CN103529646B - Color filter green coloring composition and color filter - Google Patents

Color filter green coloring composition and color filter Download PDF

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Publication number
CN103529646B
CN103529646B CN201310349447.5A CN201310349447A CN103529646B CN 103529646 B CN103529646 B CN 103529646B CN 201310349447 A CN201310349447 A CN 201310349447A CN 103529646 B CN103529646 B CN 103529646B
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pigment
methyl
color filter
resin
weight
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CN103529646A (en
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宫泽由昌
中村高士
吉泽俊启
西田充志
有吉泰
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Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators

Abstract

The present invention relates to color filter green coloring composition and color filter.Disclose color filter green coloring composition, it contains (A) at least comprises the pigment carrier of resin, its precursor or their potpourri containing the pigment composition of zinc halide phthalocyanine color and (B), also 35 ~ 100mg containing being selected from (a) amine value? the basic resin type spreading agent of KOH/g, (b) have the pigment derivative of alkali subtituent and at least a kind of (c) mixed organic solvents, and it is 8.0 ~ 10.0 (cal/cm that described mixed organic solvents contains solubility parameters (SP value) 3) 1/2, boiling point under 760mmHg is the organic solvent (c1) of 140 ~ 159 DEG C; Be 8.0 ~ 10.0 (cal/cm with solubility parameters (SP value) 3) 1/2, boiling point under 760mmHg is the organic solvent (c2) of 160 ~ 200 DEG C.

Description

Color filter green coloring composition and color filter
The divisional application that the application is the applying date is on November 24th, 2008, application number is 200810182161.1, denomination of invention is the application of " color filter green coloring composition and color filter ".
Technical field
The present invention relates to the color filter green coloring composition used in the preparation of the color filter for color liquid crystal display arrangement, colour pick-up tube element etc., and use its color filter formed.
Background technology
Liquid crystal indicator is that the type employing twisted-nematic (TN) type liquid crystal just becomes mainstream type by being clipped in liquid crystal layer between 2 pieces of polaroids and controlling the polarisation of light degree through the 1st piece of polaroid and controlling to carry out through the light quantity of the 2nd piece of polaroid the display device that shows.Liquid crystal indicator can carry out colour display by arranging color filter between 2 pieces of polaroids, in recent years, owing to starting color filter to be applied to TV or personal computer monitor etc., so improve its high contrast ratio, the requirement of high brightness.
By color filter that is parallel for the color filter of fine band (striped) shape of two or more different form and aspect joint (Off イ Le タ セ グ メ Application ト) or cross-over configuration on the surface that color filter is included in the transparency carriers such as glass, or by fine color filter joint with the color filter of arrangement mode certain in length and breadth configuration.Color filter joint with several microns ~ hundreds of micron is fine like this and fitly configure in the mode arranged for regulation often kind of form and aspect.
Usually, in color liquid crystal display arrangement, by for driving the transparency electrode of liquid crystal to be formed by evaporation or sputtering on color filter, and then to be formed thereon for making liquid crystal in the alignment films of certain orientation orientation.In order to fully obtain the performance of these transparency electrodes and alignment films, it is formed needs to carry out under the high temperature of general more than 200 DEG C, preferably more than 230 DEG C.Therefore, at present as the preparation method of color filter, the method being referred to as pigment dispersion method using the pigment of photostability, excellent heat resistance as colorant becomes the method for main flow.
But, the General Decentralized light scattering etc. of color filter owing to causing because of pigment of pigment, and have the problem of the polarization degree disorder making LCD Controlling.That is, when required shield light (OFF state), light leaks, and must through (ON state) during light, transmitted light be decayed, the problem that in the display device therefore producing ON state and OFF state, the ratio (contrast ratio) of brightness is low.
In order to realize the high brightness of color filter, high contrast ratio, be that the pigment contained in color filter joint is carried out miniaturization process up to now.But, (be the particle being referred to as semifinished product (Network Le one De) of 10 ~ 100 μm by the particle diameter prepared by chemical reaction even if simple by pigment, by pigmentation process until become the pigment of the potpourri of the offspring of primary particle and its cohesion) utilize various miniaturization disposal route to carry out miniaturization, the pigment having carried out the miniaturization of primary particle or offspring generally also easily condenses, and also forms the pigment solid content of huge bulk when too carrying out miniaturization.And then for the pigment carrying out miniaturization, even if be dispersed in the pigment carrier containing resin etc., and again make the offspring of pigment make its stabilization close to primary particle as much as possible, it is also very difficult for obtaining stable coloured composition.
The pigment carrying out miniaturization is dispersed in coloured composition in pigment carrier often along with the time, the cohesion etc. of pigment particles occurred, thus causes high viscosity, manifest thixotropy.The viscosity of this coloured composition raises, poor flow quality causes the problem on preparation manipulation or in value of the product, causes various problem.Such as, the color filter joint of color filter is generally formed by being spin-coated on glass substrate by coloured composition, pigment dispersion forms by described coloured composition in the pigment carrier containing monomer and resin, if use the coloured composition of high viscosity, poor flow quality, then cause the film that can not obtain uniform film thickness because spin coating is bad, levelling is bad etc., from instead of preferred.
Color filter is by being coated with drying on the transparent substrate by color composition for color filter (below also referred to as being coating fluid), and formation thickness is that the film of about 0.2 ~ 5 μm is prepared like this.Coating method has spin-coating method or mouth mould rubbing method etc., suitably can use according to its feature.
Spin-coating method is widely used in film forming method on less substrate, this coating process is while make transparency carrier rotate with certain rotation number, while drip coating fluid at transparency carrier central part, centrifugal force is utilized to be launched thinly by coating fluid, by controlling to be suitable for the rotation number of the transparency carrier of this coating fluid or rotational time etc., and form the film expecting thickness on the surface of transparency carrier.But, come from and utilize by rotating the centrifugal force that causes and by principle such for very thin for film expansion, have the shortcoming that the rotation center part of transparency carrier is too thickening compared with intermediate portion with the coating film thickness of peripheral part.In patent documentation 1, describe the coating fluid composition containing more than 50 % by weight boiling points or the solvent of vapor pressure in particular range being made the spin coating mode of the surface smoothness excellence of film.
When the size of substrate is large, in the mode making substrate rotate that spin-coating method is such, the load for device is large, therefore adopts mouth mould rubbing method.Mouth mould coating method discharges coating fluid from slit, moves this slit and will expect that on substrate the film of thickness is formed at the coating process on the surface of transparency carrier.But, for this structure, relative to the working direction of slit, the bar shaped being easy to produce vertical direction is uneven, in addition, in slit opening portion, coating fluid exposes and in an atmosphere dry solidification occurs, and produces condensation product thus, and the bar shaped that coating working direction occurs is uneven, this condensation product is mixed in coating material, forms film shortcoming.And then film peripheral part swells, and compared with portion of substrate center, has the problem that film is thickening.
In order to eliminate the problem of this film unevenness in mouth mould rubbing method, carry out the trial described in following patent documentation.
In patent documentation 2 and 3, disclose by containing high boiling solvent, prevent coating fluid dry solidification, and do not produce the method for condensation product.
[patent documentation 1] Unexamined Patent 6-3521 publication
[patent documentation 2] JP 2003-55566 publication
[patent documentation 3] JP 2004-346218 publication
On the other hand, for above-mentioned color filter, not only require high contrast ratio, also require high brightness.Being generally and having obtained high lightness, when being dispersed in pigment carrier by pigment, having made it close to primary particle, improved the transparency of dispersion, make dispersion have high-transmission rate in spectrophotometric spectra, obtain high lightness thus.
But, (red bluish-green as 3 kinds of primary colors of filter substrate; RGB) a kind of green in generally uses halogenated copper phthalocyanine pigment (such as C.I. pigment green 36 or C.I. pigment Green 7) as body pigment, as long as but use halogenated copper phthalocyanine, be just difficult to take into account high contrast ratio and high brightness.
In order to address these problems, bring into use zinc halide phthalocyanine color central metal being replaced to zinc from existing halogenated copper phthalocyanine pigment, be used as playing distinct tone and color viewing area there is the look material of high colouring power widely.
