oxide group of 1 to 4 carbon atom such as inferior ethoxyl or inferior propoxy-.W 2Chain-like structure or sub-branched alkyl such as ethylidene, propylidene or the butylidene of 2 to 10 carbon atoms of expression wherein preferably have the alkylidene group of 2 or 3 carbon atoms.Y 2The expression hydrogen atom or-CO-R 2(R 2Expression has the alkyl of 1 to 10 carbon atom, as ethyl, propyl group, butyl, amyl group or hexyl, and the alkyl of wherein preferred 2 to 5 carbon atoms such as ethyl, propyl group, butyl or amyl group).Q represents 1 to 20 integer, preferred 5 to 10 integer.
Figure A20071014718700312
In last formula V, W 3Table 1 is to the alkyl of 50 carbon atoms or have the hydroxyalkyl of 1 to 5 hydroxyl and 1 to 50 carbon atom, the alkyl such as the octadecyl of wherein preferred 10 to 20 carbon atoms, or have the hydroxyalkyl such as the monohydroxy octadecyl of 1 or 2 hydroxyl and 10 to 20 carbon atoms.
Formula (I) or the content of repeating unit in graft copolymer of the present invention of (II) representing are high more good more.This content is generally 50mol% or more, preferred 70mol% or more.This graft copolymer can have the repeating unit of formula (I) expression and the repeating unit of formula (II) expression simultaneously, and its content is than not restriction especially.The repeating unit content of formula (I) is the bigger the better.Formula (I) or (II) total amount of repeating unit of expression be generally 1 to 100, preferred 10 to 70, more preferably 20 to 50.Graft copolymer can comprise the repeating unit except that formula (I) and repeating unit (II).The example of other repeating unit comprises alkylidene group and alkylene oxide group.Graft copolymer of the present invention preferably have as its end group-NH 2Or-R 1-NH 2(R wherein 1Have and above-mentioned R 1Identical implication).
To notice that graft copolymer of the present invention can be chain-like structure or branching.
The weight-average molecular weight of dispersion agent is preferably 3000 to 100000, preferred especially 5000 to 50000 (measuring by GPC).When weight-average molecular weight is lower than 3000, can not prevents the coloring material agglomeration, and thickening or gelling take place sometimes.On the other hand, when it surpassed 100000, it is not enough that the retrogradation of dispersion agent own and its solubleness in organic solvent become.In above-mentioned extraneous weight-average molecular weight is not preferred.
Dispersion agent is generally 10 to 300 weight % with respect to the coloring material components contents in the coloured composition, preferred 20 to 100 weight %, preferred especially 30 to 80 weight %.When the dispersion agent components contents was too low, the adsorptive power deficiency of itself and coloring material can not prevent agglomeration like this.So sometimes, cause thickening or gelling.On the other hand, when content was too high, it is too thick that film becomes, and the liquid crystal cells after forming colour filter structure cell takes place sometimes during forming and controls failure at interval.Therefore not preferred at above-mentioned extraneous content.
This dispersion agent can be synthetic with currently known methods, for example can use the method that is described among the clear 63-30057 of Japanese patent application.
A-B segmented copolymer and/or B-A-B segmented copolymer that [1-3-3] is made up of the B block of block A that has quaternary ammonium salt in its side chain and no quaternary ammonium salt
The block A that constitutes the segmented copolymer of dispersion agent has quaternary ammonium salt, and is preferred-N +R 1aR 2aR 3aY -(condition is R to the quaternary ammonium salt of expression 1a, R 2aAnd R 3aRepresent hydrogen atom or can substituted ring texture or the alkyl of chain-like structure or R independently of one another 1a, R 2aAnd R 3aIn at least two mutually coupling form ring structure, Y -The expression counter ion) quaternary ammonium salt of expression.This quaternary ammonium salt can be directly and the main chain bonding maybe can be by divalent linker and main chain bonding.
-N +R 1aR 2aR 3aY -In, R 1a, R 2aAnd R 3aIn the example of the ring structure that forms of at least two mutual couplings comprise that 5-to 7-unit contains two fused rings that condense acquisition in azepine monocycle and these the assorted monocycles.Nitrogen heterocyclic ring preferably is not an aromatic nucleus, wherein more preferably saturated heterocyclic.Be concrete example below:
Figure A20071014718700321
(wherein R shows R 1aTo R 3aIn any one).
These ring structures can have other substituting group.
For-N +R 1aR 2aR 3aY -In R 1aTo R 3a, more preferably can have the alkyl of substituent 1 to 3 carbon atom and can have a substituent phenyl.
For block A, especially preferably has the block of the part-structure of following formula (1) expression.
(in formula (1), R 1a, R 2aAnd R 3aRepresent hydrogen atom or can substituted chain-like structure alkyl or R independently of one another 1a, R 2aAnd R 3aIn at least two mutually coupling form ring structure, R 4aExpression hydrogen atom or methyl, X represents divalent linker, Y -The expression counter anion).
In following formula (1), divalent linker X comprise alkylidene group with 1 to 10 carbon atom, arylidene ,-CONH-R 5a-and-COO-R 6a-(condition is R 5aAnd R 6aRepresent direct key independently of one another, have the alkylidene group of 1 to 10 carbon atom or have 1 to 10 carbon atom ether (R 7a-O-R 8a-: R 7aAnd R 8aRepresent alkylidene group independently of one another)), preferred-COO-R 6a-.
As Y -The example of counter anion comprise Cl -, Br -, I -, ClO 4 -, BF 4 -, CH 3COO -And PF 6 -
A block A can have two or the more a plurality of part-structure that contains above-mentioned specific quaternary ammonium salt.In the case, these contain two of quaternary ammonium salt or more a plurality of part-structure and introduce among the block A with random copolymers or segmented copolymer form.Block A can have the part-structure that does not contain quaternary ammonium salt.The example of this part-structure comprises the part-structure of (methyl) acrylate-ester-monomer derived, and this structure will be described below.
Although the content of this no quaternary ammonium salt (quaternary-ammonium-base-free) part-structure among the block A is preferably 0 to 50 weight %, more preferably 0 to 20 weight %, most preferably block A does not contain this no quaternary ammonium moiety structure.
On the other hand, the B block that constitutes the dispersion agent segmented copolymer comprises the polymer architecture that obtains by the copolymerization comonomer, the example of these comonomers is styrene monomers, as vinylbenzene and alpha-methyl styrene, (methyl) acrylate monomer is as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) glycidyl acrylate, (methyl) benzyl acrylate, (methyl) Hydroxyethyl acrylate, ethyl propylene acid glycidyl ester and (methyl) vinylformic acid N, the N-dimethylamino ethyl ester; (methyl) acrylate monomers is as (methyl) vinylformic acid muriate; (methyl) acrylamide monomer is as (methyl) acrylamide, N hydroxymethyl acrylamide, N,N-DMAA and N, N-dimethylaminoethyl acrylamide; Vinyl-acetic ester; Vinyl cyanide; Glycidyl allyl ether and Ba Dousuan glycidyl ether; With N-methacrylic morpholide.
B block is preferably the part-structure derived from (methyl) acrylate monomer of following formula (II) expression.Term used herein " (methyl) acrylic acid or the like " and " (methyl) acrylate " are represented " acrylic acid or the like or methacrylic " and " acrylate or methacrylic ester " respectively.For example " (methyl) vinylformic acid " is meant " acrylic or methacrylic acid ".
(in formula (II), R 9aExpression hydrogen atom or methyl, R 10aExpression can have the alkyl of a substituent ring texture or chain-like structure, can have a substituent allyl group and maybe can have a substituent aralkyl).
A B block can comprise the part-structure of above-mentioned two or more (methyl) acrylate-ester-monomer derived.Obviously, this B block comprises the part-structure except that them.When the part-structure of two or more monomer derived is present in the B block of no quaternary ammonium salt, the each several part structure can random copolymers or the segmented copolymer form introduce in the B block.When B block comprised part-structure except that (methyl) acrylate-monomer-deutero-part-structure, the content of part-structure in B block except that (methyl) acrylate monomer was preferably 0 to 50 weight %, more preferably 0 to 20 weight %.B block does not most preferably comprise the part-structure except that (methyl) acrylate A monomer.
Be used for A-B block or the B-A-B segmented copolymer type polymer compound of dispersion agent of the present invention for each free block A and B block composition, this segmented copolymer for example can be by following living polymerization preparation.
Living polymerization comprises living anion polymerization, cation activity polymerization and radical living polymerization.Living anion polymerization uses negatively charged ion as the polymerization activity material, and preferably by following path representation:
The radical living polymerization method for example provides in below the path, and wherein the polymerization activity material is a free radical.
(living anion polymerization method)
When
Monomer 1:
Figure A20071014718700351
Monomer 2:
Figure A20071014718700352
Figure A20071014718700353
Organo-metallic (M) compound
Figure A20071014718700355
Figure A20071014718700356
(radical living polymerization method: the nitroxyl method)
When
Monomer 1:
Figure A20071014718700361
Monomer 2:
Figure A20071014718700362
Figure A20071014718700363
(radical living polymerization method: the ATRP method)
When
Monomer 1:
Figure A20071014718700371
Monomer 2:
Figure A20071014718700373
The dispersion agent that uses among the present invention can be synthetic according to the known way of describing in the document below for example: Japanese patent laid-open 9-62002, " P.Lutz, P.Masson; et al., Polym.Bull.12,79 (1984) ", " B.C.Anderson, G.D.Andrews, et al.; Macromolecules, 14,1601 (1981) ", " K.Hatada, K.Ute, et al.; Polym.J.17,977 (1985), 18; 1037 (1986) ", " Koichi Migite and Koichi Hatada, Polymer Application; 36,366 (1987) ", " Toshinobu Higashimura; Mitsuo Sawamoto, Kobunshi Ronbunshu, 46; 189 (1989) ", " M.Kuroki, T.Aida, J.Am.Chem.Sic., 109,4737 (1987) "; " Takuzo Aida and Shohei Inoue, J.Syn.Org.Chem.Jap., 43,300 (1985) " or " D.Y.Sogoh, W.R.Hertler, et al., Macromolecules, 20,1473 (1987) ".
Promptly being used in dispersion agent of the present invention is A-B segmented copolymer or B-A-B segmented copolymer, the block A/ B block ratio (weight ratio) that constitutes this multipolymer also fall into common 1/99 or higher, especially 5/95 or higher and be not more than 80/20 usually, be not more than in 60/40 scope especially.Outside above-mentioned scope, can not always obtain good thermotolerance and dispersion stabilization simultaneously.
Quaternary ammonium salt is generally 0.1 to 10mmol in the amount that is used for 1g A-B segmented copolymer of the present invention or B-A-B segmented copolymer.Outside this scope, can not always obtain good thermotolerance and dispersibility energy simultaneously.
This segmented copolymer can comprise during preparation the amino that produces sometimes, and its amine value is about 1 to 100mg-KOH/g." amine value " is with the amino value that obtains of sour neutralization titration alkalescence, and it is represented corresponding to the value of the acid number mg with KOH.
The acid number of this segmented copolymer is low more good more, although depend on the acidic group kind that whether exists or be used to measure acid number.This segmented copolymer has the common 10mg-KOH/g of acid number or lower, and has weight-average molecular weight (using polystyrene standards to measure) 1000 or bigger, but is no more than 100,000.The molecular weight of segmented copolymer is lower than 1000 and causes dispersion stability to reduce, and is tending towards reducing developing performance and resolving power and surpass 100,000.Necessary is that segmented copolymer is the graft copolymer of nitrogen atom.In the present invention, use the combination of this specific dispersion agent and particular adhesive (will be described below) can be during developing between the filming of substrate and colored resin composition formation, to reach high cohesive force, and it is residual to suppress undissolved material, keeps dispersion stability simultaneously.
Dispersion agent of the present invention removes above-mentioned block copolymerization beyond the region of objective existence, the phosphorous acid esters type of preferred package dispersion agent.Add this phosphate type dispersion agent, improve the solubleness during developing.
For phosphoric acid ester, can use uncle or uncle's ester in any.Yet, consider dispersing property, preferred uncle's ester.To be included in its end with the example of structure of phosphoric acid bonding part and have for example polycaprolactone and polyethers polyoxyethylene glycol for example of the structure of hydroxyl such as polyester.It can be the multipolymer between polyester and the polyethers.This phosphoric acid ester can have two keys as (methyl) acrylate at polyester and/or polyether chain end in addition, and with the compound formation multipolymer of another free redical polymerization.
More specifically, the phosphoric acid ester with part-structure of following structural formula (3) expression is preferred.
Figure A20071014718700381
This phosphoric acid ester for example can be opened the method preparation of describing among the clear 58-128393 by clear 50-22536 of Japanese patent application or Japanese Patent spy.
This phosphate type dispersion agent has molecular weight general 200 or bigger, but is not more than 5000, preferably is not more than 1000.Add it during developing, improving solubleness, so the excessive increase of molecular weight not preferred.
This phosphate type dispersion agent is common 5 weight parts or bigger with respect to the content of 100 parts of block copolymer, preferred 10 weight parts or bigger, but be not more than 100 weight parts usually, preferably be not more than 80 weight parts.When the content of phosphoric acid ester was too low, enough solubleness did not appear during developing.On the other hand, when the content of phosphoric acid ester was too high, its effect was saturated, and on the contrary, dispersion stabilization might reduce.
[1-4] resin glue
When filter substrate prepared on the transparency carrier by liquid is applied to, colored resin composition of the present invention was suitable as coating fluid and uses.Use example as the composition of the curable colored resin composition that is used for colour filter will be described below.
Resin glue of the present invention can comprise following any resin.
[1-4-1]
In the present invention, can be used alone or in combination the resin of the structure that epoxy moieties that has the unsaturated compound (b) by containing epoxy group(ing) separately and the carboxyl addition that contains carboxy resin (a) obtain.
To containing the no particular restriction of carboxy resin (a), generally can obtain by the carboxylic polymerisable monomer of polymerization.The example of carboxylic polymerisable monomer comprises (methyl) vinylformic acid, toxilic acid (acid anhydride), Ba Dousuan, methylene-succinic acid, fumaric acid, 2-(methyl) acryloxy ethyl succinic acid, 2-acryloxy ethyl hexanodioic acid, 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy ethyl hexahydrophthalic acid, 2-(methyl) acryloxy ethyl toxilic acid, 2-(methacryloxypropyl Succinic Acid, 2-(methacryloxypropyl hexanodioic acid, 2-(methyl) propyl group acyloxy propyl group hydrogen phthalic acid, 2-(methyl) propyl group acyloxy propyl group phthalic acid, 2-(methyl) propyl group acyloxy propyl group toxilic acid, 2-(methyl) propyl group acyloxy butyl Succinic Acid, 2-(methyl) propyl group acyloxy butyl hexanodioic acid, 2-(methyl) propyl group acyloxy butyl hydrogen phthalic acid, 2-(methyl) propyl group acyloxy butyl phthalic acid, 2-(methyl) propyl group acyloxy butyl toxilic acid, by with lactone such as 6-caprolactone, beta-propiolactone, the monomer that gamma-butyrolactone or δ-Wu Neizhi and the addition of (methyl) vinylformic acid obtain and by with acid (acid anhydride) as Succinic Acid (acid anhydride), the monomer that phthalic acid (acid anhydride) or toxilic acid (acid anhydride) and the addition of hydroxyalkyl (methyl) acrylate obtain.
Wherein, preferred (methyl) vinylformic acid and 2-(methyl) acryloxy ethyl succinic acid, more preferably (methyl) vinylformic acid.Multiple in these monomers of use capable of being combined.
Carboxylic resin (a) can be the multipolymer that obtains by another monomer copolymerization with above-mentioned carboxylic polymerisable monomer and no carboxyl.Although another monomer is not had particular restriction, but its example comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) vinylformic acid cyclohexyl ester, (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid phenoxy group methyl esters, (methyl) 2-ethylhexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, glycerine list (methyl) acrylate, (methyl) vinylformic acid tetrahydrofuran base ester, vinylbenzene and its derivative, alpha-methyl styrene and big monomer are as the poly-big monomer of (methyl) methyl acrylate, the big monomer of polystyrene, the poly-big monomer of (methyl) vinylformic acid 2-hydroxyethyl ester, the big monomer of polyoxyethylene glycol, big monomer of polypropylene glycol and the big monomer of polycaprolactone.
Wherein, optimization styrene, methacrylic acid ester methyl ester, methacrylic acid cyclohexyl ester, benzyl methacrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid hydroxypropyl ester, (methyl) butyl acrylate and (methyl) isobutyl acrylate.Multiple in these monomers of use capable of being combined.
In this specification sheets, term " (methyl) propylene～" and " (methyl) acrylate " refer to " propylene～or methacrylic～" and " acrylate or methacrylic ester " respectively, for example, term " (methyl) vinylformic acid " is meant " acrylic or methacrylic acid ".
Consider the dispersibility energy of pigment, carboxylic resin (a) preferably has hydroxyl.Especially preferably contain (methyl) acrylic acid hydroxy alkyl ester as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) Propylene glycol monoacrylate or (methyl) vinylformic acid 4-hydroxyl butyl ester or glycerine list (methyl) acrylate multipolymer as comonomer.
Object lesson comprises that the polymerisable monomer of no hydroxyl is as (methyl) methyl acrylate, (methyl) benzyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid cyclohexyl ester or cyclohexyl maleimide; The polymerisable monomer of hydroxyl is as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) Propylene glycol monoacrylate or (methyl) vinylformic acid 4-hydroxyl butyl ester; (methyl) vinylformic acid.
In addition, the object lesson of preferred resin comprises (methyl) vinylformic acid/(methyl) acrylate copolymer, and wherein (methyl) methyl acrylate, (methyl) benzyl acrylate, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate or (methyl) vinylformic acid 2-hydroxyl ethyl ester are as (methyl) acrylate; Vinylbenzene/(methyl) acrylic copolymer; Vinylbenzene/alpha-methyl styrene/(methyl) acrylic copolymer; With cyclohexyl maleimide/(methyl) acrylic copolymer.
The acid number that " contains carboxy resin (a) " among the present invention is general 30 to 500KOH-mg/g, and preferred 40 to 350KOH-mg/g, and more preferably 50 to 300KOH-mg/g.When adding had the compound of ethylenically unsaturated group and epoxide group, the ratio of introducing the carboxyl of " containing carboxy resin " was general 10mol% or bigger, preferred 30mol% or bigger, but generally be not more than 90mol%, preferably be not more than 80mol%.Too low introducing has the side chain deficiency of ethylenical unsaturated double bonds than being tending towards hindering enough dispersing propertys because introduce.On the other hand, too high introducing is than the solubleness that is tending towards destroying colored resin composition.
The weight-average molecular weight that carboxylic resin (a) among the present invention has is by using the gpc measurement of polystyrene standards, general 2000 or bigger, preferred 3000 or bigger, more preferably 4000 or bigger, but generally be not more than 100000, preferably be not more than 80000, more preferably no more than 5000.When weight-average molecular weight was too low, liquid stabilising was bad, and too high weight ratio is tending towards damaging the stability of colored resin composition.
Term " unsaturated compound (b) that contains epoxy group(ing) " is meant the compound that has ethylenically unsaturated group and epoxide group in an one molecule.
The example that contains the unsaturated compound (b) of epoxy group(ing) comprises that acyclic contains the unsaturated compound of epoxy group(ing) as (methyl) glycidyl acrylate, glycidyl allyl ether, α-Yi Jibingxisuan glycidyl ester, crotonyl c glycidyl ether, glycidyl ether (different) crotonate and (methyl) vinylformic acid 4-hydroxyl butyl ester glycidyl ether.Consider thermotolerance and dispersibility energy, the preferred alicyclic epoxy unsaturated compound that contains.
The example of the alicyclic ring epoxy group(ing) of the alicyclic unsaturated compound that contains epoxy group(ing) comprises 2,3-oxirane ring amyl group, 3,4-epoxycyclohexyl and 7,8-epoxy [three rings [5.2.1.0] last of the ten Heavenly stems-2-yl] base.Preferably derived from the ethylenic unsaturated bond of (methyl) acryl.Specifically alicyclic contains the compound that the epoxy alefinically unsaturated compounds comprises (methyl) vinylformic acid (3, the 4-epoxycyclohexyl) methyl esters and following chemical formula (1) to (15) expression:
Figure A20071014718700411
(R wherein 1bExpression hydrogen atom or methyl).
Figure A20071014718700412
(R wherein 1bExpression hydrogen atom or methyl, R 2bThe alkylidene group of 1 to 10 carbon atom of expression).
Figure A20071014718700421
(R wherein 1bExpression hydrogen atom or methyl, R 2bThe alkylidene group of 1 to 10 carbon atom of expression).
Figure A20071014718700422
(R wherein 1bExpression hydrogen atom or methyl, R 2bThe alkylidene group of 1 to 10 carbon atom of expression, R 3bThe alkyl of 1 to 10 carbon atom of expression, k represents 0 or 1 to 10 integer).
Figure A20071014718700423
(R wherein 1bExpression hydrogen atom or methyl, R 2bThe alkylidene group of 1 to 10 carbon atom of expression).
Figure A20071014718700424
(R wherein 1bS represents hydrogen atom or methyl, R independently of one another 2bThe alkylidene group of 1 to 10 carbon atom of expression).
Figure A20071014718700425
(R wherein 1bS represents hydrogen atom or methyl, R independently of one another 2bThe alkylidene group of 1 to 10 carbon atom of expression).
Figure A20071014718700426
(R wherein 1bExpression hydrogen atom or methyl, R 2bThe alkylidene group of 1 to 10 carbon atom of expression).
Figure A20071014718700431
(R wherein 1bExpression hydrogen atom or methyl, R 2bThe alkylidene group of 1 to 10 carbon atom of expression).
Figure A20071014718700432
(R wherein 1bExpression hydrogen atom or methyl, R 2bThe alkylidene group of 1 to 10 carbon atom of expression).
Figure A20071014718700433
(R wherein 1bExpression hydrogen atom or methyl, R 2bThe alkylidene group of 1 to 10 carbon atom of expression).
Figure A20071014718700434
(R wherein 1bExpression hydrogen atom or methyl).
Figure A20071014718700435
(R wherein 1bExpression hydrogen atom or methyl).
Figure A20071014718700436
(R wherein 1bExpression hydrogen atom or methyl, R 2bThe alkylidene group of 1 to 10 carbon atom of expression).
(R wherein 1bExpression hydrogen atom or methyl).
At following formula (1) in (15), R 2bExample comprise methylene radical, ethylidene, propylidene and butylidene, wherein preferred methylene radical, ethylidene and propylidene.At following formula (1) in (15), preferred formula (3).
In above-claimed cpd, preferred especially (methyl) vinylformic acid 3,4-epoxycyclohexyl methyl esters.Use capable of being combined contains two or more of unsaturated compound of epoxy group(ing).
Resin with structure that the carboxyl addition of epoxy group(ing) by will being used for the unsaturated compound (b) that contains epoxy group(ing) of the present invention and carboxylic resin (a) obtains, needn't obtain with containing the reaction of epoxy unsaturated compound by carboxylic resin, but can finally have said structure.
Currently known methods can be used for unsaturated compound (b) reaction of the carboxyl and the epoxy of carboxylic resin (a).
For example, with the unsaturated compound of carboxylic resin (a) and epoxy (b under 50 to 150 ℃ of temperature of reaction in organic solvent in the presence of catalyzer stoichiometric number hours extremely tens of hours, the example of above-mentioned catalyzer is tertiary amine such as triethylamine or benzyl methylamine, quaternary ammonium salt such as chlorination dodecyl trimethyl ammonium, Tetramethylammonium chloride, etamon chloride, tetrabutylammonium chloride or benzyltriethylammonium chloride, pyridine or triphenylphosphine, wherein epoxy compounds can be introduced in the carboxyl that contains carboxy resin.
So the acid number of the resin glue of preparation is general 10 to 200KOH-mg/g, and is preferred 20 to 150, more preferably 30 to 150.Its weight-average molecular weight (Mw) by using the gpc measurement of polystyrene standards, is general 2000 or bigger, preferred 4000 or bigger, more preferably 5000 or bigger, but generally be not more than 20000, preferably be not more than 90000,, especially preferably be not more than 30000 more preferably no more than 50000.The binding agent acid number liquid stabilising of too little weight-average molecular weight is poor, and the resin glue of too big weight-average molecular weight is tending towards damaging solubleness.The ratio of resin glue in the total solid matters of colored resin composition is general 10 to 80 weight %, preferred 20 to 70 weight %.The ratio of itself and coloring material is general 20 to 300 weight %, preferred 30 to 200 weight %, more preferably 40 to 100 weight %.
[1-4-2]
In the present invention, the resin glue of the nonnitrogenous atom except that above-mentioned resin glue can be used alone or in combination.Particularly preferred resin glue has and obtains structure by the following method: with about 5 to 90mol% contain epoxy (methyl) acrylate (A) and about 10 to 95mol% another can with free redical polymerization compound (B) copolymerization of component (A) copolymerization, with the epoxide group addition of unsaturated monoprotic acid (C) with 10 to 100mol% component A, and with the hydroxyl addition of multi-anhydride (D) with the generation of 10 to 100mol% addition components (C).This resin glue will be explained below.
＜(A) contain epoxy (methyl) acrylate 〉
The example that contains epoxy (methyl) acrylate comprises (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxy butyl ester, (methyl) vinylformic acid (3, the 4-epoxycyclohexyl) methyl esters and (methyl) vinylformic acid 4-hydroxy butyl ester glycidyl ether.Wherein preferred (methyl) glycidyl acrylate.
Containing the content of epoxy (methyl) acrylate (A) in comonomer is general 5mol% or bigger, preferred 20mol% or bigger, and more preferably 30mol% or bigger, but generally be not more than 90mol%, preferably be not more than 80mol%, more preferably no more than 70mol%.Too high content causes other component concentration to reduce, and this may cause thermotolerance and intensity to reduce.Cross when low when content, the quantitative change of polymerizable components and alkali soluble constituent gets not enough.Therefore not preferred at above-mentioned extraneous content.
＜(B) can with the compound of another free redical polymerization of component (A) copolymerization
Component (B) preferably comprises list (methyl) acrylate of the structure with following formula (VI) expression:
Figure A20071014718700451
Following formula (VI), R 3To R 8Represent hydrogen atom independently of one another or have alkyl such as methyl, ethyl or the propyl group of 1 to 3 carbon atom.R 9And R 10Represent hydrogen atom independently of one another or have alkyl such as methyl, ethyl or the propyl group of 1 to 3 carbon atom, but or coupling form ring.Pass through R 9And R 10The ring that coupling forms is preferably the aliphatic hydrocrbon ring.This aliphatic hydrocrbon ring can be saturated or undersaturated, and preferably has 5 or 6 carbon atoms.
In list (methyl) acrylate of formula (VI) expression, especially preferably have following formula (VII), (VIII) or (IX) those of expression.
Figure A20071014718700461
For list (methyl) acrylate of structure with formula (VI), can use known, those of for example following structural formula (X) expression.
Figure A20071014718700462
(in following formula (X), R 11Expression hydrogen atom or methyl, R 12The group of expression (VI) representative).
The content of list (methyl) acrylate in comonomer with structure of formula (VI) is general 10mol% or bigger, preferred 15mol% or bigger, but generally be not more than 90mol%, preferably be not more than 70mol%, more preferably no more than 50mol%.List (methyl) acrylate with this structure can have improved thermotolerance and intensity.
Although to the no particular restriction of component (B), its object lesson comprise vinylbenzene and vinylbenzene α-, adjacent-,-, right-alkyl, nitro, cyano group, acid amides and ester derivative; Diolefine such as divinyl, 2, the 3-dimethylbutadiene; Isoprene and chloroprene; (methyl) acrylate is as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl ester, (methyl) vinylformic acid isopropyl esters, (methyl) n-butylacrylate, (methyl) vinylformic acid sec-butyl ester, (methyl) vinylformic acid tertiary butyl ester, (methyl) vinylformic acid pentyl ester, (methyl) vinylformic acid neo-pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid Lauryl Ester, (methyl) dodecylacrylate, (methyl) vinylformic acid cyclopentyl ester, (methyl) vinylformic acid cyclohexyl ester, (methyl) vinylformic acid 2-methylcyclohexyl ester, (methyl) vinylformic acid dicyclohexyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid adamantane esters, (methyl) vinylformic acid allyl ester, (methyl) vinylformic acid propargyl ester, (methyl) phenyl acrylate, (methyl) vinylformic acid naphthyl ester, (methyl) vinylformic acid anthryl ester, (methyl) vinylformic acid anthraquinonyl ester, (methyl) vinylformic acid piperonyl ester, (methyl) vinylformic acid salicyl ester, (methyl) vinylformic acid furyl ester, (methyl) vinylformic acid furfuryl ester, (methyl) vinylformic acid tetrahydrofuran base ester, (methyl) vinylformic acid pyranyl ester, (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid styroyl ester, (methyl) vinylformic acid cresyl ester, (methyl) vinylformic acid 1,1,1-trifluoroethyl ester, (methyl) vinylformic acid perfluor ethyl ester, (methyl) vinylformic acid perfluor n-propyl ester, (methyl) vinylformic acid perfluor isopropyl esters, (methyl) vinylformic acid trityl group ester, (methyl) vinylformic acid cumyl ester, (methyl) vinylformic acid 3-(N, N-dimethylamino) propyl diester, (methyl) vinylformic acid 2-hydroxyethyl ester and 1 (methyl) vinylformic acid 2-h hydroxypropyl ester; (methyl) acrylamide is as (Methacrylamide (methyl) vinylformic acid N, N-diformamide, (methyl) vinylformic acid N, N-diethylamide, (methyl) vinylformic acid N, N-dipropyl acidamide, (methyl) vinylformic acid N, N-diisopropyl amide and (methyl) vinylformic acid anthryl acid amides; Vinyl compound is as (methyl) vinylformic acid N-anilide, (methyl) propylene acyl cyanide, propenal, vinylchlorid, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine and vinyl-acetic ester; Unsaturated carboxylic acid diester such as citraconic acid diethyl ester, ethyl maleate, DEF and diethyl itaconate; Single maleimide such as N-phenylmaleimide, N-cyclohexyl maleimide, N-lauryl maleimide and N-(4-hydroxyphenyl) maleimide; And N-(methyl) acryl maleimide.At least a compound that use is selected from vinylbenzene, (methyl) vinylformic acid benzyl ester and the single maleimide is effective for obtaining further improved thermotolerance and intensity.
The content of component (B) in comonomer is general 10mol% or bigger, preferred 20mol% or bigger, and more preferably 30mol% or bigger, but generally be not more than 95mol%, preferably be not more than 80mol%, more preferably no more than 70mol%.Too high component (B) content causes the add-on (because of component (A) reduces) of insufficient polymerizable components and alkali soluble constituent, and too low content infringement thermotolerance and intensity.Therefore not preferred at above-mentioned extraneous content.
＜(C) unsaturated monoprotic acid 〉
With contained epoxide group addition in the multipolymer of unsaturated monoprotic acid (C) and 10 to 100mol% components (A) and component (B).
For component (C), can use known substance, as have the carboxylic acid of ethylenic unsaturated bond.Object lesson comprise monocarboxylic acid such as vinylformic acid, methacrylic acid, Ba Dousuan, neighbour-,-or to vinyl benzoic acid, and (methyl) vinylformic acid of replacing of α-alkylhalide group, alkoxyl group, halogen, nitro or cyano group.Wherein, preferred vinylformic acid and methacrylic acid.
The additional proportion of contained epoxide group is general 10mol% or bigger in the multipolymer of component (C) with respect to component (A) and component (B), preferred 30mol% or bigger, and more preferably 50mol% or bigger, but generally be not more than 100mol%.When this ratio is too low, exist the residual epoxide group unfriendly influence time rely on the danger of stability etc.
＜(D) multi-anhydride 〉
Multi-anhydride (D) is added to the hydroxyl addition that forms on the epoxide group of multipolymer of component (A) and component (B) with 10 to 100mol% by component (C).
Add multi-anhydride (D) so that resin glue of the present invention is alkaline soluble, and can use known unit acid anhydrides.Example comprises dibasic acid anhydride such as maleic anhydride, Succinic anhydried, itaconic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride and chlorendic anhydride; Multi-anhydride is as 1,2,4-benzenetricarboxylic anhydride, pyromellitic acid dianhydride, benzophenone tetracarboxylic anhydride and biphenyltetracarboxyacid acid acid anhydride.Wherein, preferred Tetra Hydro Phthalic Anhydride and Succinic anhydried.
The additional proportion of multi-anhydride is general 10mol% or bigger, preferred 20mol% or bigger, more preferably 30mol% or bigger, but generally be not more than 100mol%, preferably be not more than 90mol%, more preferably no more than 80mol%, calculate by all hydroxyls that are shaped as by component (C) and adding of epoxide group.Too high additional proportion reduces film sometimes and keeps ratio during developing, and low excessively additional proportion makes the solubleness deficiency.
＜prepare the method for resin glue 〉
Known solution polymerization process is adopted in the copolyreaction of component (A) and component (B).Although do not have particular restriction to being used for the polymeric solvent, if its inertia in radical polymerization, can use normally used organic solvent.Object lesson comprises ethyl acetate, acetate isopropyl esters, ethylene glycol monomethyl ether acetate such as cellulose ethanoate and butyl cellulose acetic ester; Diglycol monotertiary alkyl oxide acetic ester such as glycol ether monomethyl ether acetate, Trivalin SF acetic ester and acetate of butyl carbitol; The propylene-glycol monoalky lether acetic ester; Acetic ester such as dipropylene glycol monoalky lether acetate; Ethylene glycol bisthioglycolate alkyl oxide, glycol ether dialkyl ether such as methyl carbitol, ethyl carbitol and diethylene glycol monobutyl ether; The triglycol dialkyl ether; The propylene glycol dialkyl ether; The dipropylene glycol dialkyl ether; Ether is as 1,4-dioxane and tetrahydrofuran (THF); Ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and pimelinketone; Hydrocarbon such as benzene,toluene,xylene, octane and decane; Petroleum solvent such as sherwood oil, raw gasline, hydrogenation raw gasline and industrial naptha; Lactate such as methyl lactate; Lactate such as methyl lactate, ethyl lactate and n-Butyl lactate; Methyl-sulphoxide and N-Methyl pyrrolidone.These solvents can use separately or use with its two or more mixing.
The consumption of solvent is general 30 weight parts or bigger, preferred 50 weight parts or bigger, but generally be not more than 1000 weight parts, preferably be not more than 800 weight parts, by 100 weight part resin glues.Make it be difficult to control molecular weight in above-mentioned extraneous amount.
Do not have particular restriction to being used for initiator of the present invention,, can use normally used organic peroxide catalyst and azo-compound as long as it can cause radical polymerization.Object lesson comprises the known compound that is categorized as ketone peroxide, ketal peroxide, hydroperoxide, diallyl superoxide, diacyl peroxide, mistake ester and crosses two carbonic ethers.Azo-compound also is effective.
Object lesson comprises benzoyl peroxide; dicumyl peroxide; the peroxidation di-isopropyl; peroxidation two-tertiary butyl; TBPB tertiary butyl perbenzoate; uncle's hexyl perbenzoate; t-butyl peroxy-2-ethylhexanoate; uncle's hexyl peroxide-2-ethylamino benzonitrile acid esters; 1; two (t-butyl peroxy)-3 of 1-; 3; the 5-trimethyl-cyclohexane; 2; 5-dimethyl-2; two (t-butyl peroxy) hexyls-3 of 5-; 3-sec.-propyl hydroperoxide; tert-butyl hydroperoxide; the superoxide dicumyl; the dicumyl hydroperoxide; acetyl peroxide; two (4-tert-butylcyclohexyl) crosses two carbonic ethers; di-isopropyl is crossed two carbonic ethers; the peroxidation isobutyl-; 3; 3; 5-trimethyl acetyl base superoxide; lauroyl peroxide; 1; two (t-butyl peroxy) 3 of 1-; 3; the 5-trimethyl-cyclohexane; 1; two (the uncle's hexyl peroxides) 3 of 1-; 3, the 5-trimethylcyclohexanone; the two carboxamides of Diisopropyl azodicarboxylate and azo.According to polymerization temperature, select to have the radical initiator of suitable transformation period.
The amount of radical initiator is common 0.5 weight part or bigger, preferred 1 weight part or bigger, but generally be not more than 20 weight parts, and preferably be not more than 10 weight parts, be used for the monomer total amount of copolyreaction based on 100 weight parts.
Polymerization can be carried out by the following method: the monomer and the radical polymerization initiator that will be used for copolyreaction are dissolved in solvent, and under agitation heat gained solution, or monomer is added dropwise in the solvent that heats and stir with radical initiator.As another way, monomer dropping can be gone into by radical initiator to add in the mixture that obtains in the solvent heating then.Although reaction accent condition can freely change according to target molecular weight, temperature of reaction is general 70 ℃ or higher, preferred 80 ℃ or higher, but generally be not more than 150 ℃, preferably be not more than 130 ℃.Reaction times is general 2 hours or bigger, preferred 3 hours or bigger, but generally be not more than 20 hours, preferably be not more than 10 hours.
Multi-anhydride (D) can carry out with currently known methods with the addition to the multipolymer of the unsaturated monoprotic acid of its addition (D).
In addition, in the present invention, glycidyl (methyl) acrylate or the glycidyl ether with polymerizable unsaturated group can be added on some carboxyls that form by addition multi-anhydride (D), with further improvement photosensitivity, the glycidyl ether that maybe will not have polymerizable unsaturated group adds on some carboxyls that form by addition multi-anhydride (D), to improve developing performance.Their uses capable of being combined.Some examples of the glycidyl ether compound of no polymerizable unsaturated group comprise glycidyl ether (" DENACOL EX-111 ", " DENACOL EX-121 ", " DENACOLEX-141 ", " DENACOL EX-145 ", " DENACOL EX-146 ", " DENACOLEX-171 " and " DENACOL EX-192 " with phenyl or alkyl, all be trade(brand)name, the product of Nagase Kasei Kogyo).
Resin glue of the present invention has weight-average molecular weight (Mw), by GPC (gel permeation chromatography) general 2000 or bigger, preferred 3000 or bigger, more preferably 5000 or bigger, be not more than 100000 usually, preferably be not more than 50000, more preferably no more than 10000, especially preferably be not more than 8000.Weight-average molecular weight is lower than 2000 and causes bad thermotolerance and film strength, and weight-average molecular weight causes insufficient developer solubility above 100000.In above-mentioned extraneous weight-average molecular weight is not preferred.When using the die head coating, weight-average molecular weight preferably is not more than 10000, does the agglomeration aggravation when preventing to be coated with at the die lip top.Molecular weight distribution (Mw/Mn) is preferably 2 to 5.
The content of resin glue in colored resin composition of the present invention is general 10 weight % or bigger, and preferred 20 weight % or bigger, but generally be not more than 80 weight % preferably are not more than 70 weight %, separately based on the total solids of resin combination.The ratio of resin glue and coloring material is general 20 weight % or bigger, preferred 30 weight % or bigger, and more preferably 50 weight % or bigger, but generally be not more than 500 weight %, preferably be not more than 300 weight %, more preferably no more than 200 weight %.
This resin structure is known, as finding in Japanese patent laid-open 8-297366 or Japanese Patent spy open the description of 2001-89533.Yet as mentioned above, the required dispersion agent that has ad hoc structure by mixing brings required effect.
[1-5] organic carboxyl acid, organic carboxyl acid acid anhydride
Colored resin composition of the present invention can comprise and has molecular weight 1000 or lower organic carboxyl acid and/or organic carboxyl acid acid anhydride.When composition comprised the amino formate dispersion agent as dispersion agent, it was preferred adding it.
The example of organic carboxyl acid compound comprises aliphatic carboxylic acid and aromatic carboxylic acid.The object lesson of aliphatic carboxylic acid comprises monoprotic acid such as formic acid, propionic acid, butyric acid, valeric acid, PIVALIC ACID CRUDE (25), caproic acid, oxyacetic acid, vinylformic acid and methacrylic acid; Dicarboxylic acid such as oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, cyclohexane dicarboxylic acid, cyclohexane dicarboxylic acid, methylene-succinic acid, citraconic acid, toxilic acid and fumaric acid; With tricarboxylic acid such as tricarballylic acid and equisetic acid (aconitic acid).Aromatic carboxylic acid comprises the carboxylic acid that has with the phenyl Direct Bonding carboxyl of phenylformic acid, phthalic acid etc.; With the carboxylic acid that has by carbon bond and phenyl Direct Bonding carboxyl.Wherein, molecular weight preferred 600 or lower, preferred especially 50 to 500, more specifically, preferred toxilic acid, Succinic Acid and methylene-succinic acid.
The example of organic acid carboxylic acid anhydride comprises aliphatic carboxylic acid acid anhydride and aromatic tricarboxylic acid anhydride.The object lesson of aliphatic carboxylic acid acid anhydride comprises diacetyl oxide, Trichloroacetic anhydride, trifluoroacetic anhydride, Tetra Hydro Phthalic Anhydride, Succinic anhydried, maleic anhydride, itaconic anhydride, Pyroglutaric acid, 1,2-cyclohexane dicarboxylic acid acid anhydride, Octadecane base Succinic anhydried and 5-norbornylene-2, the 3-dicarboxylic anhydride.The example of aromatic tricarboxylic acid anhydride comprises Tetra hydro Phthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, pyromellitic acid dianhydride and naphthalic anhydride.Wherein, preferably have molecular weight 600 or lower, particularly 50 to 500 those, particularly, preferred maleic anhydride, Succinic anhydried and itaconic anhydride.
Organic carboxyl acid and/or the content of organic carboxyl acid acid anhydride in total solid matters are general 0.01 to 10 weight %, preferred 0.03 to 5 weight %, more preferably 0.05 to 3 weight %.
Add molecular weight and be not more than the residual quantity of the not dissolved substance that 1000 organic carboxyl acid and/or organic carboxyl acid acid anhydride can reduce coloured composition.Although molecular weight is not more than the method that 1000 organic carboxyl acid adds in the colored resin composition to be proposed in patent 3293171, but the cohesive force that image-region has taken place in the method inevitably reduces, and the result is tending towards taking place that the development edge narrows down, pixel is peeled off and white defective.According to the present invention, in the combination of dispersion agent and resin glue, add organic carboxyl acid and/or organic carboxyl acid acid anhydride and can not cause this phenomenon, but only effective to the residual quantity that reduces dissolved substance not.