[patent documentation 4] Unexamined Patent 10-130547 publication
[patent documentation 5] JP 2001-141922 publication
[patent documentation 6] JP 2007-204658 publication
But zinc halide phthalocyanine green pigment acidity compared with halogenated copper phthalocyanine green pigment is high.Therefore, zinc halide phthalocyanine green pigment is difficult to dispersion than halogenated copper phthalocyanine green pigment.Disperse bad coloured composition that the cohesion etc. of pigment particles often occurs in time, thus cause high viscosity, manifest thixotropy.The viscosity of this coloured composition raises, poor flow quality causes the problem on preparation manipulation or in value of the product, causes various problem.Such as, the color filter joint of color filter is generally formed by being spin-coated on glass substrate by coloured composition, described coloured composition dispersed color in the pigment carrier containing monomer and resin forms, if use the coloured composition of high viscosity, poor flow quality, then cause the film that can not obtain uniform film thickness because spin coating is bad, levelling is bad etc., from instead of preferred.
In addition, known zinc halide phthalocyanine color is different from the chemical property of existing halogenated copper phthalocyanine pigment, and is difficult to the pigment of dispersion.Therefore, only use the spreading agent being suitable for existing halogenated copper phthalocyanine pigment or other pigment, be difficult to zinc halide phthalocyanine color stably to disperse under the state of color characteristics maintaining its excellence.
On the other hand, in order to obtain the zinc halide phthalocyanine color dispersion of high fluidity, use must can bring the spreading agent of more bad impact to each patience in a large number, in order to maintain high pigment levels, the amount of the pigment carrier composition of each patience of minimizing maintenance of having to, result is difficult to take into account each patience, mobility and color characteristics.
And then, zinc halide phthalocyanine color is different from existing halogenated copper phthalocyanine pigment, the solubleness of its pigment itself is different, therefore for the solvent of the most applicable dispersion halogenated copper phthalocyanine pigment, zinc halide phthalocyanine color and its compatibility are too good, when being used for disperseing ZnPc pigment by these solvents, pigment itself is dissolved in solvent, has the problem that can not obtain the dispersion with high contrast ratio and high brightness.
And then, for the coloured composition (patent documentation 1 ~ 3) employing the zinc halide phthalocyanine color that solvent used in the dispersion of halogenated copper phthalocyanine pigment carries out disperseing, due to spin coating mode as above or the such coating method of mouth mould coating method and the proterties of coating fluid that uses wherein, and have and produce the shortcoming that thickness is uneven or bar shaped is uneven.
Here, thickness inequality refers to that the homogeneity of thickness is insufficient, can be divided into the film thickness uniformity of " film thickness uniformity (end) ", i.e. end face portion and " film thickness uniformity (beyond end) ", the i.e. homogeneity these 2 kinds here from substrate center to end face.In addition, bar shaped inequality can be divided into 2 kinds: " horizontal stripe shape uneven ", namely in mouth mould coating method, the inequality of strip that produces on the direction vertical with the working direction of slit, and " taeniae shape is uneven ", in mouth mould coating method, namely come from the inequality of the strip in slit working direction of the condensation product in slit opening portion.
Summary of the invention
Therefore, the object of the present invention is to provide the stable color filter green coloring composition of mobility and each patience excellence, and use its lightness and the high color filter of contrast ratio.
In addition, the object of the present invention is to provide color filter green coloring composition (green anticorrosive additive material), with the color filter with the color filter joint using it to be formed, described color filter green coloring composition can reduce viewed shortcoming in the film of the coating material utilizing spin coating mode and mouth mould rubbing method to be formed, and then can form lightness and the high color filter of contrast ratio.
Above-mentioned problem can be solved by color filter green coloring composition, and described color filter green coloring composition contains:
(A) at least containing zinc halide phthalocyanine color pigment composition and
(B) pigment carrier of resin, its precursor or their potpourri is comprised, and
Containing being selected from:
(a) amine value be 35 ~ 100mgKOH/g basic resin type spreading agent,
(b) have alkali subtituent pigment derivative and
C at least a kind of () mixed organic solvents forms, it is 8.0 ~ 10.0 (cal/cm that described mixed organic solvents contains solubility parameters (SP value) 3) 1/2, boiling point under 760mmHg is the organic solvent (c1) of 140 ~ 159 DEG C; Be 8.0 ~ 10.0 (cal/cm with solubility parameters (SP value) 3) 1/2, boiling point under 760mmHg is the organic solvent (c2) of 160 ~ 200 DEG C.
In the preferred version of color filter green coloring composition of the present invention, when acid value being denoted as X (mgKOH/g), weight-average molecular weight is when being denoted as Y, and the resin forming above-mentioned pigment carrier (B) is the resin of condition simultaneously all meeting following formula (F), (G) and (H):
(F)Y＞-750X+51000
(G)Y＞940X-79000
(H)Y＞8000。
In the preferred version of color filter green coloring composition of the present invention, when being benchmark with the general assembly (TW) of the above-mentioned pigment composition (A) [having the situation simply referred to as pigment composition (A) below] containing zinc halide phthalocyanine color, the content of above-mentioned basic resin type spreading agent (a) is 0.001 ~ 50 % by weight.
In the preferred version of color filter green coloring composition of the present invention, above-mentioned basic resin type spreading agent (a) being comprises the block copolymer resin of base copolymer block (a1) and pigment carrier compatibility copolymer block (a2), such as, utilize the block copolymer resin that living polymerization obtains.
In the preferred version of color filter green coloring composition of the present invention, when being benchmark with the general assembly (TW) of above-mentioned pigment composition (A), the content of above-mentioned pigment derivative (b) is 0.001 ~ 40 % by weight.
In the preferred version of color filter green coloring composition of the present invention, above-mentioned organic solvent (c1) is the solvent of more than at least a kind being selected from propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, ethylene glycol monomethyl ether acetic acid ester and ethylene glycol monomethyl ether acetate.
In the preferred version of color filter green coloring composition of the present invention, above-mentioned organic solvent (c2) is the solvent of more than at least a kind being selected from cyclohexyl acetate, propylene-glycol diacetate, diethylene glycol diethyl ether and 3-ethoxyl ethyl propionate.
In the preferred version of color filter green coloring composition of the present invention, when being benchmark with the total amount of above-mentioned mixed organic solvents (c), above-mentioned organic solvent (c1) is 50 % by weight ~ 95 % by weight, and above-mentioned organic solvent (c2) is 5 % by weight ~ 50 % by weight.
In the preferred version of color filter green coloring composition of the present invention, and then containing Photoepolymerizationinitiater initiater.
In the preferred version of color filter green coloring composition of the present invention, containing above-mentioned basic resin type spreading agent (a) and above-mentioned pigment derivative (b).
In the preferred version of color filter green coloring composition of the present invention, containing above-mentioned basic resin type spreading agent (a) and above-mentioned mixed organic solvents (c).
In the preferred version of color filter green coloring composition of the present invention, containing above-mentioned pigment derivative (b) and above-mentioned mixed organic solvents (c).
In the preferred version of color filter green coloring composition of the present invention, containing above-mentioned basic resin type spreading agent (a), above-mentioned pigment derivative (b) and above-mentioned mixed organic solvents (c).
In addition, the present invention relates to color filter, it is characterized in that, there is green color filter joint (green Off イ Le タ セ グ メ Application ト) formed by above-mentioned color filter green coloring composition.
Color filter green coloring composition of the present invention is by least containing the pigment composition of zinc halide phthalocyanine color containing (A); (B) pigment carrier of resin, its precursor or their potpourri is comprised, and then containing be selected from above-mentioned basic resin type spreading agent (a), above-mentioned pigment derivative (b) and above-mentioned mixed organic solvents (c) at least a kind, thus high flowing can be formed and stable pigment dispersion, by using said composition, high brightness can be formed and the color filter of high contrast ratio.In addition, can be formed in viewed existing shortcoming in the film of coating material and reduce, contrast ratio and the high color filter of lightness.
Especially, when above-mentioned basic resin type spreading agent (a) being comprises the block copolymer resin of base copolymer block (a1) and pigment carrier compatibility copolymer block (a2), and then become the pigment dispersion of the color filter that can form high contrast ratio.
And then when containing above-mentioned basic resin type spreading agent (a) with when having the pigment derivative (b) of alkali subtituent, initial contrast ratio uprises, and ageing stability is also good.
Accompanying drawing explanation
[Fig. 1] is for measuring the mode declaration pattern specification figure of the determinator of contrast ratio.