[1-5] photopolymerizable monomer
Although photopolymerizable monomer is not had particular restriction,, but preferably has the addition polymerization compound (this compound is hereinafter referred to as " olefinic compounds ") of at least one olefinic double bond as long as it is the lower molecular weight polymerizable compound.Olefinic compounds is the compound with an olefinic double bond, when the pigmentary resin composition is exposed to activation ray following time, addition polymerization and crosslinked by the effect of polymerization starter (will be described below) takes place.In the present invention, term " monomer " is meant the notion opposite with so-called polymer substance, except the monomer of narrow sense, also comprises dimer, tripolymer and oligopolymer.
The example of olefinic compounds comprises the esters of unsaturated carboxylic acids of monohydroxy compound; the esters of unsaturated carboxylic acids of aliphatic series polyol; the esters of unsaturated carboxylic acids of fragrance polyol; can pass through the ester of unsaturated carboxylic acid, poly carboxylic acid and polyol such as above-mentioned aliphatic series polyol or fragrant polyol esterification acquisition and react the olefinic compounds that obtains and have the carbamate skeleton by polyisocyanate compound and the oxy-compound that contains (methyl) acryl.
The esters of unsaturated carboxylic acids of aliphatic series polyol comprises glycol diacrylate, triethylene glycol diacrylate, Viscoat 295, trimethylolethane trimethacrylate acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, Dipentaerythritol tetraacrylate, Dipentaerythritol five acrylate, dipentaerythritol acrylate and glycerine acrylate.Other example comprises methacrylic acid, itaconic ester, crotonate and maleic acid ester, and the acrylate moiety by these acrylate becomes methacrylic acid moieties, methylene-succinic acid part, Ba Dousuan part and toxilic acid respectively and partly obtains.
The esters of unsaturated carboxylic acids of fragrance polyol comprises quinhydrones diacrylate, quinhydrones dimethacrylate, Resorcinol diacrylate, Resorcinol dimethacrylate and biphenyl 3 phenol triacrylate.
The ester that obtains by unsaturated carboxylic acid, poly carboxylic acid and polyol esterification can respectively do for oneself one matter or mixture.Typical example comprises the condenses of vinylformic acid, phthalic acid and ethylene glycol, the condenses of vinylformic acid, toxilic acid and glycol ether, the condenses of methacrylic acid, terephthalic acid and tetramethylolmethane, and the condenses of vinylformic acid, hexanodioic acid butyleneglycol and glycerine.
Comprise aliphatic vulcabond such as hexamethylene diisocyanate or trimethylammonium hexamethylene diisocyanate by polyisocyanate compound and the oxy-compound reaction olefinic compounds that obtain and that have the carbamate skeleton that contains (methyl) acryl; alicyclic diisocyanate such as cyclohexyl diisocyanate or isophorone diisocyanate; or aromatic diisocyanate such as tolylene diisocyanate or diphenylmethanediisocyanate and contain the oxy-compound such as the vinylformic acid 2-hydroxyethyl ester of (methyl) acryl; methacrylic acid 2-hydroxyethyl ester; 3-hydroxyl (1; 1; 1-three acryloyl-oxy ylmethyls) propane or 3-hydroxyl (1; 1,1 trimethylammonium propenyl acyloxy methyl) reactor product of propane.
In addition, olefinic compounds of the present invention can use acrylamide such as ethylenebis acrylamide, allyl ester such as diallyl phthalate and contain the compound such as the phthalic acid divinyl ester of vinyl.
The mixing ratio of olefinic compounds in the total solids of colored resin composition of the present invention is general 0 weight % or bigger, preferred 5 weight % or bigger, more preferably 10 weight % or bigger, but generally be not more than 80 weight %, preferably be not more than 70 weight %, more preferably no more than 50 weight %, especially preferably be not more than 40 weight %.The ratio of itself and coloring material is general 0 weight % or bigger, preferred 5 weight % or bigger, more preferably 10 weight % or bigger, preferred especially 20 weight % or bigger, but generally be not more than 200 weight %, preferably be not more than 100 weight %, more preferably no more than 80 weight %.
[1-6] Photoepolymerizationinitiater initiater system
When colored resin composition of the present invention comprises olefinic compounds as monomer component, the preferred Photoepolymerizationinitiater initiater system component that has direct absorb light or also generated polymerization activation free radical by the photosensitization function with induced decomposition reaction or hydrogen abstraction reaction thus that adds.Term used herein " Photoepolymerizationinitiater initiater system component " is meant the mixture of Photoepolymerizationinitiater initiater, promotor and additive such as photosensitive colored dose.
The example that constitutes the polymerization starter of Photoepolymerizationinitiater initiater system component comprises metallocene compound such as titanocene compound, for example describes among clear 59-152396 of Japanese Patent Application Laid-Open and the clear 61-151197 of Japanese Patent Application Laid-Open; Free radical activator such as hexa-aryl bi-imidazole derivative, monochloromethyl-s-pyrrolotriazine derivatives, N-aryl-a-amino acid such as N-phenylglycine, N-aryl-alpha-amino group hydrochlorate and N-aryl-α-An Jisuanzhi, for example the Japanese Patent spy opens and describes among clear 58-403023, the clear 45-37377 of Japanese patent application and the Japanese patent laid-open 10-39503; And dialkyl benzene ethyl ketone, bitter almond oil camphor and thioxanthone derivates, " Fine Chemicals " (Vol.20 for example, No.4, March 1 issue, 16-26 (1991)) describe in, but and luxuriant and xanthene dye or alpha-aminoalkyl benzophenone compound of titanium and have the system that the compound that contains the addition polymerization ethylenic unsaturated bond of amino or carbamate groups is used in combination wherein.
The object lesson that can be used for polymerization starter of the present invention comprises:
Halomethylation pyrrolotriazine derivatives such as 2-(4-p-methoxy-phenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-methoxyl group naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-oxyethyl group naphthyl)-4, two (trichloromethyl)-s-triazines of 6-and 2-(4-ethoxy carbonyl naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-;
The  oxadiazole derivative of halomethylation such as 2-trichloromethyl-5-(2 '-benzofuryl)-1,3,4- diazole, 2-trichloromethyl-5-[β-(2 '-benzofuryl) vinyl]-1,3,4- diazole, 2-trichloromethyl-5-[β-(2 '-(6 "-benzofuryl) vinyl)]-1,3,4- diazole and 2-trichloromethyl-5-furyl-1; 3,4- diazole;
Imdazole derivatives such as 2-(2 '-chloro-phenyl-)-4,5-diphenyl-imidazole dimer, 2-(2 '-chloro-phenyl-)-4, two (3 '-p-methoxy-phenyl) imidazoles dimers of 5-, 2-(2 '-fluorophenyl)-4,5-diphenylimidazolidin-4-one dimer, 2-(2 '-p-methoxy-phenyl)-4,5-diphenyl-imidazole dimer and (4 '-p-methoxy-phenyl)-4,5-diphenyl-imidazole dimer;
Benzoin alkylether such as benzoin methyl ether, bitter almond oil camphor phenyl ether, bitter almond oil camphor isobutyl ether and bitter almond oil camphor isopropyl ether;
Anthraquinone derivative such as 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone and 1-chloroanthraquinone;
Benzophenone derivative such as benzophenone, Michler ketone, 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chlorobenzophenone and 4-bromo benzophenone and 2-carboxyl benzophenone;
Acetophenone derivs is as 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 2,2-diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-aminomethyl phenyl acetone, 1-hydroxyl-1-methylethyl-(right-isopropyl phenyl) ketone, 1-hydroxyl-1-(right-dodecylphenyl) ketone, 2-methyl-(4 '-(methyl sulphur) phenyl)-2-morpholine-1-acetone and 1,1,1-trichloromethyl-(right-butyl phenyl) ketone;
Thioxanthone derivates such as thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-clopenthixal ketone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone and 2,4-di-isopropyl thioxanthone;
Benzoate derivatives such as right-dimethylaminobenzoic acid ethyl ester and right-diethylamino ethyl benzoate; Acridine derivatives such as 9-phenylacridine and 9-(right-p-methoxy-phenyl) acridine; The azophenlyene derivative is as 9,10-dimethylbiphenyl azophenlyene;
Anthracyclinone derivatives such as benzanthrone;
The luxuriant derivative of titanium is as two-cyclopentadienyl-Ti-two-chlorine, two-cyclopentadienyl-Ti-pair-phenyl, two-cyclopentadienyl-Ti-two-2,3,4,5,6-penta fluoro benzene-1-base, two-cyclopentadienyl-Ti-two-2,3,5,6-tetra fluoro benzene-1-base, two-cyclopentadienyl-Ti-is two-2,4,6-trifluoro-benzene-1-base, two-cyclopentadienyl-Ti-2,6-two-fluorobenzene-1-base, two-cyclopentadienyl-Ti-2,4-two fluorobenzene-1-base, two-methyl cyclopentadienyl-Ti-two-2,3,4,5,6-penta fluoro benzene-1-base, two-methyl cyclopentadienyl-Ti-is two-2,6-two-fluorobenzene-1-base and two-cyclopentadienyl-Ti-2,6-two-fluoro-3-(pyr-1-yl)-benzene-1-base; With
Alpha-aminoalkyl benzophenone compound such as 2-methyl isophthalic acid-[4-(methyl sulphur) phenyl]-2-morpholine propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1-; 4-dimethyl aminoethyl benzoic ether, 4-dimethylamino isoamylbenzene manthanoate, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino Propiophenone, 2-ethylhexyl-1; 4-dimethylaminobenzoic acid ester, 2, two (the 4-diethylamino benzylidene) pimelinketone of 5-, 7-diethylamino-3-(4-diethylamino benzoyl) tonka bean camphor and 4-(diethylamino) phenyl styryl ketone.
As the promotor that constitutes the Photoepolymerizationinitiater initiater system component, for example, can use N, N-dialkylamino phenylformic acid alkyl ester such as N, N-dimethylaminobenzoic acid ethyl ester, have heterocyclic sulfhydryl compound such as 2-mercaptobenzothiazole, 2-sulfydryl benzoxazol and 2-mercaptobenzimidazole and aliphatic multifunctional sulfhydryl compound.For each Photoepolymerizationinitiater initiater and promotor, two or more compounds can be used as mixture.
The blending of Photoepolymerizationinitiater initiater system component in colored resin composition total solids of the present invention is than being general 0.1 weight % or bigger, preferred 0.5 weight % or bigger, more preferably 0.7 weight % or bigger, but generally be not more than 30 weight %, preferably be not more than 20 weight %, more preferably no more than 10 weight %.Cross low blending than becoming the reason of reduction sometimes to exposing light beam susceptibility.Too high blending causes the failure of developing than sometimes, reason is that the solubleness of unexposed portion in photographic developer is low.Although multiple Photoepolymerizationinitiater initiater and multiple promotor can be mixed use, preferably combination is used imdazole derivatives, alpha-aminoalkyl benzophenone compound and is contained the heterocyclic sulfhydryl compound.
For improving induction sensitivity, can sensitizing dye be added in the Photoepolymerizationinitiater initiater system component on demand according to the wavelength of visual exposure light source.The example of sensitizing dye comprises the xanthane dyestuff, as be described among Japanese patent laid-open 4-221958 and the flat 4-219756 of Te Kai, has the heterocyclic coumarine dye, as be described among Japanese patent laid-open 3-239703 and the flat 5-289335 of Te Kai, 3-ketone coumarin compound, as be described among Japanese patent laid-open 3-239703 and the flat 5-289335 of Te Kai, methylene pyrroles (pyrromethene) dyestuff, as be described among the Japanese patent laid-open 6-19240, and dyestuff, as be described in the Japanese Patent spy and open clear 47-2528 and the clear 54-155292 of Te Kai with dialkyl amido benzene skeleton, the clear 45-37377 of Japanese patent application, open clear 48-84183 with the Japanese Patent spy, the spy opens clear 52-112681, the spy opens clear 58-15503, the spy opens clear 60-88005, the spy opens clear 59-56403, Te Kaiping 2-69, the spy opens clear 57-168088, Te Kaiping 5-107761, among the flat 4-288818 of Te Kaiping 5-210240 and Te Kai.
In these sensitizing dyves, preferably contain amino-sensitizing dye, more preferably in an one molecule, have the compound of amino and phenyl.More preferred example comprises that the benzophenone compound is as 4,4 '-dimethylamino benzophenone, 4,4 '-diethylamino benzophenone, 2-Uvinul A Plus, 4-Uvinul A Plus, 4,4 '-diamino benzophenone, 3,3 '-diamino benzophenone and 3,4-diamino benzophenone; With contain right-dialkyl amido phenyl-compound such as s2-(right-dimethylaminophenyl) benzoxazol, 2-(right-the diethylamino phenyl) benzoxazol, 2-(right-dimethylaminophenyl) benzo [4,5] benzoxazol, 2-(right-dimethylaminophenyl) benzo [6,7] benzoxazol, 2, two (right-the diethylamino phenyl) 1 of 5-, 3,4- azoles, 2-(right-dimethylaminophenyl) benzothiazole, 2-(right-the diethylamino phenyl) benzothiazole, 2-(right-dimethylaminophenyl) benzoglyoxaline, 2-(right-the diethylamino phenyl) benzoglyoxaline, 2, two (right-the diethylamino phenyl) 1 of 5-, 3, the 4-thiadiazoles, (right-dimethylaminophenyl) pyridine, (right-the diethylamino phenyl) pyridine, (right-dimethylaminophenyl) quinoline, (right-the diethylamino phenyl) quinoline, (right-dimethylaminophenyl) pyrimidine and (right-the diethylamino phenyl) pyrimidine, wherein most preferably 4,4 '-the dialkyl amido benzophenone.
The blending of sensitizing dye in colored resin composition of the present invention is than being general 0 weight % or bigger, preferred 0.2 weight % or bigger, more preferably 0.5 weight % or bigger, but generally be not more than 20 weight %, preferably be not more than 15 weight %, more preferably no more than 10 weight %, according to the total solids meter of chromoresin composition.
[1-7] other solid
As mentioned above, if need, colored resin composition of the present invention can comprise the solid except that said components.These solid examples comprise dispersing auxiliary, tensio-active agent, thermal polymerization inhibitor, softening agent, shelf-stable agent, surface protectant, bonding improving agent and development improving agent.For example can use pigment derivative as dispersing auxiliary.
The example of pigment derivative comprises the derivative of azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone (quinophthalone), iso-dihydro-indole, two  piperazines, anthraquinone, indanthrene, perylene, perinone, diketopyrrolo-pyrrole (diketopyrrolopyrrole) and two  piperazine pigment.The substituting group of pigment derivative be for example with pigment skeleton Direct Bonding or sulfonic group, sulfoamido or its quaternary salt by alkyl, aryl or heterocyclic radical bonding, phthalimido methyl, dialkyl amino alkyl, hydroxyl, carboxyl, amide group etc.Preferred sulfoamido or its quaternary salt and sulfonic group, wherein more preferably sulfonic group.Pigment skeleton can be by a plurality of replacements in these substituting groups, or pigment derivative can be the different mixtures that replace the compound of numbers.The object lesson of pigment derivative comprise sulfonic acid, the phthalocyanine pigment of azo pigment sulfonic acid, quinophthalone pigment sulfonic acid, anthraquinone pigment sulfonic acid, quinacridone pigment sulfonic acid, diketopyrrolo-pyrrole pigment sulfonic acid and the sulfonic acid of two  piperazine pigment.
For improving dispersing of pigments performance and dispersion stabilization, can add pigment derivative or its analogue as dispersion agent.The example of pigment derivative comprises the derivative of azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, iso-dihydro-indole, isoindoline, two  piperazines, anthraquinone, indanthrene, perylene, perinone, diketopyrrolo-pyrrole and two  piperazine pigment.The substituting group of pigment derivative be for example with pigment skeleton Direct Bonding or sulfonic group, sulfoamido or its quaternary salt by alkyl, aryl or heterocyclic radical bonding, phthalimido methyl, dialkyl amino alkyl, hydroxyl, carboxyl, amide group etc.Preferred sulfoamido or its quaternary salt and sulfonic group, wherein more preferably sulfonic group.The pigment skeleton can be by a plurality of replacements in these substituting groups, or pigment derivative can be the different mixtures that replace the compound of numbers.The object lesson of pigment derivative comprise sulfonic acid, the phthalocyanine pigment of azo pigment sulfonic acid, quinophthalone pigment sulfonic acid, the sulfonic acid of isoindoline pigment, the sulfonic acid of anthraquinone pigment, the sulfonic acid of quinacridone pigment, the sulfonic acid of diketopyrrolo-pyrrole (diketopyrrolopyrrole) pigment and the sulfonic acid of two  piperazine pigment.Wherein, the sulfonic acid of the sulfonic acid of the sulfonic acid of the sulfonic acid of the sulfonic acid of the sulfonic acid of the sulfonic acid of the sulfonic acid of the sulfonic acid of preferred pigments Huang 138, pigment yellow 13 9, Pigment red 254, Pigment red 255, Pigment red 264, Pigment red 272, Pigment red 209, pigment orange 71 and pigment Violet 23, the wherein more preferably sulfonic acid of the sulfonic acid of pigment yellow 13 8 and Pigment red 254.Pigment derivative is general 0.1 weight % or bigger but be not more than 30 weight % with respect to the amount of pigment, preferably is not more than 20 weight %, more preferably no more than 10 weight %, further more preferably no more than 5 weight %.When this amount too hour, not exclusively show its effect, but too big amount is destroyed dispersing property and dispersion stabilization.
Although any useful as surfactants in negatively charged ion, positively charged ion, nonionic and the amphoterics, it is preferred using nonionogenic tenside, because it has very low disadvantageous effect to various performances.Tensio-active agent is general 0.001 weight % or bigger with respect to the concentration of total composition, preferred 0.005 weight % or bigger, more preferably 0.01 weight % or bigger, 0.03 weight % or bigger most preferably, but generally be not more than 10 weight %, preferably be not more than 1 weight %,, most preferably be not more than 0.3 weight %. more preferably no more than 0.5 weight %
As the example of thermal polymerization inhibitor, use quinhydrones, right-methoxyphenol, 1, catechol, 2, the 6-tertiary butyl-p-Cresol and 2-Naphthol.The amount of thermal polymerization inhibitor by the total solids of composition, is preferably 0 weight % or bigger but be not more than 3 weight %.
For softening agent, use dioctyl phthalate (DOP), phthalic acid dodecyl ester, triethylene glycol dieaprylate, phthalic acid dimethyl diol ester, tritolyl phosphate, Octyl adipate, Uniflex DBS and triacetyl glycerine.The amount of softening agent by the total solids of composition, preferably is not more than 10 weight %.
[2] feature of colored resin composition (resist)
Colored resin composition of the present invention (resist) owing to use above-mentioned concrete binding agent and dispersion agent, therefore have feature such as good perviousness, during developing with the substrate high adhesive property and the low residue of dissolved substance not.If necessary, it can have feature such as low viscosity velocity of variation, good fusion again and high voltage holding ratio.These features will be described below.
[2-1] through performance
For through performance, the reflectivity of each red, green and blue color pixel is based on the observed value assessment that obtains by following method, and this method will specifically describe below.
The colored resin composition that will assess is applied on the square glass substrate of 5cm (" AN100 ", the product of Asahi Glass) by spin-coating method, then this substrate is heated 3 minutes on 80 ℃ of hot plates.With the whole surface of substrate at exposure energy 100mJ/cm 2Following exposure, the 0.1% weight sodium carbonate aqueous solution of following with 23 ℃ sprays development 30 seconds under hydraulic pressure 0.3MPa.This substrate was toasted 30 minutes down at 230 ℃ in the hot air circulate baking oven.Control coating condition is so that thickness the satisfying in color coordinate in the cie color system of baking after stain resin combination film: x=0.60 (to redness), y=0.55 (for green) and y=0.14 (for blueness) (light source C separately).
With Hitachi, the spectrophotometric " U-3500 " that Ltd. produces is used to measure colourity.
Red colored resin combination of the present invention has in the cie color system in the scope that the Y value falls into following The Representation Equation:
Y≥200y-41.4(y＜0.34)
Y≥100y-7.4(y≥0.34)
This Y value preferably falls in the scope of one of following equation:
Y≥200y-40.9(y＜0.34)
Y≥100y-6.9(y≥0.34)
Green coloring resin combination of the present invention has in the cie color system in the scope that the Y value falls into following The Representation Equation:
Y≥240x-7.1
This Y value preferably falls in the scope of following equation:
Y≥240x-6.6
Blue-colored resin combination of the present invention has in the cie color system in the scope that the Y value falls into following The Representation Equation:
Y≥20x+16.2
This Y value preferably falls in the scope of following equation:
Y≥20x+16.4
Use the present invention to have good diactinic colored resin composition, improve the transmitance of colour filter thus, and then improved LCD brightness, this helps forming bright-coloured image.
[2-2] development cohesive force
The development cohesive force is according to the minimum pattern width assessment of measuring by the following method.This method will specifically describe below.
The colored resin composition that will assess is applied to the build that obtains 1.3 μ m on the glass substrate.With it at 60 ℃ down after dry 1 minute, with substrate 110 ℃ of following heat dryings 2 minutes, then with it at exposure energy 300mJ/cm 2Descend by 150 μ m slits through having the test photomask exposure of the linear open section that is provided with at interval with live width 1 μ m.Then, then with the 0.1% weight sodium carbonate aqueous solution under 23 ℃ of photographic developer temperature at hydraulic pressure 0.2kg/cm 2Under developed 60 seconds, then water is at hydraulic pressure 3kg/cm 2Following spray washing 30 seconds forms pattern thus.Measure then as the residual minimum pattern width of line image.