Symbol description
(1) nitometer
(2) mask
(3) polaroid
(4) coloured composition dry coating
(5) glass substrate
(6) polaroid
(7) back light unit
Embodiment
First, enumerate preferred embodiment color filter green coloring composition of the present invention is described in detail.
And, in the description, when being expressed as " (methyl) acryloyl ((メ タ) ア Network リ ロ イ Le) ", " (methyl) acryloyl group ((メ タ) ア Network リ Le) ", " (methyl) acrylic acid ", " (methyl) acrylate ", time " (methyl) acryloxy ", if be not particularly described, then represent " acryloyl and/or methacryl " respectively, " acryloyl group and/or methacryl ", " acrylic acid and/or methacrylic acid ", " acrylate and/or methacrylate ", " acryloxy and/or methacryloxy ".
Color filter green coloring composition of the present invention contains (A) pigment composition at least containing zinc halide phthalocyanine color; (B) comprise the pigment carrier of resin, its precursor or their potpourri, in the 1st embodiment, and then contain the basic resin type spreading agent that (a) amine value is 35 ~ 100mgKOH/g;
In the 2nd embodiment, there is containing above-mentioned basic resin type spreading agent (a) and/or (b) pigment derivative of alkali subtituent;
In the 3rd embodiment, be 8.0 ~ 10.0 (cal/cm containing above-mentioned basic resin type spreading agent (a) and/or above-mentioned pigment derivative (b) and/or (c) containing solubility parameters (SP value) 3) 1/2, boiling point under 760mmHg is the organic solvent (c1) of 140 ~ 159 DEG C; Be 8.0 ~ 10.0 (cal/cm with solubility parameters (SP value) 3) 1/2, boiling point under 760mmHg is the mixed organic solvents of the organic solvent (c2) of 160 ~ 200 DEG C.
That is, can contain simultaneously above-mentioned basic resin type spreading agent (a), above-mentioned pigment derivative (b) and above-mentioned mixed organic solvents (c) any 2 kinds, or whole 3 kinds.
[pigment composition (A)]
The feature of color filter green coloring composition of the present invention is, employs at least containing the pigment composition (A) of zinc halide phthalocyanine color as body pigment.
When representing typical zinc halide phthalocyanine color with color index (C.I) number, C.I. naphthol green 58 etc. can be enumerated.By using zinc halide phthalocyanine color as body pigment, can obtain with the not getable high lightness of other viridine greens.And then, the pigment obtained by known manufacture method can be used.Especially, following such pigment can be used, namely, when utilizing look material, the method described in 67 [9], 547-554 (1994), and when using n-hexylamine to measure as alkaline matter, the acidic functionality amount of this surface of pigments is preferably 100 μm of more than ol/g, and then preferred 200 μm of more than ol/g.
Not only containing as the zinc halide phthalocyanine of body pigment in pigment composition (A), for color adaptation or complementary color object can also and with other viridine green or yellow uitramarine.
As can and other viridine green, can enumerate C.I. pigment Green 7,10,36, the viridine green of 37 etc.In addition, as can and yellow uitramarine, C.I. pigment yellow 1 can be enumerated, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, the yellow uitramarine of 214 grades.
Wherein, consider from the angle that can expand chroma areas, preferably also with C.I. pigment yellow 13 8,139,150,185 etc.
In whole nonvolatile component of coloured composition of the present invention, consider from the angle obtaining sufficient color reproducibility, the concentration of preferred pigment composition (A) is 10 ~ 90 % by weight, more preferably 15 ~ 80 % by weight, most preferably 20 ~ 70 % by weight.When the concentration of pigment composition (A) is less than 10 % by weight, sufficient color reproducibility can not be obtained, when more than 90 % by weight, the concentration step-down of pigment carrier, the bad stability of coloured composition.
As the ratio of particularly preferred pigment, such as, when being benchmark with the general assembly (TW) of pigment composition (A), zinc halide phthalocyanine color is 50 ~ 100 % by weight, and halogenated copper phthalocyanine pigment is 0 ~ 50 % by weight, and yellow uitramarine is 0 ~ 50 % by weight.
More preferably with pigment composition (A) for benchmark, zinc halide phthalocyanine color is 50 ~ 90 % by weight, and halogenated copper phthalocyanine pigment is 5 ~ 45 % by weight, and yellow uitramarine is 5 ~ 45 % by weight.Utilize the composition of this pigment, can chroma areas be expanded.
For the green coloring composition of the present invention employing zinc halide phthalocyanine color, when being coated on glass substrate etc., identical colourity to be formed with the green coloring composition employing halogenated copper phthalocyanine, and when measuring the transmissivity of film, near 530nm, be shown as the transmissivity higher than the film of the coloured composition employing copper phthalocyanine near 450nm.Especially for the peak value of transmissivity, be shown as about about 50% high transmissivity, be about the value of 90%.Therefore, by combined with the backlight generally used in color liquid crystal display arrangement, the not getable high brightness of coloured composition employing the copper phthalocyanine such as C.I. pigment green 36 or C.I. pigment Green 7 can be obtained.
[miniaturization of pigment]
The pigment used in green coloring composition of the present invention can carry out salt milled processed and form with miniaturization uses, and preferably uses the pigment of miniaturization.
Salt milled processed refers to the mixing roll using kneader, two roller mills, three-roll mill, bowl mill, vertical ball mill or sand mill etc., the potpourri of pigment and water-soluble inorganic salt and water-miscible organic solvent is heated while after carrying out mechanically milling, is removed the process of water-soluble inorganic salt and water-miscible organic solvent by washing.Water-soluble inorganic salt plays a role as broken auxiliary agent, utilizes the high rigidity of inorganic salts to carry out broken pigment, produce active face thus, carry out crystalline growth during salt grinding.Therefore, time mixing, the fragmentation of pigment and crystalline growth carry out simultaneously, and according to compounding conditions, the primary particle size of the pigment obtained is different.
In order to promote crystalline growth by heating, preferred heating-up temperature is 40 ~ 150 DEG C.When heating-up temperature is less than 40 DEG C, fully crystalline growth can not occur, the shape of pigment particles, close to amorphous, is not therefore preferred.On the other hand, when heating-up temperature is more than 150 DEG C, crystalline growth too carries out, and the primary particle size of pigment becomes large, and the colouring material therefore as color composition for color filter is not preferred.In addition, the mixing time of salt milled processed is considered from the angle of the balance of expense needed for the size-grade distribution of the primary particle of salt milled processed pigment and salt milled processed, is preferably 2 ~ 24 hours.
By by condition optimization when pigment being carried out to salt milled processed, 1 particle diameter can be obtained very fine, the narrow range distributed in addition, there is the pigment of narrow size-grade distribution.
The primary particle size that the viridine green used in green coloring composition of the present invention is tried to achieve by TEM (transmission electron microscope) is preferably the scope of 20 ~ 100nm.When less than 20nm, dispersion in organic solvent becomes difficult.In addition when larger than 100nm, sufficient contrast ratio can not be obtained.Particularly preferred scope is the scope of 25 ~ 85nm.
As the water-soluble inorganic salt used in salt milled processed, sodium chloride, barium chloride, potassium chloride or sodium sulphate etc. can be used, consider preferably to use sodium chloride (salt) from the angle of price.Consider from treatment effeciency and production efficiency these two aspects, during using the general assembly (TW) of pigment composition (A) as benchmark, the use amount of water-soluble inorganic salt is preferably 50 ~ 2,000 % by weight, and most preferably 300 ~ 1,000 % by weight.
Water-miscible organic solvent has the function of moistening pigment and water-soluble inorganic salt, as long as it dissolves (mixing) and does not substantially dissolve the solvent of the inorganic salts of use in water, is not particularly limited.But because temperature when salt grinds raises, solvent is in the state being easy to evaporate, so consider from the angle of security, preferred boiling point is the high boiling solvent of more than 120 DEG C.Such as can use 2-methyl cellosolve, butoxy ethanol, 2-(isoamoxy) ethanol, 2-(own oxygen base) ethanol, diglycol, carbiphene, diethylene glycol monobutyl ehter, triethylene glycol, triethylene glycol monomethyl ether, liquid polyglycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, or the polypropylene glycol etc. of liquid state.During using the general assembly (TW) of pigment composition (A) as benchmark, water-miscible organic solvent preferably uses the amount of 5 ~ 1,000 % by weight, most preferably uses the amount of 50 ~ 500 % by weight.
When carrying out salt milled processed, also resin can be added as required.The kind of the resin used is not particularly limited, and can use natural resin, modified natural resin, synthetic resin or the synthetic resin etc. with natural resin modification.The resin used is at room temperature solid, is preferably water-insoluble, and and then preferably can be partially dissolved in above-mentioned organic solvent.During using the general assembly (TW) of pigment composition (A) as benchmark, the use amount of resin is preferably the scope of 5 ~ 200 % by weight.
[pigment carrier (B)]
In green coloring composition of the present invention, except pigment composition (A), also containing the pigment carrier (B) comprising resin, its precursor or their potpourri.
The pigment carrier (B) used in green coloring composition of the present invention, is that the full wavelength region may spectral transmission of 400 ~ 700nm in visible region is preferably more than 80%, is more preferably the resin of more than 95%, its precursor or their potpourri.Resin contains thermoplastic resin, heat-curing resin or active energy ray-curable resin, its precursor comprises and utilizes active energy beam to irradiate to be cured and to generate monomer or the oligomer of transparent resin, can by they separately or two or more mixing use.During using the general assembly (TW) of pigment composition (A) as benchmark, pigment carrier (B) can use the amount of 30 ~ 500 % by weight.When being less than 30 % by weight, film forming and each patience are not enough, when than more than 500 % by weight time, pigment concentration is low, can not apparent color characteristic.
When acid value being denoted as X (mgKOH/g), weight-average molecular weight is when being denoted as Y, and the resin preferably forming above-mentioned pigment carrier (B) is the resin of condition simultaneously all meeting following formula (F), (G) and (H):
(F)Y＞-750X+51000
(G)Y＞940X-79000
(H)Y＞8000。
When form above-mentioned pigment carrier (B) resin meet above formula (F), (G) and (H) full terms time, owing to having good acid value scope, so the resin type spreading agent be adsorbed on pigment and above-mentioned resin can maintain suitable interaction, in addition due to good molecular weight ranges, so the function of the steric hindrance as vector resin moderately can be played, thus good disperse state can be maintained, be therefore preferred.Especially, the pigment derivative (b) used in basic resin type spreading agent (a) that uses in following 1st embodiment of the present invention and/or following 2nd embodiment of the present invention can be made to adsorb well on the surface of the pigment.On the contrary, when the resin forming above-mentioned pigment carrier (B) does not meet the condition of above formula (F), absorption above-mentioned basic resin type spreading agent (a) is on the surface of the pigment too weak with the interaction of above-mentioned resin, therefore can not maintain good disperse state due to the reason of pigment agglomeration etc.When not meeting the condition of above formula (G), above-mentioned interaction is too strong, and the resin type spreading agent be therefore adsorbed on pigment is stripped, and can not maintains good disperse state due to the reason of pigment agglomeration etc.In addition, when not meeting the condition of above formula (H), because molecular weight is too little, so above-mentioned resin can not play the effect as steric hindrance, thus form dispersion due to the reason of pigment agglomeration etc. bad.In addition, preferred Y≤60000, and then preferred Y≤50000.If Y is more than 60000, then occurring when using as the painted resist of following alkali developable the situation that developability is bad, is not therefore preferred.
Thermoplastic resin can enumerate such as butyral resin, styrene-maleic acid copolymer, haloflex, chlorinated polypropylene, Polyvinylchloride, vinyl chloride-acetate base ester copolymer, polyvinyl acetate base ester, polyurethane series resin, vibrin, acrylic resin, alkyd resin, polystyrene resin, polyamide, rubber series resin, thermoprene system resin, cellulose family, tygon (HDPE, LDPE), polybutadiene, polyimide resin etc.
In addition, heat-curing resin can enumerate such as epoxy resin, benzoguanamine resin, Abietyl modified maleic acid resin, Abietyl modified fumaric resin, melamine resin, urea resin and phenolics etc.
When using with the form of the painted resist of following alkali developable, preferably use the alkali soluble resins with acidic-group of (methyl) acrylic copolymer resin (alkaline soluble acrylic resin) etc.In order to disperse zinc halide phthalocyanine color well, the weight-average molecular weight (Mw) of alkali soluble resins preferably 10, the scope of 000 ~ 100,000, more preferably 30,000 ~ 80, the scope of 000.Number-average molecular weight (Mn) is preferably 5,000 ~ 50 in addition, and the scope of 000, the value of preferred Mw/Mn is less than 10.
Further, in the present invention, the molecular weight distribution [weight-average molecular weight (Mw), number-average molecular weight (Mn)] of resin utilizes GPC to measure with following condition.
Device: GPC-150C (ウ オ mono-タ mono-ズ society)
Pillar: GMH-HT30cm2 connects (eastern ソ mono-society system)
Temperature: 135 DEG C
Solvent: o-dichlorobenzene (adding 0.1%2,6-di-tert-butyl-4-methy phenol (ア イ オ ノ mono-Le))
Flow velocity: 1.0ml/min
Sample: the sample injecting 0.4ml0.15%
Measure by above condition, when the molecular weight of calculation sample, use the molecular weight calibration curve utilizing monodisperse polystyrene standard model to make.And then, calculated by polyethylene conversion with the conversion formula of being derived by Mark-Houwink viscosity formula.
Active energy ray-curable resin can use following resin; it makes to have isocyanate group, aldehyde radical or epoxy radicals isoreactivity substituent (methyl) acyclic compound or cinnamic acid and have hydroxyl, carboxyl or the substituent linear polymeric of amino isoreactivity to react, thus group such as photocrosslinking reaction such as introducing (methyl) acryloyl group or styryl etc. forms in this wire macromolecule.In addition, can also use following such resin, the wire macromolecule containing acid anhydrides such as styrene-maleic anhydride copolymer or alpha-olefin-copolymer-maleic anhydride is carried out half-esterification forming by its (methyl) acyclic compound utilizing (methyl) hydroxyalkyl acrylates etc. to have hydroxyl.