Colored resin composition of the present invention has minimum pattern width 10 μ m or lower, preferred 8 μ m or lower.
The colored resin composition that uses the present invention to have the premium properties cohesive force can form no white defective and have high-quality colour filter.
[2-3] do not dissolve resistates
Do not dissolve the spectral reflectance assessment that the amount of resistates is measured by the following method.This method will specifically describe below.
30 * 100mm part of the non-pixel region (on obscure glass) of the colour filter that the colored resin composition that use will be assessed obtains is at pressure 1kgf/cm 2The following cloth made from mean sizes 3 μ m or littler polyester macrofiber (for example " Toraysee MK Clean Cloth ", the product of Toray Industries) friction.Gained cloth is fixed on the square round log end of 1cm * 1cm that resin is made, and it is used the 0.1cc alcohol dipping by suction pipe.The spectral reflectance of the 1cm * 1cm of this cloth is by " UV-3100S ", and (spectrophotometer that it is made for Shimadzu Corporation) measured under the condition of using integrating sphere.Table 5 is given in λ=500nm (being equivalent to red resistates), 450nm (being equivalent to green resistates) and the spectral reflectance of 550nm when (being equivalent to blue residue).
Among the present invention, respectively be equivalent to red 500nm, be equivalent to green 450nm and the spectral reflectance that is equivalent under the blue 550nm is 95% or bigger, preferred 97% or bigger.
Use the present invention's remaining colored resin composition that does not seldom dissolve resistates on substrate can form the high quality colour filter, this colour filter does not have and sees through or contrast gradient reduces, and cause hardly ito thin film peel off or during liquid crystal forms step sealing property reduce.
[2-4] viscosity velocity of variation
The viscosity velocity of variation is assessed as follows, and this method will be discussed in more detail below.
Just prepared the back and this resin combination places 7 days in 23 ℃ thermostatic bath after at the colored resin composition that will assess, with Toki Sangyo Co., the viscosity (20rpm) of E type viscometer " RE-80L " the measurement composition that Ltd. makes.
The viscosity variation that colored resin composition of the present invention produced after 7 days is not more than 10% with respect to initial viscosity, preferably is not more than 5%, more preferably no more than 3%.
Therefore colored resin composition of the present invention has the low viscosity velocity of variation, has good storing stability, it can be under the same process condition life-time service.
[2-5] be resolvability again
Resolvability is assessed by the following method again.This method will be explained below in detail.
The colored resin composition that utilizes spin-coating method to assess is spun on and obtains the dry film that thickness is 2.5 μ m on the square glass substrate of 50mm.After the dry air 60 minutes, substrate is soaked in the solvent of this colored resin composition of 6.25g, make it redispersion after, began to soak 10 minutes, use NikkisoCo., " Microtrac UPA " analysing particulates distribution of sizes that Ltd. makes, and based on this volume calculated median size mv.
Colored resin composition of the present invention has volume average particle size 200nm or lower in redispersion liquid, preferred 150nm or lower
The colored resin composition that the present invention has good resolvability again forms foreign matter in die ends because of dry agglomeration hardly, has therefore suppressed foreign matter inductive defective and can form the high quality colour filter by high yield.
[2-6] voltage retention
Voltage retention is assessed by the following method.This method is specific explanations below.
Preparation has the square non-alkali glass (" AN-100 " at 2.5cm, the product of Asahi Glass) the electrode base board A of the ito thin film that forms on the side surface of substrate and has the electrode base board B that is formed centrally (wherein the wide taking-up electrode of 2mm is connected with the square ito thin film of 1cm) in glass substrate one side of the square same type of 2.5cm.On electrode base board A and B by behind the spin application aligning film material (" Sunever 7492 ", the product of Nissan Chemical), with its on 110 ℃ hot plate dry 1 minute.In this hot air circulate baking oven, they were heated 1 hour down at 200 ℃, form the thick film of 70nm thus.
The electrode base board A that utilizes spin-coating method that the colored resin composition of each embodiment is scribbled aligning film material goes up and heating 3 minutes on 80 ℃ hot plate.With whole surface at exposure energy 100mJ/cm 2After the following exposure, under hydraulic pressure 0.3MPa, spray development 30 seconds, then in 230 ℃ hot air circulate baking oven, toasted 30 minutes with 23 ℃ of 0.1 weight % aqueous sodium carbonate.Control coating condition is to obtain the coloured composition film of thickness 1.7 μ m after baking.After the Resins, epoxy that will contain the silicon-dioxide bead of diameter 5 μ m by divider is applied to the periphery that has been coated with the electrode base board B of oriented layer thereon, the surface of the coating colored resin composition of this electrode of substrate A is arranged at the reverse side of gained substrate, simultaneously with its outward flange displacement 3mm separately.They were heated 2 hours under pressurized adhesion in 180 ℃ hot air circulate baking oven.Liquid crystal (" MLC-6846-000 ", Merck Ltd., the product of Japan) is injected so acquisition negative crystal born of the same parents, and divide the sealing agent sealing at its edge with UV-curable, so finish the liquid crystal cells that is used for the measuring voltage conservation rate this structure cell.With the annealing of gained liquid crystal cells (in the hot air circulate baking oven, heating 2.5 hours under 105 ℃), pulsed voltage 5V is put on each electrode base board A and the B with pulse-repetition 60Hz, thus the measuring voltage conservation rate.
In the present invention, voltage retention is generally 80% or bigger, and preferred 90% or bigger.
The colour filter with high voltage holding ratio with colored resin composition of the present invention forms produces display defect hardly in the time of in being installed in liquid-crystal display, therefore have high quality.
[3] preparation colored resin composition (liquid coating that is used for colour filter)
The preparation method of colored resin composition of the present invention is described below.
At first take by weighing coloring material, solvent and the dispersion agent of predetermined amount.In the dispersion treatment step, coloring material is disperseed to prepare thus the colored resin composition (liquid of similar printing ink) of liquid form.In this dispersion treatment step, can use lacquer setter, sand mill, ball mill, roller mill, burrstone mill, micronizer mill, homogenizer or its analogue.By this dispersion, coloring material can be converted into fine particle, so can improve the coating characteristics of colored resin composition, and improve transmitance as the filter substrate of product.
When the dispersion staining material, preferably use resin glue or dispersing auxiliary combination as needs.For the resin glue that uses between matter era at dispersion staining, preferred especially use has the resin that adds to the structure that obtains on the carboxy moiety of carboxylic resin by the epoxy moieties of the unsaturated compound that will contain epoxy.On the other hand, when coloring material is dispersed in the sand mill, preferably use diameter 0.1 to several millimeters granulated glass sphere or zirconium white bead.Coloring material is in temperature common 0 ℃ or higher, preferred room temperature or higher, but generally be not higher than 100 ℃, preferably not being higher than 80 ℃ disperses down. and jitter time is controlled on demand, because reasonably the time changes according to the composition of the liquid of similar printing ink { coloring material, solvent and have the dispersion agent of nitrogen-containing functional group }, sand mill size etc.
In will liquid, sneak into the photopolymerizable monomer, photopolymerization initiator system composition of coloring material, solvent, resin glue and non-essential predetermined amount and be mixed with the homodisperse liquid solution with other component except that said components by the similar printing ink that disperse to obtain.Be preferably alkali soluble resin with the resin glue of the liquid mixing of similar printing ink.The epoxy moieties of the above-mentioned evenly unsaturated compound (b) by containing epoxy group(ing) and the no nitrogen-atoms resin glue of the structure of the carboxyl addition acquisition of carboxylic resin (a); By 5 to 90mol% contain epoxy (methyl) acrylate (A) with 10 to 95mol% can and another free redical polymerization compound (B) polymerization of component (A) copolymerization, with the epoxy group(ing) addition of unsaturated monoprotic acid (C) and 10 to 100mol% components (A) with multi-anhydride (D) and 10 to the 100mol% photosensitive resins that obtain by the hydroxyls of addition (C) generation; And have weight-average molecular weight Mw2000 to 10000; Or the like be particularly preferred.Above-mentioned resin can use with another resin combination.
Preferred bases soluble resin (in the case, " resin " is meant the resin with weight-average molecular weight 1000 or bigger (passing through gpc measurement)) more than 60 weight % in photosensitive colored resin combination.When the amount of alkali soluble resin was lower than 60 weight %, solubleness was not enough sometimes.
In addition, in the alkali soluble resin component, the content of the no nitrogen-atoms resin glue of the structure that the epoxy moieties with the unsaturated compound by containing epoxy group(ing) and the carboxyl addition that contains carboxy resin obtain is high more good more.It is generally 30 weight % or bigger, preferred 50 weight % or bigger, more preferably 80 weight % or bigger.When content was lower than 30 weight %, the photopolymerization effect and the photosensitivity that can not produce the unsaturated link(age) that comes from the resin reduced sometimes.
The mixing ratio of resin in photosensitive colored resin combination is general 5 to 60 weight %, and preferred 10 to 50 weight % are by the total solid weight of photosensitive colored resin combination.
During each dispersion treatment step and mixing step, fine dust can be sneaked in the liquid of the similar printing ink of gained sometimes, filters by strainer or its analogue like this.
[4] preparation filter substrate
Explained later colour filter of the present invention.
Colour filter of the present invention is characterised in that with above-mentioned colored resin composition and forms pixel on substrate.
[4-1] transparency carrier (upholder)
Transparency carrier to colour filter does not have particular restriction, as long as it is transparent and have enough intensity.The examples of material that is used for it comprises thermoplastic resin sheet, for example vibrin such as polyethylene terephthalate, polyolefin resin such as polypropylene or polyethylene, polycarbonate, polymethylmethacrylate or polysulfones; Thermosetting resin sheet such as Resins, epoxy, unsaturated polyester resin or poly-(methyl) acrylic resin; With various glass.Consider thermotolerance, preferred glass and heat-resistant resin.
The fast black base thing of transparency carrier and formation substrate can be carried out Corona discharge Treatment, ozonize or form silane coupling agent or processing such as resin such as carbamate resins film, to improve its surperficial rerum natura such as adhesive property.Transparency carrier has common 0.05mm of thickness or bigger, preferred 0.1mm or bigger, but generally is not more than 10mm, preferably is not more than 7mm.When substrate carried out the film forming processing with resin, its thickness was common 0.01 μ m or bigger, preferred 0.05 μ m or bigger, but generally be not more than 10 μ m, preferably be not more than 5 μ m.
[4-2] fast black base thing
Colour filter of the present invention can form redness, green and blue pixel image thereon and prepare then usually by the fast black base thing is covered on the transparency carrier.With the resist of above-mentioned colored resin composition as coating fluid at least a in formation black, redness, green and the blueness.Each pixel image is by following formation: coating fluid is applied on the obscure glass surface of transparency carrier (when forming the black resist), maybe when forming redness, green or blue resist, coating fluid is applied to forming on the resin black color base thing surface on the transparency carrier or being applied on the metal black color base thing surface of using chromium cpd or the formation of another shading metallic substance, follows heat drying, image exposure, development and thermofixation.
The fast black base thing forms on transparency carrier by shading metallic film or the photosensitive colored resin combination that use is used for the fast black base thing.For the shading metallic substance, use chromium cpd such as chromium metal, chromic oxide and chromium nitride, nickel/tungstenalloy etc.Can use by these materials are stacked gradually and form the multilayer that obtains.
This metal photomask generally forms by sputter.The fast black base thing is by following formation: form required film like pattern by using positive light anti-etching agent, with mix the etchant etching (when film is made by chromium cpd) that obtains with perchloric acid and/or nitric acid by cerous nitrate two ammoniums, or when film is made by another material, use the etchant etching that is fit to this material, be exclusively used in this stripper by use then and peel off positive light anti-etching agent.
In the case, at first deposit or sputter at above-mentioned metal of formation or metal oxide film on the transparency carrier by steam.After forming colored resin composition on the gained film and filming,, form the resist pattern thus with this exposure and of filming with light shield development with striped, mosaic or trilateral repeat patterns.Then the gained film etching is formed the fast black base thing.
When utilizing the fast black base thing to form the fast black base thing, use the colored resin composition that does not contain black material with colored resin composition.This fast black base thing, for example can according to be used to form mode like following redness, green and the blue pixel images category, by be used alone or in combination black colorant material such as carbon black, graphite, ferric oxide, nigrosine, cyanine is black or titanium is black, or mix the colored resin composition that contains the black colorant material that redness, green and the blue pigments chosen as required or dyestuff obtain form from inorganic or pigment dyestuff or dyestuff by using.
[4-3] forms pixel
The colored resin composition that will contain redness, green and blue a kind of coloring material is coated with on the transparency carrier that is coated with the fast black base thing thereon.After the drying, with light shield be positioned over film on.Through this light shield, carry out image exposure and development and, form pigmented layer thus if necessary thermofixation or photocuring form pixel image.The colour filter image can carry out aforesaid operations in three kinds of colors (red, green and blue) each and form.
The colored resin composition that is used for colour filter for example can be by coatings such as spin coating, the excellent coating that winds the line, flow coat, die head coating, roller coat, sprayings.Wherein, through taking all factors into consideration, preferred die head coating, because it can reduce the consumption of coating liquid greatly, not being subjected to produce moisture etc. as spin-coating method influences, and does not according to said method produce foreign matter.
Too thick filming makes the image developing difficulty, and makes slit control difficulty simultaneously in liquid crystal cells formation step.On the other hand, too thin filming is difficult to improve pigment concentration, disturbs required color to develop sometimes.The thickness of film according to elcometer, is general 0.2 μ m or bigger, preferred 0.5 μ m or bigger, and more preferably 0.8 μ m or bigger, and generally be not more than 20 μ m, preferably be not more than 10 μ m, more preferably no more than 5 μ m.
[4-4] dry coating
After being applied to colored resin composition on the substrate, the film that so obtains is preferably used hot plate, IR baking oven or convection oven drying.Dry film generally includes preliminarily dried and reheat drying.The preliminarily dried condition is chosen on demand according to performance of the siccative of the kind of solvent composition, use etc.Determine according to the performance of the moisture eliminator of the kind of solvent composition or use etc. separately drying temperature and time of drying that more specifically, drying temperature is general 40 ℃ or higher, preferred 50 ℃ or higher, but generally be not more than 80 ℃, preferably be not more than 70 ℃.Be general 15 seconds or longer time of drying, and preferred 30 seconds or longer, it generally was no more than 5 minutes, preferably was no more than 3 minutes.
The reheat drying preferably is higher than under the preliminarily dried temperature in temperature carries out.More specifically, this temperature is general 50 ℃ or higher, preferred 70 ℃ or higher, but generally be not higher than 200 ℃, and preferably be not higher than 160 ℃, especially preferably be not higher than 130 ℃.Change according to Heating temperature time of drying, but be general 10 seconds or longer, and preferred 15 seconds or longer, and generally no longer than 10 minutes, preferably no longer than 5 minutes.Drying temperature is high more, and is good more with the cohesive force of substrate.Drying will be decomposed resin glue and be induced thermopolymerization under too high temperature, and this can cause the failure of developing by chance.In addition, the drying step of film can be by under reduced pressure carrying out, and is dry under elevated temperature not in promptly when decompression.
[4-5] step of exposure
Image exposure carries out on filming by minus base article pattern being covered colored resin composition, and by this mask pattern, film is exposed under ultraviolet or the visible light source.For preventing to reduce the photosensitivity of photopolymerizable layer,, can form the oxygen screen layer as behind the polyvinyl alcohol layer on the photopolymerizable layer, exposing if necessary because of oxygen.The light source that is used for image exposure there is not particular restriction.The example of light source comprises lamp such as xenon lamp, halogen lamp, tungsten lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc and luminescent lamp and laser such as argon laser, YAG laser, excited state laser, nitrogen laser, helium cadmium laser and semiconductor laser.When being exposed to specific wavelength following time, film can use spectral filter.
[4-6] development step
Colour filter of the present invention can be by following production: will be with filming that colored resin composition of the present invention obtains with above-mentioned light source exposure, then with organic solvent or contain tensio-active agent and the development of the aqueous solution of basic cpd, on substrate, form image thus.This aqueous solution further comprises organic solvent, buffer reagent, coordination agent dyestuff or pigment.
The example of basic cpd comprises inorganic alkaline compound, as sodium hydroxide, potassium hydroxide, lithium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, water glass, Starso, sodium phosphate, potassiumphosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate and ammonium hydroxide, organic basic compound such as monoethanolamine, diethanolamine or trolamine thanomin, single methylamine, dimethylamine or Trimethylamine 99, mono aminoethane, diethylamine or triethylamine, single isopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine (DIPA) or tri-isopropanolamine, ethyleneimine, the ethylene imines, Tetramethylammonium hydroxide (TMAH) and choline.In these basic cpds two or more use with form of mixtures.
The example of tensio-active agent comprises nonionogenic tenside such as Voranol EP 2001, polyoxyethylene alkylaryl ether, polyxyethylated ester, alkyl sorbitol dehydration ester and single monoglyceride alkyl ester, anion surfactant such as alkylbenzene sulfonate, sulfonated alkyl naphathalene, alkyl-sulphate, alkylsulfonate, sulfosuccinate and amphoterics such as alkyl betaine and amino acid.
Representative examples of organic comprises Virahol, benzylalcohol, ethyl cellulose, butyl cellulose, benzyl cellulose, propylene glycol and diacetone alcohol.When making up, can use these organic solvents separately with the aqueous solution.
Although development conditions is not had particular restriction, development temperature is common 10 ℃ or higher, particularly 15 ℃ or higher, and more preferably 20 ℃ or higher, generally be not higher than 50 ℃, particularly be not higher than 45 ℃, more preferably no higher than 40 ℃.Development can develop, spray development by dip-coating, brush to develop and ultrasonic development in any carry out.
Colour filter of the present invention also can will contain solvent, phthalocyanine pigment by (1) and be applied on the substrate as coloring material and the polyimide curable colored resin composition as resin glue, and the mode that forms pixel image by etching is produced then.In addition, it can use the colored resin composition that contains phthalocyanine pigment as coloring printing ink by for example (2), and directly forms the method production of pixel image on transparency carrier by printer; Or (3) use the colored resin composition contain phthalocyanine pigment as galvanic deposit liquid, immerses this substrate in galvanic deposit liquid and the method that makes on the ITO electrode sedimentary coloured film be shaped to predetermined pattern is carried out.Another example of this method comprises that (4) coating contains the colored resin composition of phthalocyanine pigment, and the gained film is applied on the transparency carrier, peels off this film, and carries out image exposure and develop forming pixel image; (5) use the colored resin composition contain phthalocyanine pigment as coloring printing ink and form the method for pixel image by ink-jet printer.According to the method for the colored resin composition that is used for colour filter, choose suitable method and produce colour filter.
[4-7] thermofixation is handled
With the colour filter thermofixation after developing.As the thermofixation condition, the temperature range of choosing is common 100 ℃ or higher, preferred 150 ℃ or higher, but generally be not higher than 280 ℃, preferably be not higher than 250 ℃.The thermal curing time of choosing is 5 minutes or longer, but no longer than 60 minutes.The pattern of finishing a kind of color after one group of these step forms.Should organize sequence of steps repeats to form colour filter thus to form black, redness, green and blue pattern.The patterning order of these four kinds of colors is not subjected to the restriction of above-mentioned order.
[4-8] forms transparency electrode
Colour filter of the present invention form on the image as the transparency electrode of ITO etc. after, be used as the parts of colour or liquid-crystal display.Be to improve surface flatness and weather resistance, the topcoat that polymeric amide or polyimide are made covers on the image on demand.In using as plane interscan pattern (IPS pattern), some does not form transparency electrode.
[5] liquid-crystal display (plate)
The method of production liquid-crystal display of the present invention (plate) is described below.Liquid-crystal display of the present invention is generally produced by the following method: form alignment films on colour filter of the present invention, the spacing piece spraying on this alignment films, by substrate opposed with it is connected to form liquid crystal cells, is poured into this liquid crystal in the gained liquid structure cell; And it is connected with opposite electrode.As alignment films, resin molding is to suit as polyimide film.For forming alignment films, adopt intaglio printing and/or flexographic printing usually, and the thickness of alignment films is tens nanometer.After baking and the curing, the alignment films of so solidifying and obtaining is carried out surface treatment by being exposed under the ultraviolet ray or using cloth to wipe with to wipe away.So can obtain to help to regulate the condition of surface that liquid crystal tilts.
The size of spacing piece is determined according to the slit (at interval) between alignment films and the opposite electrode substrate, but common preferred 2 to 8 μ m.The light spacing piece of being made by transparent resin film (PS) forms on filter substrate by photolithography, and can be used for substituting spacing piece.Usually substrate for array is made opposed electrode base board, preferred especially TFT (thin film transistor).
Panel with counter substrate is aimed at the slit and is changed according to the purposes of liquid-crystal display, but the scope of selecting for use usually is 2 μ m or thicker but be not more than 8 μ m.Panel is with after counter substrate is aimed at, and part that will be except that liquid crystal injecting port is with sealing agent such as epoxy sealing.The sealing agent is solidified down by being exposed to UV ray and/or heating, thus in its peripheral encapsulated liquid crystals unit.