Can enumerate such as the monomer of resin precursor and oligomer, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) isoamyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid cetyl, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, the different myristyl ester of (methyl) acrylic acid, (methyl) stearyl acrylate base ester, or the straight chain of (methyl) acrylic acid iso stearyl ester etc. or side chain (methyl) alkyl acrylate,
(methyl) acrylate base ester class of (methyl) cyclohexyl acrylate, (methyl) t-butylcyclohexyl ester, (methyl) acrylic acid two ring pentyl ester, (methyl) acrylic acid two cyclopentyloxy ethyl ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester or (methyl) isobornyl acrylate etc.;
(methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) perfluoroethyl are for (methyl) fluoroalkyl base ester class of octyl group ethyl ester or (methyl) acrylic acid tetrafluoro propyl ester etc.;
(methyl) acryloxy modified dimethyl polysiloxane (siloxane macromer) class;
(methyl) esters of acrylic acid with heterocycle of (methyl) acrylic acid tetrahydro furfuryl ester or (methyl) acrylic acid-3-methyl-3-oxetanyl ester etc.;
(methyl) benzyl acrylate, (methyl) acrylate, phenoxy group polyglycol (methyl) acrylate, (methyl) acrylic acid are to cumylphenoxy ethyl ester, (methyl) esters of acrylic acid with aromatic ring to cumylphenoxy polyglycol (methyl) acrylate or Nonylphenoxy polyglycol (methyl) acrylate etc.;
(methyl) acrylic acid-2-methoxy acrylate, (methyl) acrylic acid-2-ethoxy ethyl ester, (methyl) acrylic acid-3-methoxybutyl, (methyl) acrylic acid-2-methoxyl propyl ester, diethylene glycol monomethyl ether (methyl) acrylate, carbiphene (methyl) acrylate, triethylene glycol monomethyl ether (methyl) acrylate, triethylene glycol monoethyl ether (methyl) acrylate, diglycol monotertiary-2-ethyl hexyl ether (methyl) acrylate, dipropylene glycol monomethyl ether (methyl) acrylate, tripropylene glycol list (methyl) acrylate, polyethyleneglycol lauryl ether (methyl) acrylate, or (gathering) alkylene glycol monoalkyl ethers (methyl) esters of acrylic acid of polyethyleneglycol stearyl ether (methyl) acrylate etc.,
(methyl) acrylic acid, acrylic acid dimer, phthalic acid-2-(methyl) acryloyloxyethyl ester, phthalic acid-2-(methyl) acryloxy propyl ester, hexahydro-phthalic acid-2-(methyl) acryloyloxyethyl ester, hexahydro-phthalic acid-2-(methyl) acryloxy propyl ester, ethylene-oxide-modified succinic acid (methyl) acrylate, (methyl) senecioate-carboxyethyl, or (methyl) esters of acrylic acid with carboxyl of ω-carboxy-polycaprolactone (methyl) acrylate etc.,
(methyl) 2-hydroxyethyl acrylate, (methyl) acrylic acid-2-hydroxypropyl ester, (methyl) acrylic acid-2-hydroxyl butyl ester, (methyl) acrylic acid-4-hydroxyl butyl ester, 2-acryloyl-oxyethyl-2-hydroxyethyl (methyl) phthalic ester, diglycol monotertiary (methyl) acrylate, dipropylene glycol list (methyl) acrylate, polyethyleneglycol (methyl) acrylate, propylene glycol list (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polytetramethylene glycol list (methyl) acrylate, poly-(ethylene glycol and 1,2-propylene glycol) single (methyl) acrylate, poly-(ethylene glycol-butylene glycol) single (methyl) acrylate, poly-(propylene glycol-butylene glycol) single (methyl) acrylate, or (methyl) esters of acrylic acid with hydroxyl of glycerine (methyl) acrylate etc.,
Ethylene glycol bisthioglycolate (methyl) acrylate, diglycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, poly-(ethylene glycol and 1,2-propylene glycol) two (methyl) acrylate, poly-(ethylene glycol-butylene glycol) two (methyl) acrylate, poly-(propylene glycol-butylene glycol) two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, 1,3-BDO two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, or 2-ethyl, (gathering) aklylene glycol two (methyl) esters of acrylic acid of 2-butyl propylene glycol two (methyl) acrylate etc.,
Dihydroxymethyl bicyclopentane two (methyl) acrylate, hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylate, stearic acid modified pentaerythrite two (methyl) acrylate, ethylene-oxide-modified bisphenol-A two (methyl) acrylate, epoxy pronane modification bisphenol-A two (methyl) acrylate, tetrahydrofuran modified bisphenol A two (methyl) acrylate, ethylene-oxide-modified Bisphenol F two (methyl) acrylate, epoxy pronane modification Bisphenol F two (methyl) acrylate, tetrahydrofuran modified bisphenol F bis-(methyl) acrylate, dizinc acrylate resin, ethylene-oxide-modified tricresyl phosphate acrylate, or two (methyl) esters of acrylic acid of glycerine two (methyl) acrylate etc.,
(methyl) esters of acrylic acid with tertiary amino of (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid lignocaine ethyl ester, (methyl) acrylate propyl ester or (methyl) acrylic acid lignocaine propyl ester etc.;
Multitube energy (methyl) acrylate more than trifunctional of glycerine three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate or dipentaerythritol six (methyl) acrylate etc.;
Glycerin triglycidyl ether-(methyl) acrylic acid adduct, glycerol diglycidyl ether-(methyl) acrylic acid adduct, polyglycereol polyglycidyl ether-(methyl) acrylic acid adduct, 1,6-butanediol diglycidyl ether-(methyl) acrylic acid adduct, alkyl glycidyl ether-(methyl) acrylic acid adduct, allyl glycidyl ether-(methyl) acrylic acid adduct, phenyl glycidyl ether-(methyl) acrylic acid adduct, styrene oxide-(methyl) acrylic acid adduct, bisphenol A diglycidyl ether-(methyl) acrylic acid adduct, epoxy pronane modification bisphenol A diglycidyl ether-(methyl) acrylic acid adduct, Bisphenol F diglycidyl ether-(methyl) acrylic acid adduct, chloropropylene oxide modification phthalic acid-(methyl) acrylic acid adduct, chloropropylene oxide modification hexahydrophthalic acid-(methyl) acrylic acid adduct, ethylene glycol diglycidylether-(methyl) acrylic acid adduct, polyethyleneglycol diglycidylether-(methyl) acrylic acid adduct, propylene glycol diglycidylether-(methyl) acrylic acid adduct, polyethyleneglycol diglycidylether-(methyl) acrylic acid adduct, phenol novolak resin type epoxy resin (Off エ ノ mono-Le ノ ボ ラ Star Network type エ Port キ シ resin)-(methyl) acrylic acid adduct, cresol novolak type epoxy resin (Network レ ゾ mono-Le ノ ボ ラ Star Network type エ Port キ シ resin)-(methyl) acrylic acid adduct, or epoxy (methyl) esters of acrylic acid of other epoxy resin-(methyl) acrylic acid adduct etc.,
(methyl) acryloyl modified resin oligomer class of (methyl) acryloyl modification isocyanuric acid ester, (methyl) acryloyl modified polyurethane, (methyl) acryloyl modified poly ester, (methyl) acryloyl modified cyanurotriamide, (methyl) acryloyl modified polyorganosiloxane, (methyl) acryloyl modified polybutadiene or (methyl) acryloyl modified rosin etc.;
The vinyl of styrene, α-methyl styrene, vinyl-acetic ester, (methyl) vinyl acrylate or (methyl) allyl acrylate etc.;
The vinyl ethers of hydroxyethyl vinylethers, ethylene glycol divinyl ether or pentaerythrite trivinyl ether etc.;
The amide-type of (methyl) acrylamide, N-methylol (methyl) acrylamide or N-vinyl formamide etc.; Or
Vinyl cyanide etc.These compounds can be used alone, or two or more is used in combination, but it is not limited to these compounds.
[basic resin type spreading agent (a)]
The feature of green coloring composition of the present invention is, the zinc halide phthalocyanine using central metal to have zinc is used as the main pigments of pigment composition (A), above-mentioned zinc halide phthalocyanine is compared with the general halogenated copper phthalocyanine pigment used in green coloring composition, be the acid pigment that central metal has zinc, this surface of pigments has negative charge.Therefore, in the 1st embodiment of the present invention, by using basic resin type spreading agent (a) with 35 ~ 100mgKOH/g amine value high like this as the resin type spreading agent used when pigment disperses, it can be made to become abundant to the absorption of acid pigment, and dispersion can obtain sufficient mobility.
The number-average molecular weight of basic resin type spreading agent (a) that the present invention uses is preferably 500 ~ 50000 usually, especially, and then preferably 3000 ~ 30000.When above-mentioned number-average molecular weight is less than 500, the steric repulsion effect caused by pigment affinity groups, with the effect of the compatibility of pigment carrier and when using solvent and the effect of the compatibility of pigment carrier and solvent diminish, be difficult to the cohesion preventing pigment, the viscosity of dispersion raises.In addition, when number-average molecular weight is more than 50000, the addition of the resin required for dispersion increases, and causes the reduction of the pigment concentration in film.
In the 1st embodiment of the present invention, amine value is used to be basic resin type spreading agent (a) of 35 ~ 100mgKOH/g.The amine value of basic resin type spreading agent (a) and then be preferably 50 ~ 75mgKOH/g.When amine value is less than 35mgKOH/g, can not be adsorbed on that pigment to be formed dispersion bad fully, when more than 100mgKOH/g, due to for the absorption of the acid ingredient in pigment carrier or reaction, and the adsorption efficiency for zinc halide phthalocyanine color is deteriorated, form dispersion bad.
Amine value is that basic resin type spreading agent (a) of 35 ~ 100mgKOH/g can use ethene base system, carbamate system, Polyester, polyethers system or various types of resin system such as polyamide-based, but the ethene base system monomer copolymer type of easy, each patience excellence of preferred resin design, specifically, the copolymer resin of the vinyl monomer unit preferably containing N, N-disubstituted amido and (methyl) alkyl acrylate monomer units and other ethene base system monomeric unit.
Containing N, the vinyl monomer unit of N-disubstituted amido can be enumerated, (methyl) acrylic acid-N, N-dimethylaminoethyl, (methyl) acrylic acid-N, N-lignocaine ethyl ester, (methyl) acrylic acid-N, N-dimethylamino propyl ester, (methyl) acrylic acid-N, N-lignocaine propyl ester, N, N-dimethylaminoethyl (methyl) acrylamide or N, N-diethyllaminoethyl (methyl) acrylamide etc., but it is not limited to these compounds.These monomeric units are adsorbed on as the monomeric unit containing basic group on the high zinc halide phthalocyanine color of acidity.
(methyl) alkyl acrylate monomer units can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) cyclohexyl acrylate, (methyl) stearyl acrylate base ester, or the unsaturated monocarboxylic of (methyl) lauryl acrylate etc. and carbon number be 1 ~ 18 alkylol react (methyl) esters of acrylic acid etc. of gained, but it is not limited to these compounds.These monomeric units play a role as pigment carrier affinity groups.
Other ethene base system monomeric unit can enumerate the ethene base system monomer class containing itrile group such as (methyl) vinyl cyanide, styrene, α-methyl styrene, or the ethene base system aromatic monomer class of (methyl) benzyl acrylate etc., (methyl) 2-Hydroxy ethyl acrylate, (methyl) hydroxypropyl acrylate, or the ethene base system monomer class containing hydroxyl such as polyglycol (methyl) acrylate, (methyl) acrylamide, N,N-DMAA, NIPA, or the ethene base system monomer class containing amide group such as diacetone acrylamide, the ethene base system monomer class of N-methylol (methyl) acrylamide or dihydroxymethyl (methyl) acrylamide etc., the ethene base system monomer class containing alkoxyl-methyl such as N-methoxyl methyl (methyl) acrylamide or N-fourth oxygen methyl (methyl) acrylamide, ethene, propylene, or the olefines of isoprene etc., the dienes of chlorbutadiene or butadiene etc., methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, or the vinyl ethers of IVE etc., the fatty acid vinyl ester class etc. of vinyl-acetic ester or vinyl propionate base ester etc., can suitably use above-claimed cpd according to object, but be not limited to these compounds.
Can also enumerate and will there is the comb shape basic resin type spreading agent of the modifications such as the polymkeric substance of the monomeric unit containing primary amino radical such as allylamine or polyethyleneimine, polyethylene polyamine, poly-(hydroxy) polyamine (Port リ キ シ リ レ Application Port リ (ヒ De ロ キ シ プ ロ ピ レ Application) Port リ ア ミ Application) of Parylene or poly-(aminomethylation) epoxy resin with vibrin, acryl resin or polyether resin etc.
The commercially available product of this basic resin type spreading agent can enumerate the BYK-161,163,164,167,174,184,2000,2050 of such as PVC Star Network ケ ミ mono-ジ ヤ パ Application society, or the SOLSPERSE-34750 of Japanese Le one Block リ ゾ mono-Le society, the EFKA4300 of 56000, チ バ ジ ヤ パ Application societies, 4330,4046,4060,4080 etc.
As basic resin type spreading agent (a) of color filter green coloring composition of the present invention, particularly preferably comprise the block copolymer resin of base copolymer block (a1) and pigment carrier compatibility copolymer block (a2).Below, basic resin type spreading agent is described.
(basic resin type spreading agent)
The basic resin type spreading agent of color filter green coloring composition of the present invention there is the position (hereinafter referred to as adsorption section) that is adsorbed on pigment and bring prevent the cohesion between pigment, improve dispersed effect, for the high position (hereinafter referred to as compatibility portion) of the compatibility of pigment carrier.Zinc halide phthalocyanine is high due to acidity, so when compatibility portion and adsorption section random arrangement, becomes not enough, form dispersion bad to the absorption of pigment.In the 1st embodiment of the present invention, by following block copolymer resin is used as resin type spreading agent (a), can provide and not damage its look characteristic, fine and low viscosity and the green coloring composition of Absorbable organic halogens dispersion for zinc halide phthalocyanine color, described block copolymer resin is the separately existence on the same molecule of the base copolymer block (a1) as the adsorption section for zinc halide phthalocyanine color and the pigment carrier compatibility copolymer block (a2) as the compatibility portion for pigment carrier.
Form the base copolymer block (a1) of block copolymer resin and pigment carrier compatibility copolymer block (a2) can select various resin system respectively, preferred resin designs the easy and vinyl based copolymer of each patience excellence.
Below each copolymer block is described.
< base copolymer block (a1) >
The object lesson of base copolymer block (a1) can be enumerated has (methyl) acrylic acid-N, N-dimethylaminoethyl, (methyl) acrylic acid-N, N-lignocaine ethyl ester, (methyl) acrylic acid-N, N-dimethylamino propyl ester, (methyl) acrylic acid-N, N-lignocaine propyl ester, N, N-dimethylaminoethyl (methyl) acrylamide, or N, N-diethyllaminoethyl (methyl) acrylamides etc. are containing N, the multipolymer of the ethene base system monomeric unit of N-disubstituted amido, there is the polymkeric substance that allylamine etc. contains the monomeric unit of primary amino radical, or polyethyleneimine, polyethylene polyamine, Parylene gathers (hydroxy) polyamine, or poly-(aminomethylation) epoxy resin etc., but it is not limited to these compounds.
Wherein, the particularly preferably resin design of segmented copolymer easy and each patience excellence, have containing N, the multipolymer of the ethene base system monomeric unit of N-disubstituted amido, what now contain in base copolymer block (a1) contains N, the ethene base system monomeric unit of N-disubstituted amido is preferably 60 ~ 100 % by weight, and then preferably 80 ~ 100 % by weight, as removing containing N, ethene base system monomeric unit beyond the ethene base system monomeric unit of N-disubstituted amido, the ethene base system monomeric unit preferably illustrated in pigment carrier compatibility copolymer block (a2).
< pigment carrier compatibility copolymer block (a2) >
Pigment carrier compatibility copolymer block (a2) is the easy and ethene base system monomer copolymer of each patience excellence of the resin design of segmented copolymer, and then ethene base system monomeric unit is preferably containing (methyl) alkyl acrylate, special in pigment carrier compatibility copolymer block (a2), preferably containing 60 ~ 100 % by weight, and then preferably 80 ~ 100 % by weight.(methyl) alkyl acrylate can enumerate such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) cyclohexyl acrylate, (methyl) stearyl acrylate base ester, or the unsaturated monocarboxylic of (methyl) lauryl acrylate etc. and carbon number be 1 ~ 18 alkylol react (methyl) esters of acrylic acid etc. of gained, but it is not limited to these compounds.
In pigment carrier compatibility copolymer block (a2), be preferably 0 % by weight containing amino ethene base system monomeric unit, but also can containing the amount being less than 10 % by weight.
As other ethene base system monomeric unit that also can contain in base copolymer block (a1) and pigment carrier compatibility copolymer block (a2), the ethene base system monomer class that such as (methyl) vinyl cyanide etc. contains itrile group can be enumerated, styrene, α-methyl styrene, or the ethene base system aromatic monomer class of (methyl) benzyl acrylate etc., (methyl) 2-Hydroxy ethyl acrylate, (methyl) hydroxypropyl acrylate, or the ethene base system monomer class containing hydroxyl such as polyglycol (methyl) acrylate, (methyl) acrylamide, N, N-DMAA, NIPA, or the ethene base system monomer class containing amide group such as diacetone acrylamide, the ethene base system monomer class of N-methylol (methyl) acrylamide or dihydroxymethyl (methyl) acrylamide etc., the ethene base system monomer class containing alkoxyl-methyl such as N-methoxyl methyl (methyl) acrylamide or N-fourth oxygen methyl (methyl) acrylamide, ethene, propylene, or the olefines of isoprene etc.,
The dienes of chlorbutadiene or butadiene etc., the vinyl ethers of methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether or IVE etc., or the fatty acid vinyl ester class etc. of vinyl-acetic ester or vinyl propionate base ester etc., but it is not limited to these compounds.
< block copolymer resin >
Above-mentioned resin type spreading agent (a) used in the 1st embodiment of the present invention can use known method to prepare, especially, preferably (1) uses the method for living polymerization, or the polymkeric substance coupling method that (2) make the precursor (a11) having the base copolymer block (a1) of functional group at end react with the precursor (a21) having the pigment carrier compatibility copolymer block (a2) of functional group at end.Wherein, particularly preferably (1) uses the method for living polymerization.