To be cut into each panel at the liquid crystal cells of its periphery sealing.Liquid crystal injecting port is immersed in the liquid crystal, reduce the pressure in the vacuum chamber simultaneously.Then, be packed in the liquid crystal cells by the pressure seepage in the chamber.Pressure in the liquid crystal cells is reduced to common 1 * 10 -2Pa or bigger, preferred 1 * 10 -3Pa or bigger, but generally be not more than 1 * 10 -7Pa preferably is not more than 1 * 10 -6Pa.When pressure reduces, preferably heat liquid crystal cells.Heating temperature is common 30 ℃ or higher, preferred 50 ℃ or higher, but be not higher than 100 ℃ usually, preferably be not higher than 90 ℃.During pressure reduced, this heating was kept 10 minutes or longer usually, but is no more than 60 minutes usually.Then liquid crystal cells is immersed in the liquid crystal.Be filled with the liquid crystal injecting port of the liquid crystal cells of liquid crystal by UV curable resin sealing, so finish liquid-crystal display (LCD panel).
Kind to liquid crystal does not have particular restriction, as long as it is usually lytropic liquid crystals, the thermotropic liquid crystal of known as fragrance, aliphatic series or polynuclear compound.For thermotropic liquid crystal, known nematic liquid crystal, smectic liquid crystal and courage steroid (cholesteric) liquid crystal.Wherein anyly all can use.
Embodiment
Following the present invention will more specifically describe by preparation example, embodiment and comparative example.The invention is not restricted to or not limited by these embodiment, only otherwise leaving main points of the present invention gets final product.Among the description embodiment below, " umber " is meant " weight part ".
＜embodiment 1 to 18 and comparative example 1 to 13 〉
＜synthesis example 1〉synthetic adhesive resin a
Propylene glycol methyl ether acetate (145 weight part) is stirred under nitrogen replacement and be heated to 120 ℃.Be added dropwise to the mono acrylic ester (" FA-513M ", Hitachi, the product of Ltd.) that vinylbenzene (20 weight part), 57 parts of glycidyl methacrylate and 82 weight parts have tricyclodecane skeleton, and under 120 ℃ continuously stirring 2 hours again.The nitrogen replacement of reactor adds 0.7 weight part, three-dimethylaminomethyl phenol and 0.12 weight part quinhydrones in 27 parts by weight of acrylic acid after replacing with air displacement, and 120 ℃ of following successive reactions 6 hours.Then, add 52 weight part Tetra Hydro Phthalic Anhydrides (THPA) and 0.7 weight part triethylamine, then 120 ℃ of reactions 3.5 hours.So to have a weight-average molecular weight Mw about 15000 for the resin glue that obtains, and passes through gpc measurement.
＜synthesis example 2〉synthetic adhesive resin b
Propylene glycol methyl ether acetate (145 weight part) is stirred under nitrogen replacement and be heated to 120 ℃.Be added dropwise to the mono acrylic ester (" FA-513M ", Hitachi, the product of Ltd.) that vinylbenzene (10 weight part), 71 parts of glycidyl methacrylate and 82 weight parts have tricyclodecane skeleton, and under 120 ℃ continuously stirring 2 hours again.The nitrogen replacement of reactor adds 0.9 weight part, three-dimethylaminomethyl phenol and 0.15 weight part quinhydrones in 34 parts by weight of acrylic acid after replacing with air displacement, and 120 ℃ of following successive reactions 6 hours.Then, add 65 weight part Tetra Hydro Phthalic Anhydrides (THPA) and 0.8 weight part triethylamine, then 120 ℃ of reactions 3.5 hours.So to have a weight-average molecular weight Mw about 17000 for the resin glue that obtains, and passes through gpc measurement.
＜synthesis example 3〉synthetic adhesive resin c
Propylene glycol methyl ether acetate (145 weight part) is stirred under nitrogen replacement and be heated to 120 ℃.Be added dropwise to the mono acrylic ester (" FA-513M " that methacrylic acid benzyl ester (18 weight part), 10 parts of methyl methacrylates, 71 parts of glycidyl methacrylate and 62 weight parts have tricyclodecane skeleton, Hitachi, Ltd. continuously stirring 2 hours again product), and under 120 ℃.The nitrogen replacement of reactor adds 0.9 weight part, three-dimethylaminomethyl phenol and 0.15 weight part quinhydrones in 34 parts by weight of acrylic acid after replacing with air displacement, and 120 ℃ of following successive reactions 6 hours.Then, add 65 weight part Tetra Hydro Phthalic Anhydrides (THPA) and 0.8 weight part triethylamine, then 120 ℃ of reactions 3.5 hours.So to have a weight-average molecular weight Mw about 13000 for the resin glue that obtains, and passes through gpc measurement.
＜synthesis example 4〉synthetic adhesive resin d
Propylene glycol methyl ether acetate (145 weight part) is stirred under nitrogen replacement and be heated to 120 ℃.Be added dropwise to vinylbenzene (30 weight part) and 34 weight part methacrylic acids, and under 120 ℃ continuously stirring 2 hours again.The nitrogen replacement of reactor adds 0.9 weight part, three-dimethylaminomethyl phenol and 0.15 weight part quinhydrones in 51 parts by weight of acrylic acid (3, the 4-epoxycyclohexyl) methyl esters after replacing with air displacement, and 120 ℃ of following successive reactions 6 hours.So to have a weight-average molecular weight Mw about 18000 for the resin glue that obtains, and passes through gpc measurement.
＜synthesis example 5〉synthetic adhesive resin e
Propylene glycol methyl ether acetate (145 weight part) is stirred under nitrogen replacement and be heated to 120 ℃.Be added dropwise to methacrylic acid benzyl ester (53 weight part), 40 parts of methyl methacrylates and 26 weight part methacrylic acids, and under 120 ℃ continuously stirring 2 hours again.The nitrogen replacement of reactor adds 0.9 weight part, three-dimethylaminomethyl phenol and 0.15 weight part quinhydrones in 40 parts by weight of acrylic acid (3, the 4-epoxycyclohexyl) methyl esters after replacing with air displacement, and 120 ℃ of following successive reactions 6 hours.So to have a weight-average molecular weight Mw about 16000 for the resin glue that obtains, and passes through gpc measurement.
＜synthesis example 6〉synthetic adhesive resin a '
Propylene glycol methyl ether acetate (145 weight part) is stirred under nitrogen replacement and be heated to 120 ℃.Be added dropwise to the mono acrylic ester (" FA-513M ", Hitachi, the product of Ltd.) that vinylbenzene (20 weight part), 57 parts of glycidyl methacrylate and 82 weight parts have tricyclodecane skeleton, and under 140 ℃ continuously stirring 2 hours again.The nitrogen replacement of reactor adds 0.7 weight part, three-dimethylaminomethyl phenol and 0.12 weight part quinhydrones in 27 parts by weight of acrylic acid after replacing with air displacement, and 120 ℃ of following successive reactions 6 hours.Then, add 52 weight part Tetra Hydro Phthalic Anhydrides (THPA) and 0.7 weight part triethylamine, then 120 ℃ of reactions 3.5 hours.So to have a weight-average molecular weight Mw about 5000 for the resin glue that obtains, and passes through gpc measurement.
＜synthesis example 7〉synthetic adhesive resin b '
Propylene glycol methyl ether acetate (145 weight part) is stirred under nitrogen replacement and be heated to 120 ℃.Be added dropwise to the mono acrylic ester (" FA-513M ", Hitachi, the product of Ltd.) that vinylbenzene (10 weight part), 71 parts of glycidyl methacrylate and 82 weight parts have tricyclodecane skeleton, and under 140 ℃ continuously stirring 2 hours again.The nitrogen replacement of reactor adds 0.9 weight part, three-dimethylaminomethyl phenol and 0.15 weight part quinhydrones in 34 parts by weight of acrylic acid after replacing with air displacement, and 120 ℃ of following successive reactions 6 hours.Then, add 65 weight part Tetra Hydro Phthalic Anhydrides (THPA) and 0.8 weight part triethylamine, then 120 ℃ of reactions 3.5 hours.So to have a weight-average molecular weight Mw about 6000 for the resin glue that obtains, and passes through gpc measurement.
＜synthesis example 8〉synthetic adhesive resin c '
Propylene glycol methyl ether acetate (145 weight part) is stirred under nitrogen replacement and be heated to 120 ℃.Be added dropwise to the mono acrylic ester (" FA-513M ", Hitachi, the product of Ltd.) that vinylbenzene (20 weight part), 57 parts of glycidyl methacrylate and 82 weight parts have tricyclodecane skeleton, and under 120 ℃ continuously stirring 2 hours again.The nitrogen replacement of reactor adds 0.7 weight part, three-dimethylaminomethyl phenol and 0.12 weight part quinhydrones in 27 parts by weight of acrylic acid after replacing with air displacement, and 120 ℃ of following successive reactions 6 hours.Then, add 52 weight part Tetra Hydro Phthalic Anhydrides (THPA) and 0.7 weight part triethylamine, then 120 ℃ of reactions 3.5 hours.So to have a weight-average molecular weight Mw about 15000 for the resin glue that obtains, and passes through gpc measurement.
＜synthesis example 9〉synthetic adhesive resin d '
Propylene glycol methyl ether acetate (145 weight part) is stirred under nitrogen replacement and be heated to 120 ℃.Be added dropwise to the mono acrylic ester (" FA-5 13M ", Hitachi, the product of Ltd.) that vinylbenzene (10 weight part), 71 parts of glycidyl methacrylate methyl and 82 weight parts have tricyclodecane skeleton, and under 120 ℃ continuously stirring 2 hours again.The nitrogen replacement of reactor adds 0.9 weight part, three-dimethylaminomethyl phenol and 0.15 weight part quinhydrones in 34 parts by weight of acrylic acid after replacing with air displacement, and 120 ℃ of following successive reactions 6 hours.Then, add 65 weight part Tetra Hydro Phthalic Anhydrides (THPA) and 0.8 weight part triethylamine, then 120 ℃ of reactions 3.5 hours.So to have a weight-average molecular weight Mw about 17000 for the resin glue that obtains, and passes through gpc measurement.
＜synthesis example 10〉synthetic adhesive resin e '
Propylene glycol methyl ether acetate (145 weight part) is stirred under nitrogen replacement and be heated to 120 ℃.Be added dropwise to vinylbenzene (30 weight part) and 34 weight part methacrylic acids, and under 140 ℃ continuously stirring 2 hours again.The nitrogen replacement of reactor adds 0.9 weight part, three-dimethylaminomethyl phenol and 0.15 weight part quinhydrones in 51 parts by weight of acrylic acid (3, the 4-epoxycyclohexyl) methyl esters after replacing with air displacement, and 120 ℃ of following successive reactions 6 hours.So to have a weight-average molecular weight Mw about 8000 for the resin glue that obtains, and passes through gpc measurement.
＜synthesis example 11〉synthetic adhesive resin f '
Propylene glycol methyl ether acetate (145 weight part) is stirred under nitrogen replacement and be heated to 120 ℃.Be added dropwise to methacrylic acid benzyl ester (53 weight part), 40 parts by weight of methylmethacrylate and 26 weight part methacrylic acids, and under 140 ℃ continuously stirring 2 hours again.The nitrogen replacement of reactor adds 0.9 weight part, three-dimethylaminomethyl phenol and 0.15 weight part quinhydrones in 40 parts by weight of acrylic acid (3, the 4-epoxycyclohexyl) methyl esters after replacing with air displacement, and 120 ℃ of following successive reactions 6 hours.So to have a weight-average molecular weight Mw about 8000 for the resin glue that obtains, and passes through gpc measurement.
＜synthesis example 12〉synthetic polycaprolactone
After mixing 5 weight part lauryl alcohols, 95 weight part caprolactones and 0.003 weight part dibutyl tin laurate, in 1 hour, reaction mixture is heated to 160 ℃.After solid content reaches 99%, stop addition reaction at once.
＜synthesis example 13〉synthetic polycaprolactone
With those similar conditions that are used for synthesis example 12 under, but use methyl alcohol to replace lauryl alcohol, react.
＜synthesis example 14〉synthesis of carbamates dispersion liquid resin
Tripolymer (32 weight part) (" MITEC GP750A " with tolylene diisocyanate, the product of MitsubishiChemical, resin content: 50 weight %, 2,4 derivatives and 2, the ratio of mixture of 6 derivatives is 8: 2 mixtures, butylacetate solution) and as the dilution of 0.01 weight part dibutyl tin laurate of catalyzer and be dissolved among the 47 weight part PGMEA (propylene glycol monomethyl ether).Under agitation, being added dropwise to 14.4 weight parts has the lauryl alkoxyl group and has molecular-weight average 2 at its end, 000 polycaprolactone (obtaining in synthesis example 12) and 9.6 weight parts have the mixture of the polyoxy butyleneglycol of molecular-weight average 1,000, then react 3 hours down at 70 ℃.Then, add 1 weight part N, N-dimethyl-1, the 3-propylene diamine, and with this mixture 40 ℃ of down heating 1 hour.Gained contains the amine value of the solution of dispersion resin to be measured by neutralization, and its value is 32mg-KOH/g.Resin content is measured (resin content is based on heating 30 minutes on 150 ℃ the hot plate to remove the changes in weight calculating after desolvating) by dry method, and its value is 40 weight %.
＜synthesis example 15〉the synthesis of carbamates dispersion resin
With synthesis example 14 similar fashion, have methoxyl group and have molecular-weight average 2 at its end but use, 000 polycaprolactone (obtaining in synthesis example 13) replaces having the lauryl alkoxyl group and have molecular-weight average 2 at its end of synthesis example 14,000 polycaprolactone obtains the dispersion resin with following structure.The gained resin has acid number 32mg-KOH/g, and its resin content is 40 weight %.
＜synthesis example 16〉the synthesis of carbamates dispersion resin
With synthesis example 14 similar fashion, have methoxyl group and have molecular-weight average 2 at its end but use, 000 polycaprolactone (in synthesis example 13, obtaining) and 3-amino-1,2, the 4-triazole replaces having the lauryl alkoxyl group and have the polycaprolactone and the N of molecular-weight average 2,000, N-dimethyl-1 at its end of synthesis example 14 respectively, ammediol amine obtains dispersion resin.The gained resin has acid number 32mg-KOH/g, and its resin content is 40 weight %.
Be the structural formula of the amino formate dispersion agent of preparation in the synthesis example 14 to 16 below.
Figure A20071014718700741
In the said structure formula, R represents the arbitrary group in the following table 1 independently of one another.
Table 1
Figure A20071014718700742
*N=14, m=16,1=17 (on average)
＜synthesis example 17〉synthetic dispersing agent A '
To have the polymine (50 weight part) of molecular weight about 5000 and the polycaprolactone of 40 weight part n=5 and mix, the gained mixture will be stirred 3 hours under 150 ℃ nitrogen atmosphere with 300 weight part propylene glycol monomethyl ether.So to have a weight-average molecular weight Mw about 9000 for the synthetic dispersion agent, passes through gpc measurement.
＜synthesis example 18〉synthetic dispersing agent B '
To have the polymine (50 weight part) of molecular weight about 5000, polycaprolactone and the 6 weight part stearic acid of 40 weight part n=5 mix with 300 weight part propylene glycol monomethyl ether, the gained mixture was stirred 3 hours under 150 ℃ nitrogen atmosphere.So to have a weight-average molecular weight Mw about 9300 for the synthetic dispersion agent, passes through gpc measurement.
＜synthesis example 19〉synthetic dispersing agent C '
To have the polymine (50 weight part) of molecular weight about 10000, polycaprolactone and the 6 weight part stearic acid of 40 weight part n=5 mix with 450 weight part propylene glycol monomethyl ether, the gained mixture was stirred 3 hours under 150 ℃ nitrogen atmosphere.So to have a weight-average molecular weight Mw about 19000 for the synthetic dispersion agent, passes through gpc measurement.
＜preparation red pigment dispersion liquid 〉
In the stainless steel solvent, drop into the calcium oxide bead that 10.00 weight part C.I. Pigment reds 177 have diameter 0.5mm as coloring material, 33.75 weight part propylene glycol monomethyl ether as the dispersion agent that provides in solvent, the 6.25 weight part tables 1 and 180 weight parts, it was disperseed 6 hours by the lacquer setter, obtain the red pigment dispersion liquid thus.
＜prepare blue dispersible pigment dispersion 〉
With the C.I. pigment Blue 15: 6 (10.00 weight parts) drop in the stainless steel vessel as the calcium oxide bead that the dispersion agent that provides in solvent, the 6.25 weight part tables 1 and 180 weight parts have diameter 0.5mm as coloring material, 33.75 weight part propylene glycol monomethyl ether, and, obtain the blue pigments dispersion liquid thus by lacquer setter dispersion 6 hours.
＜preparation veridian dispersion liquid 〉
The calcium oxide bead that dispersion agent that C.I. pigment green 36 (10.00 weight part) is provided in 4 as solvent, 6.25 weight part tables 2 as coloring material, 33.75 weight part propylene glycol monomethyl ether and 180 weight parts have diameter 0.5mm drops in the stainless steel vessel, and, obtain the blue pigments dispersion liquid thus by lacquer setter dispersion 6 hours.
Table 2
A Synthetic dispersion agent in the synthesis example 3
B Synthetic dispersion agent in the synthesis example 4
C Synthetic dispersion agent in the synthesis example 5
D " Disperbyk-2000 ", the product of BYK-Chemie (modified acroleic acid based block copolymer)
E " Disparlon DA-325 ", the product of Kusumoto Chemicals (amine salt of polyether phosphate)
Table 3
Table 4
Figure A20071014718700781
＜preparation coloured composition 〉
The curable resin composition of embodiment 1 to 18 and comparative example 1-13 is by providing the composition preparation according to table 5 with above-mentioned dispersible pigment dispersion and another component in 9.
Yet, in comparative example 9, the component that in table 5 or 6, provides, add 0.33 weight part Succinic Acid as the organic carboxyl acid component.
Table 5
The component kind The component details Add-on (weight part)
Coloring material Above-mentioned pigment dispersion 10.0
Solvent Above-mentioned pigment dispersion+propylene glycol monomethyl ether 127.0
Dispersion agent Above-mentioned pigment dispersion 6.25
Resin glue The structure that following table is described 6.5
Organic carboxyl acid, the organic carboxyl acid acid anhydride The compound of describing in the following table As described in following table
Photopolymerizable monomer 1 Olefinic compounds (a) 3.25
Photopolymerizable monomer 2 Olefinic compounds (b) 3.25
Photoepolymerizationinitiater initiater system component 1 2-mercaptobenzothiazole 0.83
Photoepolymerizationinitiater initiater system component 2 Right-the dimethylaminobenzoic acid methyl esters 0.83
Photoepolymerizationinitiater initiater system component 3 Michler ketone 0.83
[notes] (1) olefinic compounds (a) is the following formula { compound that VI} represents.
(2) olefinic compounds (b) is a Viscoat 295.
Table 6
Dispersion agent Resin glue Organic carboxyl acid, the organic carboxyl acid acid anhydride
Kind Addition (weight part)
Embodiment 1 A a Succinic anhydried 0.35
Embodiment 2 B a Succinic anhydried 0.35
Embodiment 3 C a Succinic anhydried 0.35
Embodiment 4 A b Maleic anhydride 0.35
Embodiment 5 C b Maleic anhydride 0.35
Embodiment 6 A c Maleic anhydride 0.35
Comparative example 1 C d Succinic anhydried 0.35
Comparative example 2 C e Succinic anhydried 0.35
Comparative example 3 D b Succinic anhydried 0.35
Comparative example 4 E b Do not have 0
Comparative example 5 D e Do not have 0
Figure A20071014718700801
Table 7
Resin glue Multipolymer (A) and starting monomer (B) (mol%) Component (C) (addition ratio 1)) Component (D) (addition ratio 2))
Component (A) Component (B)
Glycidyl methacrylate Vinylformic acid three ring esters in the last of the ten Heavenly stems Vinylbenzene The methacrylic acid benzyl ester Methyl methacrylate Methacrylic acid Vinylformic acid Tetrahydrophthalic acid
a 40 40 20 0 0 0 88 86
b 50 40 10 0 0 0 90 82
c 50 30 0 10 10 0 90 82
d 0 0 60 0 0 40 3) 0 0
e 0 0 0 30 30 40 4) 0 0
1) component C and multipolymer (A) and (B) in the addition of contained epoxide group than (mol%)
2) component (D) with when the addition of the hydroxyl of addition component (C) time generation than (mol%)
3) methacrylic acid (3, the 4-epoxycyclohexyl) methyl esters and the addition of 70mol% methacrylic acid
4) methacrylic acid (3, the 4-epoxycyclohexyl) methyl esters and the addition of 55mol% methacrylic acid
Table 8
Resin glue Weight-average molecular weight (Mw) The starting monomer of copolymer A and B (mol%) Component (C) (addition ratio 1)) Component (D) (addition ratio 2))
Component (A) Component (B)
Glycidyl methacrylate Vinylformic acid three ring esters in the last of the ten Heavenly stems Vinylbenzene The methacrylic acid benzyl ester Methyl methacrylate Methacrylic acid Vinylformic acid Tetrahydrophthalic acid
a’ 5000 40 40 20 0 0 0 88 86
b′ 6000 50 40 10 0 0 0 90 82
c′ 15000 40 40 20 0 0 0 88 86
d′ 17000 50 40 10 0 0 0 90 82
e’ 8000 0 0 60 0 0 40 3) 0 0
f’ 8000 0 0 0 30 30 40 4) 0 0
1) component C and multipolymer (A) and (B) in the addition of contained epoxide group than (mol%)
2) component (D) with when the addition of the hydroxyl of addition component (C) time generation than (mol%)
3) methacrylic acid (3, the 4-epoxycyclohexyl) methyl esters and the addition of 70mol% methacrylic acid
4) methacrylic acid (3, the 4-epoxycyclohexyl) methyl esters and the addition of 55mol% methacrylic acid
Table 9
Dispersion agent Resin glue
Embodiment 1 A a
Embodiment 2 B a
Embodiment 3 C a
Embodiment 4 A b
Embodiment 5 C b
Embodiment 6 A c
Embodiment 7 A’ a
Embodiment 8 B’ a
Embodiment 9 C’ a
Embodiment 10 A’ b
Embodiment 11 B’ b
Embodiment 12 A’ c
Embodiment 13 A” a′
Embodiment 14 A” b′
Embodiment 15 A "+B " (weight ratio 2: 1) a′
Embodiment 16 A "+B " (weight ratio 2: 1) b′
Embodiment 17 A "+B " (weight ratio 2: 1) c′
Embodiment 18 A "+B " (weight ratio 2: 1) d′
Comparative example 1 C d
Comparative example 2 C e
Comparative example 3 D b
Comparative example 4 E b
Comparative example 5 D e
Comparative example 6 A’ d
Comparative example 7 A’ e
Comparative example 8 D’ b
Comparative example 9 A’ d
Comparative example 10 A "+B " (weight ratio 2: 1) e′
Comparative example 11 A "+B " (weight ratio 2: 1) f
Comparative example 12 C” a′
Comparative example 13 C” b′
＜embodiment 19 to 27 and comparative example 14 and 15 〉
＜synthesis example 20〉the synthetic adhesive resin (a ")
In reactor, drop into 35 parts of propylene glycol monomethyl ether, 8.8 parts of 1-methoxyl group-2-propyl alcohol and 1.5 parts of azo polymerization initiators (" V-59 ", the product of Wako Pure Chemical), then under nitrogen atmosphere, be heated to 80 ℃.In 2 hours, be added dropwise to methacrylic acid benzyl ester (9.5 parts), 6.5 parts of methyl methacrylates, 3.5 parts of 2-hydroxymethyl ethyl propenoates and 10.7 parts of methacrylic acids.This reaction mixture was stirred 4 hours, obtain polymerization liquid thus.
In the gained polymerization liquid, add 25.5 parts of propylene glycol monomethyl ether, 0.05 part of right-methoxyphenol and 0.3 part of triphenylphosphine and make its dissolving.Then with 17.5 parts of vinylformic acid (3, the 4-epoxycyclohexyl) methyl esters is added dropwise in the gained solution, carried out under 85 ℃ 24 hours so that be reflected at, obtain in its side chain, to have the solution (following this solution being called " resin glue (a ") ") of the resin of ethylenically unsaturated group thus.(a ") has weight-average molecular weight 18000 (by using the gpc measurement of polystyrene standards) to the gained resin glue, and has acid number 50 (by the result with the KOH neutralization titration).Judge that by the acid number before and after the reaction ratio of the carboxylic acid of introducing by addition vinylformic acid (3, the 4-epoxycyclohexyl) methyl esters is 66%.
＜synthesis example 21〉synthetic adhesive resin (b ")
In reactor, drop into 35 parts of propylene glycol monomethyl ether, 8.8 parts of 1-methoxyl group-2-propyl alcohol and 1.5 parts of azo polymerization initiators (" V-59 ", the product of Wako Pure Chemical), then under nitrogen atmosphere with this mixture heating up to 80 ℃.In 2 hours, be added dropwise to 10.5 parts of methacrylic acid benzyl esters, 7.5 parts of methyl methacrylates and 11.9 parts of methacrylic acids.This reaction mixture was stirred 4 hours, obtains polymerization liquid (hereinafter referred to as " resin glue (b ") thus ").(b ") has weight-average molecular weight 12000 (by using the gpc measurement of polystyrene standards) to the gained resin glue, and has acid number 120 (by the result with the KOH neutralization titration).
＜synthesis example 22〉the synthetic adhesive resin (c ")
At first, 145 parts of propylene glycol monomethyl ether are stirred under nitrogen replacement and be heated to 120 ℃.Be added dropwise to vinylbenzene (20 parts), 57 parts of glycidyl methacrylate and 82 parts of mono acrylic esters (" FA-513M ", Hitachi, the product of Ltd.), and this reaction mixture was stirred 2 hours down at 120 ℃ with tricyclodecane skeleton.
With reaction vessel with air displacement and drop into 27.0 parts of vinylformic acid, 0.7 part of three-dimethylaminomethyl phenol and 0.12 part of quinhydrones.To be reflected under 120 ℃ and carry out continuously 6 hours.Add 52.0 parts of Tetra Hydro Phthalic Anhydrides (THPA) and 0.7 part of triethylamine then, and with this mixture 120 ℃ of down reactions 3.5 hours, obtain polymeric reaction solution (hereinafter referred to as " resin glue (c ") thus ").Gained resin glue (c ") has about 15000 (by using the gpc measurements of polystyrene standards) of weight-average molecular weight.
The kind of the dispersion agent that uses in the following examples provides in table 1.In the following manner, measure nitrogen loss on heating and dispersion agent loss on heating, the result provides in table 1.
The nitrogen loss on heating of＜measurement dispersion agent 〉
Will be after about 50 to 100mg dispersion agent weighings add in the 50ml beaker quality, and under 60 ℃ and 10mmHg vacuum-drying 48 hours so that its curing.The gained solid is used as the preceding sample of heating.To in 230 ℃ hot air circulate baking oven, heat after 30 minutes the curing dispersion agent as the heating after sample.Dispersion agent before and after the heating is carried out ultimate analysis to measure total nitrogen content with " PE2400 SeriesCHNS/OAnalyzer " (product of PERKIN ELMER).Nitrogen content is meant the nitrogen ratio in total amount, and absolute value calculates by the weight of taking advantage of the heating front and back of being measured by following method.
＜measurement dispersion agent loss on heating 〉
The weight of dispersion agent is measured with precision balance before and after the heating that obtains in aforesaid method.
Table 10
Dispersion agent Total nitrogen Weight
Before the heating (weight %) Heating back (weight %) Reservation is than (%) Before the heating (weight %) Before the heating (weight %) Reservation is than (%)
" SOLSPERSE 34750 ", the product of Zeneca 4.50 4.35 97 0.075 2 0.070 5 94
" DisperBYK-16 1 ", the product of BYK-Chemie 8.10 7.25 90 0.061 8 0.056 6 92
" DisperBYK-20 01 ", the product of BYK-Chemie 3.04 1.53 50 0.104 4 0.071 1 68
＜preparation dispersible pigment dispersion 〉
According to table 11 or the described weight ratio of table 12, C.I. Pigment green (C.I.P.G.) 36 and C.I. Pigment Yellow 73 (C.I.P.Y.) 138 are mixed as the dispersion agent described in solvent, the table 10 and resin glue (a) with (b) as coloring material, propylene glycol monomethyl ether (PGMEA).Will be with after the zirconium white bead (0.5mm diameter) of 3 times of amounts of its gross weight mix, the gained mixture dropped in the stainless steel vessel and by the lacquer setter disperseed 6 hours, prepare the veridian dispersion liquid thus.
Table 11
Coloring material Solvent Dispersion agent Resin glue
C.I.P.G.36 part by weight (%) C.I.P.Y.13 8 part by weight (%) PGMEA part by weight (%) Kind Part by weight (%) Kind Part by weight (%)
Embodiment 19 5.0 5.0 83.0 " SOLSPERSE 34750 ", manufacturer Zeneca 2.0 Resin glue (a ") 5.0
Embodiment 20 5.0 5.0 82.0 " SOLSPERSE 34750 ", manufacturer Zeneca 3.0 Resin glue (a ") 5.0
Embodiment 21 5.0 5.0 82.0 " Disper BYK-161 ", manufacturer BYK-Chemie 3.0 Resin glue (a ") 5.0
Embodiment 22 5.0 5.0 81.0 " Disper BYK-161 ", manufacturer BYK-Chemie 4.0 Resin glue (a ") 5.0
Embodiment 23 5.0 5.0 83.0 " Disper BYK-2001 ", manufacturer BYK-Chemie 2.0 Resin glue (a ") 5.0
Embodiment 24 5.0 5.0 81.0 " Disper BYK-2001 ", manufacturer BYK-Chemie 4.0 Resin glue (a ") 5.0
Table 12
Coloring material Solvent Dispersion agent Resin glue
C.I.P.G.36 part by weight (%) C.I.P.Y.13 8 part by weight (%) PGMEA part by weight (%) Kind Part by weight (%) Kind Part by weight (%)
Embodiment 25 5.0 5.0 84.0 " SOLSPERSE 34750 ", manufacturer Zeneca 6.0 Do not have 0.0
Comparative example 14 5.0 5.0 82.0 " SOLSPERSE 34750 ", manufacturer Zeneca 3.0 Resin glue (b ") 5.0
Embodiment 26 5.0 5.0 84.0 " Disper BYK-161 ", manufacturer BYK-Chemie 6.0 Do not have 0.0
Comparative example 15 5.0 5.0 82.0 " Disper BYK-161 ", manufacturer BYK-Chemie 3.0 Resin glue (b ") 5.0
Embodiment 27 5.0 5.0 79.0 " Disper BYK-161 ", manufacturer BYK-Chemie 6.0 Resin glue (a ") 5.0
＜preparation colored resin composition 〉
Each above-mentioned dispersible pigment dispersion is mixed with other component, and preparation has the colored resin composition of the solid content of describing in the table 13.It should be noted that by propylene glycol monomethyl ether this colored resin composition is diluted to total solid concentration 20 weight %.
Table 13
The component kind Concrete component Solid content ratio (%)
Dispersible pigment dispersion Above-mentioned dispersible pigment dispersion 53.0
Resin glue Resin glue (c ") 23.5
Photopolymerizable monomer 1 Olefinic compounds (d ") 7.8
Photopolymerizable monomer 2 Olefinic compounds (e ") 3.9
Photoepolymerizationinitiater initiater system component 1 2-mercaptobenzothiazole 3.9
Photoepolymerizationinitiater initiater system component 2 Right-the dimethylaminobenzoic acid methyl esters 3.9
Photoepolymerizationinitiater initiater system component 3 Tetramethyldiaminobenzophenone (Michler ketone) 3.9
Olefinic compounds in the table 13 (d ") by following formula chemical formula (17) expression, and olefinic compounds (e ") be trishydroxymethyl propyl group triacrylate.
Figure A20071014718700891
＜production colour filter 〉
On the glass substrate of long 370 * wide 470mm * thick 0.7mm, form the chromium metal film by sputter.After positive light anti-etching agent forms basic article pattern, this chromium thin film is mixed the etchant etching that obtains with passing through the cerous nitrate di-ammonium salts with perchloric acid.Peel off positive light anti-etching agent with 5% aqueous sodium hydroxide solution, form the fast black base thing thus.
The colored resin composition that will contain red colored material is applied on the gained glass substrate that is stained with the fast black base thing by the die head coating machine.Die head coating machine used herein is made by stainless steel, has length 360mm at its transverse direction.To be adjusted to 200 μ m and 100 μ m respectively from the die lip distance and the slit of glass baseplate surface.During being coated with, regulate the discharge-amount of the coating liquid of similar printing ink, to obtain build 1.3 μ m.With its 60 ℃ dry 1 minute down, then 110 ℃ of following heat dryings 2 minutes.With 330 μ m * 110 μ m joint square through having the minus photomask of the wide repeat patterns of 30 μ m, with this substrate with exposure 300mJ/cm 2Be exposed under the 2kw high voltage mercury lamp.Develop down for 23 ℃ in the photographic developer temperature with 0.1 weight % aqueous sodium carbonate then.Then with this substrate water at hydraulic pressure 3kg/cm 2Following hydro-peening 30 seconds forms red pixel thus.Then under 230 ℃, carry out thermofixation 7 minutes.
Similar with above-mentioned operation, the colored resin composition that will contain blue and veridian carries out each processing respectively, more specifically be coated with, preliminarily dried, heat drying, exposure, develop, wash with water and thermofixation, form corresponding multi color pattern thus, then form colour filter.
In a similar manner, each curable resin composition with embodiment 1 to 30 and comparative example 1 to 19 prepares 100 colour filters.
Should note, monochromatic colour filter is by the green coloring resin combination that only uses embodiment 19 to 30 and comparative example 14 to 17 and obtain with by only using the blue-colored resin combination preparation that obtains in embodiment 31 and comparative example 18 and 19, and provides these colour filters to be used for assessment (will be described below).
The white defective of＜assessment colour filter 〉
Observe whether there is white defective in the colour filter that obtains among each embodiment, white ratio of defects provides in table 14.The white defective that red, blue and green hurdle is given in respectively is red, exist on indigo plant and the green pixel.With [(longer diameter) 2+ (shorter diameter) 2] square root be that 40 μ m or bigger white portion are defined as " white defective " and the merchant by being obtained divided by the colour filter sum (100) of preparation by its colour filter number that detects any color of white defective.The result provides in table 14.
The not dissolved substance (resistates) of the non-pixel region of＜assessment colour filter 〉
With 30 * 100mm of the non-pixel region (on obscure glass) of colour filter with being soaked with alcoholic acid Toraysee MK Clean Cloth (product of Toray Industries) wiping 10 times back and forth.This Toraysee MK Clean Cloth has been fixed on the end that is formed from a resin and immerse the square round log of 0.1cc alcoholic acid 1cm * 1cm by dropper.When not observing the cohesive force of pigment and Toraysee, be evaluated as " o ", even and when observing slight cohesive force, be evaluated as " x ".In addition, the spectral reflectance of spectrophotometer " UV-3100S " 1cm * 1cm of Toraysee after measuring wiping under the condition of using the integration circle that makes by Shimadzu Corporation.Table 14 is given in λ=500nm (being equivalent to red resistates), 450nm (being equivalent to green resistates) and the 550nm (spectral reflectance that (being equivalent to blue residue) located.
The o and the border between the x that are obtained by visual inspection are equivalent to 95% spectral reflectance.
Table 14
The white defective The resistates assessment
Red (part) Blue (part) 4 Green (part) Verification and measurement ratio (%) Visual inspection Spectral reflectance (%)
500nm 450nm 550nm
Embodiment 1 0 0 0 0 ○ 98 99 98
Embodiment 2 0 0 0 0 ○ 99 99 99
Embodiment 3 0 0 0 0 ○ 99 99 98
Embodiment 4 0 0 0 0 ○ 98 99 99
Embodiment 5 0 0 0 0 ○ 99 99 99
Embodiment 6 0 0 0 0 ○ 98 99 99
Embodiment 7 0 0 0 0 ○ 99 98 97
Embodiment 8 0 0 0 0 ○ 99 99 98
Embodiment 9 0 0 0 0 ○ 98 99 98
Embodiment 10 0 0 0 0 ○ 99 98 99
Embodiment 11 0 0 0 0 ○ 99 99 98
Embodiment 12 0 0 0 0 ○ 98 99 97
Embodiment 13 0 0 0 0 ○ 98 99 97
Embodiment 14 0 0 0 0 ○ 99 99 98
Embodiment 15 0 0 0 0 ○ 99 98 98
Embodiment 16 0 0 0 0 ○ 98 99 99
Embodiment 17 0 0 0 0 ○ 98 98 99
Embodiment 18 0 0 0 0 ○ 98 99 98
Embodiment 19 ～ ～ 0 0 ○ ～ 99 ～
Embodiment 20 ～ ～ 0 0 ○ ～ 98 ～
Table 14 (continuing)
The white defective The resistates assessment
Red (part) Blue (part) Green (part) Verification and measurement ratio (%) Visual inspection Spectral reflectance (%)
500nm 450nm 550nm
Embodiment 21 ～ ～ 0 0 ○ ～ 99 ～
Embodiment 22 ～ ～ 0 0 ○ ～ 98 ～
Embodiment 23 ～ ～ 0 0 ○ ～ 98 ～
Embodiment 24 ～ ～ 0 0 ○ ～ 99 ～
Embodiment 25 ～ ～ 0 0 ○ ～ 98 ～
Embodiment 26 ～ ～ 0 0 ○ ～ 98 ～
Embodiment 27 ～ ～ 0 0 ○ ～ 99 ～
Embodiment 28 ～ ～ 0 0 ○ ～ 99 ～
Embodiment 29 ～ ～ 0 0 ○ ～ 99 ～
Embodiment 30 ～ ～ 0 0 ○ ～ 99 ～
Embodiment 31 ～ 0 ～ 0 ○ ～ ～ 99
Comparative example 1 0 0 0 0 × 85 77 80
Comparative example 2 2 1 5 8 ○ 99 98 98
Comparative example 3 0 0 0 0 × 82 72 77
Comparative example 4 0 0 0 0 × 74 67 71
Comparative example 5 3 1 4 8 × 75 68 70
Comparative example 6 0 0 0 0 × 77 70 74
Comparative example 7 2 1 5 8 ○ 99 99 98
Comparative example 8 0 0 0 0 × 81 83 80
Comparative example 9 2 2 6 10 ○ 98 99 99
Comparative example 10 0 0 0 0 × 78 82 81
Table 14 (continuing)
The white defective The resistates assessment
Red (part) Blue (part) Green (part) Verification and measurement ratio (%) Visual inspection Spectral reflectance (%)
500nm 450nm 550nm
Comparative example 11 4 1 4 9 ○ 99 98 98
Comparative example 12 0 0 0 0 × 77 79 80
Comparative example 13 0 0 0 0 × 74 76 79
Comparative example 14 ～ ～ 0 0 ○ ～ 99 ～
Comparative example 15 ～ ～ 0 0 ○ ～ 99 ～
Comparative example 16 ～ ～ 0 0 ○ ～ 99 ～
Comparative example 17 ～ ～ 0 0 × ～ 70 ～
Comparative example 18 ～ 0 ～ 0 ○ ～ ～ 99
Comparative example 19 ～ 0 ～ 0 × ～ ～ 75
Find that from table 14 in each embodiment, white defects detection rate is 0%, all do not detect resistates by visual inspection and measurement spectral reflectance.On the other hand, by visual inspection or measurement spectral reflectance, in comparative example 1 to 13,17 and 19, detect white defective or notice resistates.
Both do not detect white defective in the comparative example 14 to 16 and 18 and do not detected resistates yet, but its through performance poor (will be described below).
＜assessment through performance (measurement colourity) 〉
The colored resin composition that obtains in each embodiment and the comparative example is spun on the square glass substrate of 5cm (" AN100 ", manufacturer Asahi Glass).This substrate was heated 3 minutes on 80 ℃ hot plate.The whole surface of substrate is exposed to 100mJ/cm 2After the following exposure, spray exposure 30 seconds at hydraulic pressure 0.3MPa with 23 ℃ 0.1 weight % aqueous sodium carbonates.Then this substrate was toasted 30 minutes down at 230 ℃ in the hot air circulate baking oven.Regulate the coating condition, the film thickness that toasts the after stain resin combination like this is satisfactory, in the system of CIE colorimetric, x=0.60 (for redness), y=0.55 (for green) and y=0.14 (for blueness) separately, light source C.
Colourity Hitachi, the spectrophotometer " U-3500 " that Ltd. makes is measured.
The colourity of each colored resin composition provides in table 15.