(1) living polymerization
Living polymerization can suppress the subsidiary reaction occurred in general free radical polymerization, and then owing to can carry out the growth be polymerized equably, so can easily block polymer synthesis or the consistent resin of molecular weight.Wherein, from going for the monomer of wide region and the angle of the polymerization temperature that can be suitable for existing equipment can being adopted to consider, the atom freedom of movement base polymerization preferably using organohalogen compounds or sulfonyl halogen compound as initiating agent, using transition metal complex compound as catalyzer.Atom freedom of movement base polymerization can be used in the method described in following list of references 1 ~ 8 grade and carry out.
(list of references 1) Fukuda etc., Prog.Polym.Sci.2004,29,329
(list of references 2) Matyjaszewski etc., Chem.Rev.2001,101,2921
(list of references 3) Matyjaszewski etc., J.Am.Chem.Soc.1995,117,5614
(list of references 4) Macromolecules1995,28,7901, Science, 1996,272,866
(list of references 5) International Publication No. 96/30421 pamphlet
(list of references 6) International Publication No. 97/18247 pamphlet
(list of references 7) Unexamined Patent 9-208616 publication
(list of references 8) Unexamined Patent 8-41117 publication
In atom freedom of movement base polymerization, the transition metal complex compound of copper, ruthenium, iron or nickel etc. is used to carry out as redox catalyst.The object lesson of transition metal complex compound can enumerate the halogenated transition metal of the low atomicity such as cupric chloride (I) or copper bromide (I), but in order to control polymerization speed, the transition metal of cupric chloride (II) or copper bromide (II) contour atomicity also can be added according to known method in polymerization system.
Organic ligand can be used in above-mentioned metal complex.In order to have the reversible change of solubility for polymer solvent and redox conjugate coordination compound, and use organic ligand.The coordination atom of metal can use nitrogen-atoms, oxygen atom, phosphorus atoms or sulphur atom etc., preferred nitrogen atom or phosphorus atoms.The object lesson of organic ligand can enumerate sparteine or 2,2 '-bipyridine and derivant thereof, 1,10-phenanthroline or derivatives thereof, tetramethylethylenediamine, five methyl diethylentriamine, three (dimethyl aminoethyl) amine, hexamethyl (2-amino-ethyl) amine, triphenylphosphine or tributylphosphine etc.In above catalyzer, combinationally used by copper halide be polymerized with butanediamine, it is preferred that this angle from the control of polymerization speed, block resin molecular weight is considered.
Above-mentioned transition metal and organic coordination compounds can add respectively and generate metal complex in the polymer, also can add in polymerization system by pre-synthesis metal complex again.Especially, when transition metal is copper, preferably the former method, when transition metal is ruthenium, iron or nickel, the method for preferred the latter.The object lesson of pre-synthesis ruthenium, iron or nickel coordination compound can enumerate three (triphenylphosphine) ruthenous chloride (Ru (Cl) 2(PPh 3) 3, two (triphenylphosphine) ferrous chloride (Fe (Cl) 2(PPh 3) 2), two (triphenylphosphine) Nickel Chloride (Ni (Cl) 2(PPh 3) 2) or two (tributylphosphine) Nickel Bromide (NiBr 2(PBu 3) 2) etc.
The initiating agent used in atom freedom of movement base polymerization can use known compound, mainly can use the organohalogen compounds with reactive high carbon-halogen bond, or sulfonyl halogen compound etc.Specifically can enumerate, isobutyl ethyl bromide, bromobutyrate, chloro ethyl isobutyrate, chloro ethyl butyrate, paratoluensulfonyl chloride, bromo ethyl phenenyl or chloroethyl benzene etc.These compounds can be used alone or and use.
In above-mentioned atom freedom of movement base polymerization, the initiating agent of atom freedom of movement base polymerization suitably can be selected according to the molecular weight of the resin of synthesis, relative to free radical polymerization monomer total amount, preferably use with the ratio of 0.001 ~ 10 % by mole, more preferably 0.01 ~ 1 % by mole.In addition, the use amount of transition metal, as the form of halogenide etc., relative to initiating agent 1 mole, preferably uses with the ratio of 0.03 ~ 3 mole, more preferably 0.1 ~ 2 mole.And then its part, relative to above-mentioned transition metal (forms of halogenide etc.) 1 mole, uses with the ratio of 1 ~ 5 mole, preferably 1.2 ~ 3 mole usually.When the initiating agent that above-mentioned atom freedom of movement base is polymerized, transition metal and part use with such ratio, be preferred in the reactivity of active free radical polymerization, the molecular weight of generation polymkeric substance etc.
In addition, in the characteristic of atom freedom of movement base polymerization, at the termination end of gained resin, there is acticarbon-halogen bond, by known method, its modification can be introduced functional group.In addition, the polymerization initiator with functional group can be utilized to be polymerized, in resinous terminal introducing functional group and for various reaction.
Even if the polymerization of atom freedom of movement base also can be carried out under solvent-free state, or also can carry out under the state that there is butyl acetate, toluene, dimethylbenzene, anisole, methyl ethyl ketone or cyclohexanone equal solvent.Consider from the angle of polymerization speed especially, preferred ketone series solvent, particularly preferably methyl ethyl ketone.When the solvent is used, in order to prevent the reduction of polymerization speed, preferably its use amount to be the solvent strength after polymerization is terminated be less than 50 % by weight amount.Even if for the situation of solvent-free or a small amount of quantity of solvent, also do not have safety issue relevant with the control of heat of polymerization etc. especially, thus reduce solvent, be also preferred thus in economy or environmental cure etc.
As polymerizing condition, consider from the angle of the inactivation of polymerization speed or catalyzer, carry out with the polymerization temperature of 60 ~ 130 DEG C, although polymerization time also depends on final molecular weight or polymerization temperature, as long as the scope of about 1 ~ 100 hour.In addition, when polyreaction, in order to prevent the inactivation of the polymerization catalyst caused by oxygen, preferably carry out under the atmosphere of inert gases of nitrogen or argon etc.
In addition, after polyreaction terminates, polymerization reaction system is cooled to preferably less than 0 DEG C, more preferably about-78 DEG C, and make reaction terminating, according to known method, the removing of residual monomer and/or solvent, precipitating again in appropriate solvent can be carried out, utilize centrifuging to carry out the filtration of precipitation polymers, the washing of polymkeric substance and drying.As required utilizing known method to remove in polymerization system containing after transition metal etc., by making volatile ingredient evaporate, the block resin of the present invention's use can be obtained.The organic solvent diluting reaction mixture of the useful tetrahydrofuran of removing method, toluene or methyl ethyl ketone etc. the method for washing with water watery hydrochloric acid or ammonia spirit etc., resin solution is contacted with Zeo-karb or chelate resin, the method passed through in the pillar or filler (パ Star De) of alumina silica or clay, carries out the method etc. filtering centrifuging after adding the adsorbent of reductive agent or hydrotalcite etc.Consider from the angle of the simplicity of process, in dilute resin solution, preferably add the sour adsorbent of Zeo-karb and hydrotalcite etc. etc. and stir, ion exchange resin and sour adsorbent being filtered and obtains resin solution.
When being mixed into moisture in resin solution by refinement treatment, have the situation hindering in the present invention the block resin used to react with hardening agent, the solvent mixed with water preferably by interpolation in resin solution also carries out the process of azeotropic dehydration etc. and is removed from resin solution by moisture.
For the atom freedom of movement base polymerization used in the present invention, due to the subsidiary reaction occurred in general free radical polymerization can be suppressed, thus the initiating agent of atom freedom of movement base polymerization added when utilizing polymerization and the loading ratio of free radical polymerization monomer, freely can control the molecular weight of resin or the ratio of base copolymer block (a1) or pigment carrier compatibility copolymer block (a2).
(2) polymkeric substance coupling method
As the functional group of the end of the precursor (a11) of the base copolymer block (a1) of polymkeric substance coupling method and the precursor (a21) of pigment carrier compatibility copolymer block (a2), carboxyl, primary amino radical, hydroxyl or alkoxysilyl etc. specifically can be enumerated by preferred functional group.