Table 15
Colourity (light source C)
R G B
x y Y x y Y x y Y
Embodiment 1 0.600 0.291 17.3 0.210 0.550 44.0 0.137 0.140 19.3
Embodiment 2 0.600 0.291 17.4 0.210 0.550 44.1 0.137 0.140 19.2
Embodiment 3 0.600 0.291 17.3 0.210 0.550 43.9 0.137 0.140 19.2
Embodiment 4 0.600 0.291 17.4 0.210 0.550 44.2 0.137 0.140 19.3
Embodiment 5 0.600 0.291 17.2 0.210 0.550 44.1 0.137 0.140 19.3
Embodiment 6 0.600 0.291 17.4 0.210 0.550 44.0 0.137 0.140 19.3
Embodiment 7 0.600 0.291 17.4 0.210 0.550 44.1 0.137 0.140 19.2
Embodiment 8 0.600 0.291 17.3 0.210 0.550 44.2 0.137 0.140 19.2
Embodiment 9 0.600 0.291 17.3 0.210 0.550 44.0 0.137 0.140 19.3
Embodiment 10 0.600 0.291 17.2 0.210 0.550 43.9 0.137 0.140 19.3
Embodiment 11 0.600 0.291 17.4 0.210 0.550 44.0 0.137 0.140 19.2
Embodiment 12 0.600 0.291 17.4 0.210 O.550 44.1 0.137 0.140 19.2
Embodiment 13 0.600 0.291 17.4 0.210 0.550 43.9 0.137 0.140 19.3
Embodiment 14 0.600 0.291 17.3 0.210 0.550 44.1 0.137 0.140 19.3
Embodiment 15 0.600 0.291 17.2 0.210 0.550 44.0 0.137 0.140 19.2
Embodiment 16 0.600 0.291 17.4 0.210 0.550 44.1 0.137 0.140 19.3
Embodiment 17 0.600 0.291 17.2 0.210 0.550 44.0 0.137 0.140 19.2
Embodiment 18 0.600 0.291 17.3 0.210 0.550 44.1 0.137 0.140 19.3
Table 15 (continuing)
Colourity (light source C)
R G B
x y Y x y Y x y Y
Embodiment 19 ～ ～ ～ 0.310 0.550 67.9 ～ ～ ～
Embodiment 20 ～ ～ ～ 0.310 0.550 68.0 ～ ～ ～
Embodiment 21 ～ ～ ～ 0.310 0.550 67.6 ～ ～ ～
Embodiment 22 ～ ～ ～ 0.310 0.550 67.7 ～ ～ ～
Embodiment 23 ～ ～ ～ 0.310 0.550 68.2 ～ ～ ～
Embodiment 24 ～ ～ ～ 0.310 0.550 68.3 ～ ～ ～
Embodiment 25 ～ ～ ～ 0.310 0.550 67.9 ～ ～ ～
Embodiment 26 ～ ～ ～ 0.310 0.550 67.7 ～ ～ ～
Embodiment 27 ～ ～ ～ 0.310 0.550 67.8 ～ ～ ～
Embodiment 28 ～ ～ ～ 0.210 0.550 43.8 ～ ～ ～
Embodiment 29 ～ ～ ～ 0.210 0.550 44.6 ～ ～ ～
Embodiment 30 ～ ～ ～ 0.210 0.550 43.9 ～ ～ ～
Embodiment 31 ～ ～ ～ ～ ～ ～ 0.137 0.140 19.1
Comparative example 1 0.600 0.291 17.3 0.210 0.550 44.0 0.137 0.140 19.2
Comparative example 2 0.600 0.291 17.3 0.210 0.550 44.1 0.137 0.140 19.4
Comparative example 3 0.600 0.291 17.3 0.210 0.550 44.1 0.137 0.140 19.2
Comparative example 4 0.600 0.291 16.9 0.210 0.550 41.8 0.137 0.140 18.4
Comparative example 5 0.600 0.291 17.3 0.210 0.550 44.0 0.137 0.140 19.4
Table 15 (continuing)
Colourity (light source C)
R G B
x y Y x y Y x y Y
Comparative example 6 0.600 0.291 17.2 0.210 0.550 44.1 0.137 0.140 19.1
Comparative example 7 0.600 0.291 17.3 0.210 0.550 44.0 0.137 0.140 19.2
Comparative example 8 0.600 0.291 17.3 0.210 0.550 44.1 0.137 0.140 19.3
Comparative example 9 0.600 0.291 17.2 0.210 0.550 44.1 0.137 0.140 19.4
Comparative example 10 0.600 0.291 17.2 0.210 0.550 44.0 0.137 0.140 19.2
Comparative example 11 0.600 0.291 17.3 0.210 0.550 44.1 0.137 0.140 19.4
Comparative example 12 0.600 0.291 16.8 0.210 0.550 41.5 0.137 0.140 18.2
Comparative example 13 0.600 0.291 16.8 0.210 0.550 41.3 0.137 0.140 18.3
Comparative example 14 ～ ～ ～ 0.310 0.550 66.6 ～ ～ ～
Comparative example 15 ～ ～ ～ 0.310 0.550 66.7 ～ ～ ～
Comparative example 16 ～ ～ ～ 0.210 0.550 42.1 ～ ～ ～
Comparative example 17 ～ ～ ～ 0.210 0.550 43.0 ～ ～ ～
Comparative example 18 ～ ～ ～ ～ ～ ～ 0.137 0.140 18.7
Comparative example 19 ～ ～ ～ ～ ～ ～ 0.137 0.140 18.8
Find that from table 15 redness of Huo Deing, green and blue pixel fall into respectively in the scope of following equation in an embodiment.
Red
Y≥200y-41.4(y＜0.34)
Y≥200y-41.4(y≥0.34)
Green
Y≥240x-7.1
Blue
Y≥20x+16.2
The colourity of the blue pixel in the colourity of the green pixel in the comparative example 12 to 17 and comparative example 4,12,13,18 and 19 does not fall in the above-mentioned equation.
＜assessment development cohesiveness 〉
Each colored resin composition that obtains in embodiment and the comparative example is applied to the glass substrate that obtains thickness 1.3 μ m on the glass substrate.After 1 minute, that this glass substrate is following dry 2 minutes at 110 ℃ 60 ℃ of following dryings.The test light mask of the linear opening portion by having 1 μ m live width separately, with substrate with exposure energy 300mJ/cm 2By the exposure of 150 μ m slits, follow with 0.1 weight % aqueous sodium carbonate at 23 ℃ of photographic developer temperature, liquid pressure 0.2kg/cm 2Under developed 60 seconds.Then water is at hydraulic pressure 3kg/cm 2Following hydro-peening 30 seconds forms pattern thus.Measurement remains the minimum pattern of linearity pattern.The result provides in table 16.
Table 16
Red Green Blue
Embodiment 1 7 6 7
Embodiment 2 6 5 6
Embodiment 3 6 6 6
Embodiment 4 7 6 6
Embodiment 5 6 6 7
Embodiment 6 7 5 6
Embodiment 7 7 5 7
Embodiment 8 6 6 7
Embodiment 9 6 5 6
Embodiment 10 7 5 6
Embodiment 11 7 6 7
Embodiment 12 6 6 6
Embodiment 13 7 6 6
Embodiment 14 7 5 7
Embodiment 15 6 6 7
Embodiment 16 7 6 7
Embodiment 17 7 6 7
Embodiment 18 7 5 7
Embodiment 19 ～ 6 ～
Embodiment 20 ～ 5 ～
Embodiment 21 ～ 5 ～
Embodiment 22 ～ 5 ～
Embodiment 23 ～ 6 ～
Embodiment 24 ～ 5 ～
Embodiment 25 ～ 6 ～
Embodiment 26 ～ 6 ～
Embodiment 27 ～ 5 ～
Embodiment 28 ～ 5 ～
Embodiment 29 ～ 5 ～
Embodiment 30 ～ 6 ～
Embodiment 31 ～ ～ 6
Unit: μ m
Table 16 (continuing)
Red Green Blue
Comparative example 1 7 6 6
Comparative example 2 15 18 13
Comparative example 3 6 5 6
Comparative example 4 6 6 7
Comparative example 5 14 20 14
Comparative example 6 7 6 7
Comparative example 7 14 20 15
Comparative example 8 6 5 6
Comparative example 9 12 18 13
Comparative example 10 6 5 6
Comparative example 11 16 19 15
Comparative example 12 6 5 7
Comparative example 13 7 6 6
Comparative example 14 - 5 -
Comparative example 15 - 5 -
Comparative example 16 - 6 -
Comparative example 17 - 5 -
Comparative example 18 - - 6
Comparative example 19 - - 6
Unit: μ m
Find that from table 16 minimum pattern width is 10 μ m or lower in redness in an embodiment, green and blue any, and in some of comparative example 2,5,7,9 and 11 the minimum pattern width above 10 μ m.
＜assessment viscosity velocity of variation 〉
Place 7 days in 23 ℃ thermostatic bath after just preparing colored resin composition and with composition after, with Toki Sangyo Co., the E type viscometer " RE-80L " that Ltd. makes is measured viscosity (20rpm).The viscosity of each colored resin composition that obtains in embodiment and the comparative example and the variation of the viscosity after 7 days provide in table 17.
Table 17
Red Green Blue
Initial viscosity mPas Viscosity mPas after 7 days Velocity of variation % Initial viscosity mPas Viscosity mPas after 7 days Velocity of variation % Initial viscosity mPas Viscosity mPas after 7 days Velocity of variation %
Embodiment 1 6.03 6.09 1.0 7.50 7.56 0.8 6.24 6.30 1.0
Embodiment 2 6.24 6.27 0.5 7.32 7.41 1.2 6.42 6.51 1.4
Embodiment 3 6.33 6.39 0.9 7.26 7.35 1.2 6.36 6.45 1.4
Embodiment 4 6.18 6.18 0.0 6.99 7.05 0.9 6.21 6.27 1.0
Embodiment 5 6.21 6.33 1.9 7.47 7.53 0.8 6.18 6.18 0.0
Embodiment 6 6.03 6.03 0.0 7.20 7.32 1.7 6.27 6.33 1.0
Embodiment 7 6.21 6.18 -0.5 7.02 7.11 1.3 5.97 6.03 1.0
Embodiment 8 6.24 6.30 1.0 7.32 7.35 0.4 6.30 6.36 1.0
Embodiment 9 6.15 6.21 1.0 7.20 7.32 1.7 6.27 6.27 0.0
Embodiment 10 6.66 6.72 0.9 7.35 7.41 0.8 6.87 6.96 1.3
Embodiment 11 6.54 6.54 0.0 7.29 7.41 1.6 6.51 6.60 1.4
Embodiment 12 6.09 6.18 1.5 6.96 7.02 0.9 6.21 6.24 0.5
Embodiment 13 6.39 6.42 0.5 7.05 7.08 0.4 6.12 6.15 0.5
Embodiment 14 6.51 6.51 0.0 7.35 7.38 0.4 6.21 6.24 0.5
Embodiment 15 6.36 6.33 -0.5 7.29 7.41 1.6 6.36 6.39 0.5
Embodiment 16 6.45 6.51 0.9 7.11 7.08 -0.4 6.51 6.57 0.9
Embodiment 17 6.36 6.42 0.9 7.50 7.56 0.8 6.33 6.39 0.9
Embodiment 18 6.54 6.51 -0.5 6.93 6.99 0.9 6.66 6.69 0.5
Table 17 (continuing)
Red Green Blue
Initial viscosity mPas Viscosity mPas after 7 days Velocity of variation % Initial viscosity mPas Viscosity mPas after 7 days Velocity of variation % Initial viscosity mPas Viscosity mPas after 7 days Velocity of variation %
Embodiment 19 ～ ～ ～ 7.86 7.95 1.1 ～ ～ ～
Embodiment 20 ～ ～ ～ 7.44 7.47 0.4 ～ ～ ～
Embodiment 21 ～ ～ ～ 7.56 7.56 0.0 ～ ～ ～
Embodiment 22 ～ ～ ～ 7.11 7.14 0.4 ～ ～ ～
Embodiment 23 ～ ～ ～ 7.62 7.71 1.2 ～ ～ ～
Embodiment 24 ～ ～ ～ 6.93 6.93 0.0 ～ ～ ～
Embodiment 25 ～ ～ ～ 6.87 6.90 0.4 ～ ～ ～
Embodiment 26 ～ ～ ～ 6.75. 6.75 0.0 ～ ～ ～
Embodiment 27 ～ ～ ～ 6.42 6.42 0.0 ～ ～ ～
Embodiment 28 ～ ～ ～ 8.22 8.34 1.5 ～ ～ ～
Embodiment 29 ～ ～ ～ 8.40 8.52 1.4 ～ ～ ～
Embodiment 30 ～ ～ ～ 8.31 8.52 2.5 ～ ～ ～
Embodiment 31 ～ ～ ～ ～ ～ ～ 7.53 7.71 2.4
Comparative example 1 6.18 6.45 4.4 7.44 7.59 2.0 6.78 6.90 1.8
Comparative example 2 7.14 7.56 5.9 7.77 7.92 1.9 6.57 6.69 1.8
Comparative example 3 7.62 7.83 2.8 8.64 8.85 2.4 8.01 8.22 2.6
Comparative example 4 8.10 9.54 17.8 8.94 10.82 21.0 7.65 9.18 20.0
Comparative example 5 7.28 7.50 3.0 7.68 7.92 3.1 6.27 6.60 5.3
Table 17 (continuing)
Red Green Blue
Initial viscosity mPas Viscosity mPas after 7 days Velocity of variation % Initial viscosity mPas Viscosity mPas after 7 days Velocity of variation % Initial viscosity mPas Viscosity mPas after 7 days Velocity of variation %
Comparative example 6 6.57 6.66 1.4 7.14 7.14 0.0 6.27 6.30 0.5
Comparative example 7 6.33 6.33 0.0 6.81 6.87 0.9 6.36 6.45 1.4
Comparative example 8 7.02 7.05 0.4 7.44 7.56 1.6 6.48 6.51 0.5
Comparative example 9 6.84 6.87 0.4 7.32 7.38 0.8 6.90 6.93 0.4
Comparative example 10 6.21 6.27 1.0 7.23 7.26 0.4 6.00 6.06 1.0
Comparative example 11 6.42 6.51 1.4 6.87 6.96 1.3 6.21 6.21 0.0
Comparative example 12 8.04 10.53 31.0 8.88 9.54 7.4 8.22 9.96 21.2
Comparative example 13 7.74 9.24 19.4 8.55 10.11 18.2 8.16 10.80 32.4
Comparative example 14 ～ ～ ～ 8.25 9.87 19.6 ～ ～ ～
Comparative example 15 ～ ～ ～ 8.13 9.66 18.8 ～ ～ ～
Comparative example 16 ～ ～ ～ 12.24 16.74 36.8 ～ ～ ～
Comparative example 17 ～ ～ ～ 6.78 6.78 0.0 ～ ～ ～
Comparative example 18 ～ ～ ～ ～ ～ ～ 13.39 18.21 36.0
Comparative example 19 ～ ～ ～ ～ ～ ～ 6.42 6.45 0.5
Find that from table 17 the viscosity velocity of variation of the redness that obtains among the embodiment, green and blue any is 10% or lower, and some the viscosity velocity of variation in the color that obtains in comparative example 4,12 to 16 and 18 is above 10%.
The foreign matter defective of＜assessment colour filter 〉
For the colour filter that obtains among the embodiment, whether detection exists the foreign matter defective and verification and measurement ratio is provided in table 18.In table 18, the white defective that exists on the pixel of each redness, blueness and green provides in its hurdle.With [(longer diameter) 2+ (shorter diameter) 2] square root be that 100 μ m or bigger material are defined as " foreign matter defective " and by being defined as foreign matter defective incidence divided by the merchant that the colour filter sum (100) of preparation obtains by its colour filter number of observing any color of foreign matter.The result provides in table 18.
＜assess again resolvability (measurement volumes median size mv) 〉
On the glass substrate that each colored resin composition spin coating of obtaining in embodiment and the comparative example and 50mm is square, obtain 2.5 μ m desciccator diaphragm thickness, then did 60 minutes at sky.Then this substrate is immersed in the 6.25g solvent that constitutes coloured composition and to make its redispersion in 3 minutes.After beginning to soak 10 minutes, use Nikkiso Co., " Microtrack UPA " analysing particulates size that Ltd. makes.By this particle size distribution, volume calculated median size mv.The result provides in table 18.
As a reference, when foreign matter defective incidence was 0%, the volume average particle size in resolvability is measured again was 200nm or lower.
Table 18
Resolvability again The foreign matter defective
Red (nm) Blue (nm) Green (nm) Red (part) Blue (part) Green (part) Verification and measurement ratio (%)
Embodiment 1 110 150 90 ～ ～ ～ ～
Embodiment 2 110 140 90 ～ ～ ～ ～
Embodiment 3 120 160 100 ～ ～ ～ ～
Embodiment 4 120 140 90 ～ ～ ～ ～
Embodiment 5 130 150 100 ～ ～ ～ ～
Embodiment 6 110 140 80 ～ ～ ～ ～
Embodiment 7 120 130 100 ～ ～ ～ ～
Embodiment 8 110 140 100 ～ ～ ～ ～
Embodiment 9 130 150 100 ～ ～ ～ ～
Embodiment 10 110 130 90 ～ ～ ～ ～
Embodiment 11 120 140 90 ～ ～ ～ ～
Embodiment 12 130 130 100 ～ ～ ～ ～
Embodiment 13 120 130 100 0 0 0 0
Embodiment 14 120 130 90 0 0 0 0
Embodiment 15 110 150 100 0 0 0 0
Embodiment 16 120 140 100 0 0 0 0
Embodiment 17 270 280 270 1 2 6 9
Embodiment 18 260 300 250 2 1 5 8
Embodiment 19 ～ 130 ～ ～ ～ ～ ～
Embodiment 20 ～ 130 ～ ～ ～ ～ ～
Embodiment 21 ～ 140 ～ ～ ～ ～ ～
Embodiment 22 ～ 130 ～ ～ ～ ～ ～
Embodiment 23 ～ 180 ～ ～ ～ ～ ～
Embodiment 24 ～ 190 ～ ～ ～ ～ ～
Embodiment 25 ～ 130 ～ ～ ～ ～ ～
Embodiment 26 ～ 130 ～ ～ ～ ～ ～
Embodiment 27 ～ 140 ～ ～ ～ ～ ～
Embodiment 28 ～ 130 ～ ～ ～ ～ ～
Embodiment 29 ～ 140 ～ ～ ～ ～ ～
Embodiment 30 ～ 130 ～ ～ ～ ～ ～
Embodiment 31 ～ ～ 100 ～ ～ ～ ～
Table 18 (continuing)
Resolvability again The foreign matter defective
Red (nm) Blue (nm) Green (nm) Red (part) Blue (part) Green (part) Verification and measurement ratio (%)
Comparative example 1 110 130 100 ～ ～ ～ ～
Comparative example 2 120 140 90 ～ ～ ～ ～
Comparative example 3 280 290 240 ～ ～ ～ ～
Comparative example 4 180 220 210 ～ ～ ～ ～
Comparative example 5 300 290 270 ～ ～ ～ ～
Comparative example 6 120 130 100 ～ ～ ～ ～
Comparative example 7 110 140 90 ～ ～ ～ ～
Comparative example 8 310 290 220 ～ ～ ～ ～
Comparative example 9 110 140 90 ～ ～ ～ ～
Comparative example 10 280 280 250 1 0 2 3
Comparative example 11 110 140 100 0 0 0 0
Comparative example 12 210 230 240 2 1 4 7
Comparative example 13 210 220 210 1 1 3 5
Comparative example 14 ～ 130 ～ ～ ～ 0 0
Comparative example 15 ～ 130 ～ ～ ～ 0 0
Comparative example 16 ～ 130 ～ ～ ～ 0 0
Comparative example 17 ～ 130 ～ ～ ～ 0 0
Comparative example 18 ～ ～ 100 ～ 0 ～ 0
Comparative example 19 ～ ～ 90 ～ 0 ～ 0
Finding that from table 18 colored resin composition that obtains among the embodiment 1 to 16 and 31 does not produce the foreign matter defective, is good as the die head coating composition therefore.
＜measuring voltage conservation rate 〉
Preparation has the square non-alkali glass substrate (" AN-100 " at 2.5cm, manufacturer Asahi Glass) the electrode base board A of the ito thin film that forms on the whole surface of a side is with the electrode base board B of the 1cm ito thin film (being connected the wide taking-up electrode of 2mm to it) with the center formation on glass substrate one side of the square same type of 2.5cm.
On electrode base board A and B by behind the spin application aligning film material (" Sunever 7492 ", manufacturer Nissan Chemical), with its on 110 ℃ hot plate dry 1 minute.In this hot air circulate baking oven, it was heated 1 hour down at 200 ℃, form the thick film of 70nm thus.
The colored resin composition of each embodiment is applied to the electrode base board that has been coated with on it oriented layer, and it was heated 3 minutes on 80 ℃ hot plate.Whole surface is at exposure energy 100mJ/cm 2, after the following exposure, under pressure 0.3MPa, spray development 30 seconds with 23 ℃ 0.1 weight % aqueous sodium carbonates, then in the hot air circulate baking oven, toasting 30 minutes under 230 ℃.Control coating condition obtains the thick coloured composition film of 1.7 μ m thus after baking.
The epoxy encapsulant that will contain the silicon-dioxide bead of 5 μ m diameters by decollator is coated with the periphery of the electrode base board B that has been coated with aligning film material thereon, the surface that electrode of substrate is coated with colored resin composition is placed on gained substrate reverse side, makes the mutual displacement 3mm in its edge simultaneously.They were heated 2 hours the bonding of pressurizeing simultaneously in 180 ℃ thermal cycling baking oven.
(" MLC-6846-000 ", manufacturer Merck Ltd. Japan) inject the vacuum structure cell that so obtains, and seal with the edge of UV curable encapsulant to this structure cell, finish the liquid crystal cells that is used for the measuring voltage conservation rate thus with liquid crystal.
With gained liquid crystal cells annealing back (in the hot air circulate baking oven, heating 2.5 hours down) at 105 ℃.The 5V pulsed voltage is imposed on electrode base board A and the B with pulse-repetition 60Hz, so the measuring voltage conservation rate.
Table 19 provides the voltage retention of each coloured composition.
Table 19
Voltage retention (%)
Embodiment 19 94
Embodiment 20 89
Embodiment 21 95
Embodiment 22 90
Embodiment 23 97
Embodiment 24 93
Embodiment 25 60
Embodiment 26 71
Embodiment 27 72
Comparative example 14 93
Comparative example 15 93
From table 19, found that the composition that obtains among the embodiment 19-24 has good voltage retention.
＜embodiment 28 to 31 and comparative example 16 to 19 〉
＜synthesis example 23 〉
35 parts of propylene glycol monomethyl ether, 8.8 parts of 1-methoxyl group-2-propyl alcohol and 1.5 parts " V-59 " (a kind of azo polymerization initiator, product of Wako Pure Chemical) are dropped in the reactor, then in nitrogen atmosphere, be heated to 80 ℃.In 2 hours, be added dropwise to 9.5 parts of methacrylic acid benzyl esters, 6.5 parts of methyl methacrylates, 3.5 parts of 2-hydroxymethyl ethyl propenoates and 10.7 parts of methacrylic acids.This reaction mixture was stirred 4 hours, obtain polymerization reaction mixture.In this reaction mixture, add 25.5 parts of propylene glycol monomethyl ether.Add after 0.05 part of right-methoxyphenol and 0.3 part of triphenylphosphine make its dissolving, be added dropwise to 17.5 parts of vinylformic acid (3, the 4-epoxycyclohexyl) methyl esters,, obtain in its side chain, to have the resin of ethylenically unsaturated group thus then 85 ℃ of reactions 24 hours down.So the resin glue that obtains has weight-average molecular weight 18000 (by using the gpc measurement of polystyrene standards) and acid number 50 (with the result of KOH neutralization titration).By the introducing ratio of addition vinylformic acid (3, the 4-epoxycyclohexyl) methyl esters in carboxylic acid is 66%, is judged by the acid number before and after the reaction.
＜embodiment 28 〉
By 9.4 parts of pigment green 36s were disperseed 5 hours as solvent as resin solution (9.4 parts of resin Compositions) and 42.4 parts of propylene glycol monomethyl ether of obtaining in pigment, the 23.4 parts of synthesis examples 23, prepare green oil China ink (colored resin composition) in containing the lacquer setter of zirconium white bead.So the liquid properties of the colored resin composition of preparation provides in table 20.
The green oil China ink (10.9 parts) that so obtains is added and mixes with photosensitive resin composition, this photosensitive resin composition is in advance by mixing the resin solution that obtains in 5.5 parts of synthesis examples 23,0.73 part dipentaerythritol acrylate is as photopolymerizable monomer, 0.26 part two imidazoles are as Photoepolymerizationinitiater initiater, 0.18 part 4,4 '-two (diethylamino) benzophenone (EABF) is as photosensitizers, 0.05 part 2-mercaptobenzothiazole (2MBT) is as chain-transfer agent, 0.001 part fluorine surfactant (" FC-430 ", manufacturer Sumitomo3M) and 28.8 parts of propylene glycol monomethyl ether prepare in advance as solvent, obtain green photosensitive colored resin composition thus.
Should be spun on the glass substrate (" AN635 ", manufacturer AsahiGlass) by the photosensitive colored resin composition of green, and this substrate is passed through heat drying on 70 ℃ hot plate, obtain the thick photosensitive green layer of 1.5 μ m thus.With this film at 200mJ/cm from ultrahigh pressure mercury lamp 2Ultraviolet rays is exposure down, then by developing 120 seconds with alkaline developer drip washing and with ultrapure water washing 10 seconds, forming green pattern thus.Pattern observations their line styles of demonstration and cohesive force after the development are good.In addition, spume by unexposed portion visual inspection with halogen lamp irradiation development substrate.With this substrate be evaluated as zero, Δ and *, be respectively and do not observe its foam, substrate comprises that the part and the whole base plate that appear as slight white appear as white.Gained is the result provide in table 20.(x, y) observed value of the Y value in provides in table 21 than the colourity of color system at CIE.
＜embodiment 29 〉
Press and embodiment 28 similar modes, but use sulfonic acid that 9.4 parts of Pigment greens make the resin solution (9.4 parts of resin Compositions) that obtains in pigment, the 23.4 parts of synthesis examples 23,0.47 part of pigment yellow 13 8 as dispersing auxiliary and 42.4 parts of propylene glycol monomethyl ether as solvent, obtain green oil China ink (colored resin composition).So the liquid properties of the colored resin composition of preparation provides in table 1.Press and embodiment 28 similar modes, obtain photosensitive colored resin combination and form green pattern with top acquisition green ink.As the result of the back observation pattern that develops, they have good line style and cohesive force.The assessment result that spumes in the unexposed portion of development substrate provides in table 20.So the Y value of the pixel that obtains provides in table 21.
＜embodiment 30 〉
Pigment green 36 (9.4 parts) as resin solution (the 9.4 parts of resin Compositions) premix in homogenizer that obtains in pigment and the 23.4 parts of synthesis examples 23, then will be obtained the colored resin composition that is used to mediate 80 ℃ of following evaporating solvents 1 hour thus.The gained colored resin composition was mediated in kneader 5 hours, obtained color chip thus.During this mediates, the temperature of kneader is controlled to 80 ℃.The chip (18.8 parts) that so obtains with 42.4 parts of propylene glycol monomethyl ether swellings 12 hours, was stirred 3 hours in homogenizer then, prepare the base-material of milling thus.
The base-material of milling that so obtains was handled 10 minutes in the ball mill of filling diameter 0.3mm zirconium white bead, so prepared green ink.
By in containing the lacquer setter of zirconium white bead, disperseing to obtain in 5 hours green oil China ink (colored resin composition).The liquid properties of gained colored resin composition provides in table 1.
Similar with embodiment 28, obtain photosensitive colored resin combination and form green pattern with top acquisition green ink.As the result of the back observation pattern that develops, they have good line style and cohesive force.The assessment result that spumes in the unexposed portion of development substrate provides in table 20.So the Y value of the pixel that obtains provides in table 21.
＜comparative example 16 〉
With use among the embodiment 28 those are similar, but use methacrylic acid benzyl ester-Sipacril 2739OF (weight-average molecular weight: 15000, acid number:, obtain colored resin composition 90) as resin.The liquid properties of gained colored resin composition provides in table 20.In addition, with embodiment 28 in those similar steps in, obtain photosensitive colored resin combination and develop, even under 300s, can not dissolve unexposed part.So the Y value of the pixel that obtains provides in table 21.
＜comparative example 17 〉
With embodiment 28 in those similar steps of using, different is to use commercial amino formate dispersion agent X as resin, obtains colored resin composition.The liquid properties of gained colored resin composition provides in table 20.In addition, with embodiment 28 in those similar steps of using, form green pattern.The assessment result that spumes in the unexposed portion of development substrate provides in table 20.So the Y value of the pixel that obtains provides in table 21.
Table 20
Resin Liquid properties *1 Resistates after the development
Embodiment 28 Synthesis example 23 ○ ○
Embodiment 29 Synthesis example 23 ○ ○
Embodiment 30 Synthesis example 23 ○ ○
Comparative example 16 Methacrylic acid benzyl ester-Sipacril 2739OF (weight-average molecular weight: 15000, acid number: 90) × ～
Comparative example 17 Amino formate dispersion agent X ○ ×
*1: the viscosity of colored resin composition
Zero: low viscosity
△: slight thickening
*: thickening
Table 21
Resin Y (when x=0.234 and y=0.472)
Embodiment 28 Synthesis example 23 56.9
Embodiment 29 Synthesis example 23 58.0
Embodiment 30 Synthesis example 23 57.0
Comparative example 16 Methacrylic acid benzyl ester-Sipacril 2739OF (weight-average molecular weight: 15000, acid number: 90) 55.3
Comparative example 17 Amino formate dispersion agent X 56.1
＜embodiment 31 〉
In the lacquer setter of filling the zirconium white bead, with 9.4 parts of pigment Blue 15s: 6 as the resin solution (9.4 parts of resin Compositions) that obtains in pigment, the 23.4 parts of synthesis examples 23 and 42.4 parts of propylene glycol monomethyl ether as solvent dispersion 10 hours, obtain blue ink (colored resin composition) thus.The performance of gained colored resin composition provides in table 22.
With embodiment 28 in those similar steps of using, form blue pattern.The assessment result that spumes in the unexposed portion of development substrate provides in table 22.So the Y value of the pixel that obtains provides in table 23.
＜comparative example 18 〉
With use among the embodiment 28 those are similar, but use methacrylic acid benzyl ester-Sipacril 2739OF (weight-average molecular weight: 14000, acid number:, obtain colored resin composition 52) as resin.The liquid properties of gained colored resin composition provides in table 22.In addition, with embodiment 28 in those similar steps of using, develop, obtain photosensitive colored resin combination and develop, even under 300s, can not dissolve unexposed part.So the Y value of the pixel that obtains provides in table 23.
＜comparative example 19 〉
With those similar steps of using among the embodiment 28, but do not use commercial amino formate dispersion agent Y, obtain colored resin composition as resin.The liquid properties of gained colored resin composition provides in table 22.In addition, with embodiment 28 in those similar steps of using, form blue pattern.The assessment result that spumes in the unexposed portion of development substrate provides in table 22.So the Y value of the pixel that obtains provides in table 23.
Table 22
Resin Liquid properties *1 Resistates after the development
Embodiment 31 Synthesis example 23 ○ ○
Comparative example 18 Methacrylic acid benzyl ester-Sipacril 2739OF (weight-average molecular weight: 14000, acid number: 52) × ～
Comparative example 19 Carbamate dispersion agent Y ○ ×
*1: the viscosity of colored resin composition
Zero: low viscosity
△: slight thickening
*: thickening
Table 23
Resin Y (when x=0.134 and y=0.121)
Embodiment 31 Synthesis example 23 15.1
Comparative example 18 Methacrylic acid benzyl ester-Sipacril 2739OF (weight-average molecular weight: 14000, acid number: 52) 14.7
Comparative example 19 Amino formate dispersion agent Y 14.9
Through performance, development cohesive force, the white defective of the product that obtains in embodiment 28 to 31 and the comparative example 16 to 19, do not dissolve resistates, viscosity velocity of variation, resolvability and voltage retention be by assessing with embodiment 1 to 27 or comparative example 1 to 15 similar mode again.The result provides to table 19 at table 14.
Embodiment 1 to 31 (colored resin composition of the present invention) shows with the comparing result of comparative example 1 to 19:
(1) colored resin composition of the present invention has high-permeability energy and high density.
(2) the non-pixel region of colored resin composition of the present invention on the substrate after the development stays less undissolved resistates.
(3) colored resin composition of the present invention image cohesive force during developing is good and have a low white defective appearance.
(4) colored resin composition of the present invention has the foreign matter defective appearance of reduction during using by the die head coating.
(5) colored resin composition of the present invention produces the low viscosity variation.
(6) colored resin composition of the present invention has especially little influence to the voltage retention of liquid crystal.
The present invention describes in detail with reference to specific embodiments.Yet those skilled in the art it is evident that, can carry out various replacements and improvement to the present invention not leaving under the spirit and scope of the invention.
The present invention is based on Japanese patent application (patent application No.2002-210065), July 18 2002 applying date; Japanese patent application (patent application No.2003-30954), February 7 2003 applying date; Japanese patent application (patent application No.2003-45364), February 24 2003 applying date; Japanese patent application (patent application No.2003-47604), February 25 2003 applying date; Japanese patent application (patent application No.2003-122854), April 25 2003 applying date; Japanese patent application (patent application No.2003-124291), April 28 2003 applying date; And Japanese patent application (patent application No.2003-366100), October 27 2003 applying date; Each document integral body here is incorporated herein by reference.
Industrial applicibility
The present invention has beneficial effect as described below and has very large potentiality industrial.
1. colored resin composition of the present invention is when being applied on the substrate, and non-pixel region thereon stays not dissolving residue seldom, has the good adhesion power of substrate and can evenly form the high-concentration colorful pixel. Even during using by the die head coating, the generation of foreign matter such as dried deposit is very little. In addition, said composition has especially little impact to the voltage retention of liquid crystal, display defect can occur so hardly as showing inhomogeneous and image persistence.
2. in colour filter of the present invention, the residue that do not dissolve of colored resin composition does not remain in non-pixel region on the substrate. Therefore impact because of especially little on the liquid crystal voltage conservation rate, display defect can occur hardly as showing inhomogeneous and image persistence. Therefore, colour filter is unusual work of high quality.
3. in liquid crystal display of the present invention, the residue that do not dissolve of colored resin composition remains in non-pixel region on the substrate. Can interfere hardly the liquid crystal voltage conservation rate that shows inhomogeneities reduces. In addition, it is a kind of very high-quality liquid crystal display, because it is used quite high-quality colour filter.

Claims (29)

1. a colored resin composition comprises coloring material, solvent, dispersion agent and resin glue, wherein:
Described resin glue comprises no nitrogen-atoms resin glue, and the epoxide group that this resin has by the unsaturated compound that will contain epoxide group (b) adds to the structure that obtains on the carboxyl that contains carboxy resin (a);
This dispersion agent comprises that at least a in nitrogen atom graft copolymer (F) and A-B segmented copolymer and/or the B-A-B segmented copolymer (G), each freedom have the block A of quaternary ammonium salt and do not have a quaternary ammonium salt in its side chain B block forms; With
The weight ratio of nitrogen atom dispersion agent and coloring material is 0.01 or higher, but is not more than 0.5.
2. according to the colored resin composition of claim 1, wherein the graft copolymer of nitrogen atom (F) has the nitrogen atom repeating unit in its main chain.
3. according to the colored resin composition of claim 1, wherein nitrogen atom graft copolymer (F) has the repeating unit of following general formula (I) expression and/or the repeating unit of formula (II) expression:
Figure A2007101471870002C1
Wherein, R 1Expression has the alkylidene group of 1 to 5 carbon atom, and A represents any one group of hydrogen atom or following formula (III) to (V) expression;
Figure A2007101471870002C2
Wherein, R 1Expression has the alkylidene group of 1 to 5 carbon atom, and A represents any one group of hydrogen atom or following formula (III) to (V) expression;
W wherein 1Expression has the alkylidene group of 2 to 10 carbon atoms, and p represents 1 to 20 integer;
Figure A2007101471870002C4
Y wherein 1The expression divalent linker, W 2The alkylidene group of 2 to 10 carbon atoms of expression, Y 2The expression hydrogen atom or-CO-R 2, R 2Expression has the alkylidene group of 1 to 10 carbon atom, and q represents 1 to 20 integer;
Figure A2007101471870003C1
W wherein 3The alkyl of 1 to 50 carbon atom of expression or have the hydroxyalkyl of 1 to 50 carbon atom of 1 to 5 hydroxyl.
4. according to the colored resin composition of claim 1, it is characterized in that each freedom has the block A of quaternary ammonium salt and do not have A-B segmented copolymer that the B block of quaternary ammonium salt forms and/or the block A of B-A-B segmented copolymer (G) in its side chain, comprise the part-structure of following formula (1) expression:
Figure A2007101471870003C2
In formula (1), R 1a, R 2aAnd R 3aRepresent hydrogen atom or can substituted ring texture or the alkyl of chain-like structure or R independently of one another 1a, R 2aAnd R 3aIn at least two mutually coupling form ring structure, R 4aExpression hydrogen atom or methyl, X represents divalent linker, Y -The expression counter anion.
5. according to the colored resin composition of claim 1, wherein composition further comprises the phosphate type dispersion agent as dispersion agent.
6. according to the colored resin composition of claim 5, wherein the phosphate type dispersion agent has the partial structural formula of following formula (3) expression:
7. according to the colored resin composition of claim 1, wherein said composition comprises that having molecular weight is not more than 1000 organic carboxyl acid and/or organic carboxyl acid acid anhydride.
8. according to the colored resin composition of claim 1, wherein carboxylic resin (a) has hydroxyl.
9. according to any one colored resin composition of claim 1 to 8, wherein composition further comprises photopolymerizable monomer.
10. according to any one colored resin composition of claim 1 to 9, wherein composition further comprises the Photoepolymerizationinitiater initiater system component.
11. according to claim 1,8 and 10 any one colored resin compositions, be added to the no nitrogen-atoms resin glue of the structure that the carboxyl of carboxylic resin (a) obtains by the epoxy group(ing) of mixing coloring material, solvent, dispersion agent and having a unsaturated compound (b) by containing epoxy group(ing), with the dispersion of gained mixture with as if necessary another component is mixed acquisition with dispersion liquid.
12. a red colored resin combination that comprises coloring material, solvent and resin glue, wherein:
When pigmentary resin composition during with the coating of such film thickness, promptly CIE than the colourity x in the color system become 0.60 and at 230 ℃ baking is after 30 minutes down, this falls into by in the scope of representing as shown in the formula (1) or (2) than the Y value in the color system:
Y≥200y-41.4(y＜0.34) (1)
Y≥100y-7.4(y≥0.34) (2)
Wherein Y and y represent that respectively CIE is than reflectivity in the color system and colourity;
When pattern formed with this pigmentary resin compound, the minimum pattern width that keeps as linear image was 10 μ m or littler; With
When having area 10cm 2Non-pixel region, promptly on obscure glass with pressure 1kgf/cm 2Following to having flooded 0.1cc/cm 2During the cloth 1cm that alcoholic acid mean sizes 3 μ m or littler polyester macrofiber constitute * 1cm wiping, the spectral reflectance on the pigment attachment portion is 95% or bigger at the 500nm place.
13. a green coloring resin combination that comprises coloring material, solvent and resin glue, wherein:
When pigmentary resin composition during with the coating of such film thickness, promptly CIE becomes 0.55 and 230 ℃ of bakings after 30 minutes down than the chromaticity y in the color system, and this falls into by as shown in the formula in the scope of representing than the Y value in the color system:
Y≥240x-7.1
Wherein Y and x represent that respectively CIE is than reflectivity in the color system and colourity;
When pattern formed with this colored resin composition, the minimum pattern width that keeps as linear image was 10 μ m or littler; With
When having area 10cm 2Non-pixel region, promptly on obscure glass with pressure 1kgf/cm 2Following to having flooded 0.1cc/cm 2During the cloth 1cm that alcoholic acid mean sizes 3 μ m or littler polyester macrofiber constitute * 1cm wiping, the spectral reflectance on the pigment attachment portion is 95% or bigger at the 450nm place.
14. a blue-colored resin combination that comprises coloring material, solvent and resin glue, wherein:
When pigmentary resin composition during with the coating of such film thickness, promptly CIE becomes 0.14 and 230 ℃ of bakings after 30 minutes down than the colourity x in the color system, and this falls into by as shown in the formula in the scope of representing than the Y value in the color system:
Y≥20x+16.2
Wherein Y and x represent that respectively CIE is than reflectivity in the color system and colourity;
When pattern formed with this colored resin composition, the minimum pattern width that keeps as linear image was 10 μ m or littler; With
When having area 10cm 2Non-pixel region, promptly on obscure glass with pressure 1kgf/cm 2Following to having flooded 0.1cc/cm 2During the cloth 1cm that alcoholic acid mean sizes 3 μ m or littler polyester macrofiber constitute * 1cm wiping, the spectral reflectance on the pigment attachment portion is 95% or bigger at the 550nm place.
15. according to any one colored resin composition of claim 12 to 14, wherein when said composition when storing 7 days down for 23 ℃, its viscosity velocity of variation with respect to initial viscosity is 10% or lower.
16. according to any one colored resin composition of claim 12 to 15, it comprises coloring material, solvent and resin glue, wherein soak and redispersion in the solvent of this colored resin composition of formation the time when the dry film that forms by colored resin composition, the volume average particle size mv in redispersion liquid is 200nm or littler.
17. according to any one colored resin composition of claim 12 to 16, it comprises coloring material, solvent and resin glue, wherein when filming of forming by colored resin composition with the liquid crystal state of contact under after the annealing, during to liquid crystal applied voltages, voltage retention is 80% or bigger by the pigmentary resin layer.
18. according to any one colored resin composition of claim 12 to 17, wherein this resin glue is the resin that can obtain by the following method: (methyl) acrylate (A) that contains epoxy group(ing) with 5 to 90mol% and 10 to 95mol% another can with free redical polymerization compound (B) copolymerization of component A copolymerization, unsaturated monoprotic acid (c) added in the gained multipolymer on contained 10 to 100mol% the epoxide group, and on 10 to the 100mol% hydroxyls that produce when adding to multi-anhydride (D) by addition said components (C).
19. according to any one colored resin composition of claim 12 to 18, wherein dispersion agent comprises at least a in the following material: amino formate dispersion agent (E), nitrogen atom graft copolymer (F) and A-B segmented copolymer and/or B-A-B segmented copolymer (G), each freedom have the block A of quaternary ammonium salt and do not have a quaternary ammonium salt in its side chain B block is formed.
20. filter substrate that forms with any one colored resin composition of claim 1 to 19.
21. liquid-crystal display that forms with the filter substrate of claim 20.
22. method of producing colored resin composition (M), comprise that the resin (H) that the epoxy group(ing) that will have the unsaturated compound (b) by containing epoxy group(ing) adds to the structure that obtains on the carboxyl of carboxylic resin (a) mixes with coloring material (I), and the gained mixture disperseed with the step of preparation colored resin composition (J) with this colored resin composition (J) and resin (K) and solvent (L) blended step.
23. according to the method for the production colored resin composition of claim 22, the unsaturated compound (b) that wherein contains epoxy group(ing) is the alicyclic epoxy compound.
24. according to the method for the production colored resin composition of claim 22 or 23, wherein carboxylic resin (a) has hydroxyl.
25. according to claim 22 to 24 any one the production colored resin composition method wherein said composition comprise that pigment derivative is as dispersing auxiliary.
26. one kind by any one the colored resin composition of (M) expression of preparation method preparation of claim 22 to 25.
27. colored resin composition, comprise that the epoxy group(ing) with the unsaturated compound (b) by containing epoxy group(ing) adds to resin (H), coloring material (I), photopolymerizable monomer and the Photoepolymerizationinitiater initiater of the structure that obtains on the carboxyl of carboxylic resin (a), wherein the resin Composition of at least 60 weight % is an alkali soluble resin.
28. a filter substrate, wherein this substrate forms with the colored resin composition of claim 26 or 27.
29. a liquid-crystal display, wherein this indicating meter forms with the filter substrate of claim 28.
CN2007101471878A 2003-02-07 2004-01-16 Colored resin composition, color filter, and liquid crystal display Expired - Lifetime CN101113224B (en)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP2003030954 2003-02-07
JP30954/03 2003-02-07
JP2003045364 2003-02-24
JP45364/03 2003-02-24
JP47604/03 2003-02-25
JP2003047604 2003-02-25
JP2003122854 2003-04-25
JP122854/03 2003-04-25
JP124291/03 2003-04-28
JP2003124291 2003-04-28
JP2003366100 2003-10-27
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KR100659959B1 (en) 2006-12-22

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