As the method in the precursor (a21) of the precursor (a11) and pigment carrier compatibility copolymer block (a2) that functional end-group are incorporated into base copolymer block (a1), preferred use has the above-mentioned functional group enumerated and has the chain-transferring agent of sulfydryl, carries out the method for free radical polymerization.The chain-transferring agent with carboxyl can enumerate mercaptopropionic acid, the chain-transferring agent with primary amino radical can enumerate cysteamine, the chain-transferring agent with hydroxyl can enumerate mercaptoethanol, and the chain-transferring agent with alkoxysilyl can enumerate 3-mercaptopropyi methylmethoxysilane or 3-mercaptopropyi trimethoxy silane.
The reaction of precursor (a11) and precursor (a21) can be such as the known reactions of carrying out in order to the combination of following table 1.
The polyisocyanate compound of bonding agent can enumerate aromatic polyisocyanate, aliphatic polyisocyante, aromatic-aliphatic polyisocyanates or alicyclic polyisocyanates etc.Aromatic polyisocyanate can enumerate such as 1,3-phenylene diisocyanate, 4,4 '-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '-toluidine diisocyanate, 2,4,6-triisocyanate base toluene, 1,3,5-triisocyanate base benzene, dianisidine diisocyanate, 4,4 '-diphenyl ether diisocyanate or 4,4 ', 4 "-triphenylmethane triisocyanates etc.Aliphatic polyisocyante can enumerate such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, two isocyanic acid pentylidene esters, two isocyanic acids-1,2-sub-propyl ester, two isocyanic acids-2,3-Aden ester, two isocyanic acids-1,3-Aden ester, two isocyanic acid 12 methylene ester or two isocyanic acids-2, the sub-own ester of 4,4-trimethyl etc.Aromatic-aliphatic polyisocyanates can enumerate such as ω, ω '-diisocyanate-1,3-dimethyl benzene, ω, ω '-diisocyanate-1,4-dimethyl benzene, ω, ω '-diisocyanate-Isosorbide-5-Nitrae-diethylbenzene, 1,4-tetramethylxylene diisocyanate or 1,3-tetramethylxylene diisocyanate etc.Alicyclic polyisocyanates can enumerate such as 3-isocyanatomethyl (イ ソ シ ア ネ mono-ト メ チ Le)-3, 5, 5-tri-methyl cyclohexane diisocyanate, 1, 3-cyclopentane diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methyl-2, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 4, 4 '-methylene two (cyclohexyl isocyanate), 1, 4-bis-(isocyanatomethyl) cyclohexane, or 1, 4-bis-(isocyanatomethyl) cyclohexane etc., but be not limited to these compounds.In addition, the biuret thing also can be used together the trimethylolpropane adduct of a part of above-mentioned polyisocyanates, reacting with water, the tripolymer etc. with isocyanurate ring.
The polyepoxides of bonding agent preferably has the polyepoxides of at least 2 glycidyls.Specifically, ethylene glycol diglycidylether can be enumerated, propylene glycol diglycidylether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, trimethylolethane trimethacrylate glycidol ether, sorbitol polyglycidylether, or the aliphatic polyepoxide of pentaerythrite polyglycidyl ether etc., the aromatics polyepoxides of bisphenol-A or bisphenol F type, four glycidyl group aminophenyl methane, triglycidyl isocyanurate, or 1, 3-bis-(N, N-glycidyl-amino methyl) the glycidyl amine type epoxy compound of cyclohexane etc., but it is not limited to these compounds.
The number-average molecular weight of the segmented copolymer type basic resin type spreading agent used in the 1st embodiment of the present invention is preferably 500 ~ 50000 usually, and then preferably 3000 ~ 30000.But when above-mentioned number-average molecular weight is less than 500, the steric repulsion effect caused by pigment compatibility copolymer block (a2), with the effect of the compatibility of pigment carrier and when using solvent and the effect of the compatibility of pigment carrier and solvent diminish, be difficult to the cohesion preventing pigment, the viscosity of dispersion raises.In addition, when number-average molecular weight is more than 50000, the addition of the resin required for dispersion increases, and causes the reduction of the pigment concentration in film.
In addition, the amine value of the segmented copolymer type basic resin type spreading agent used in the 1st embodiment of the present invention is 35 ~ 100mgKOH/g, and then preferred 50 ~ 75mgKOH/g.When amine value is less than 35mgKOH/g, can not be adsorbed on that pigment to be formed dispersion bad fully, when more than 100mgKOH/g, due to for the absorption of the acid ingredient in pigment carrier or reaction, and the adsorption efficiency for pigment is deteriorated, form dispersion bad.
The formation part by weight of base copolymer block (a1) or pigment carrier compatibility copolymer block (a2) and the number-average molecular weight of respective block preferably can at random design, to make the number-average molecular weight of resin type spreading agent entirety and amine value in above-mentioned preferred scope.
In the green coloring composition of the 1st embodiment of the present invention, when being benchmark with the general assembly (TW) of pigment composition (A), the use level of basic resin type spreading agent (a) is preferably 0.001 ~ 50 % by weight, and then preferably 0.1 ~ 30 % by weight, most preferably 0.5 ~ 25 % by weight.If the use level of resin type spreading agent (a) when being benchmark with the general assembly (TW) of pigment composition (A) is less than 0.001 % by weight, then there is dispersed situation about being deteriorated, if more than 40 % by weight, then there is the situation that thermotolerance, photostability are deteriorated.
[there is the pigment derivative (b) of alkali subtituent]
The feature of green coloring composition of the present invention is, the zinc halide phthalocyanine using central metal to have zinc is used as the main pigments of pigment composition (A), above-mentioned zinc halide phthalocyanine is compared with the general halogenated copper phthalocyanine pigment used in green coloring composition, be the acid pigment that central metal has zinc, this surface of pigments has negative charge.Therefore, when use has the spreading agent of alkali subtituent, the absorption for acid pigment becomes abundant, and this pigment dispersion can find sufficient mobility and color characteristics.In the 2nd embodiment of the present invention, by using the pigment derivative (b) with alkali subtituent as spreading agent, preferred pigment dispersion can be obtained.
As mentioned above, in the 2nd embodiment of color composition for color filter of the present invention, for the object of dispersiveness improving pigment, pigment derivative (b) can be used.Pigment derivative can be set forth in organic pigment, anthraquinone, acridone or triazine the compound introduced alkali subtituent, acidic substituent or also can have substituent phthalimide methyl.
In the present invention, wherein particularly preferably alkaline derivant, alkaline derivant is the such as compound shown in following general formula (1), and it is the derivant with specific precursor skeleton, and described specific precursor skeleton has basic group.As long as have the pigment derivative of basic group, be not particularly limited, preferably use the pigment derivative with triazine ring skeleton, described triazine ring skeleton has the basic group as shown in following general formula (4).
General formula (1):
P-Lm
(wherein, in general formula (1),
P is the organic pigment residue, anthraquinone skeleton, acridone skeleton, triazine skeleton etc. of m valency,
M is the integer of 1 ~ 4,
L is for being selected from the substituting group in group as shown in general formula (2), (3) and (4).)
General formula (2):
General formula (3):
General formula (4):
(wherein, in general formula (2) ~ (4),
X is-SO 2-,-CO-,-CH 2-,-CH 2nHCOCH 2-,-CH 2nHSO 2cH 2-or Direct Bonding,
Y is-NH-,-O-or Direct Bonding,
N is the integer of 1 ~ 10,
Y 1-NH-,-NR 58-Z-NR 59-or Direct Bonding,
R 58and R 59separately represent hydrogen atom, also can have substituent carbon number be 1 ~ 36 alkyl, also can to have substituent carbon number be the thiazolinyl of 2 ~ 36 or also can have substituent phenyl,
Z represents also can have substituent alkylidene or also can have substituent arlydene,
R 50, R 51separately represent hydrogen atom, also can have substituent carbon number be 1 ~ 30 alkyl, also can have thiazolinyl or the R that substituent carbon number is 2 ~ 30 50with R 51formed one so that containing nitrogen, oxygen or sulphur atom also can have substituent heterocycle.
R 52, R 53, R 54and R 55separately represent hydrogen atom, also can have substituent carbon number be 1 ~ 20 alkyl, also can have substituent carbon number be 2 ~ 20 thiazolinyl, also can have the arlydene that substituent carbon number is 6 ~ 20,
R 56be hydrogen atom, also can have substituent carbon number be 1 ~ 20 alkyl, also can have the thiazolinyl that substituent carbon number is 2 ~ 20,
R 57the substituting group as shown in general formula (2) or the substituting group as shown in general formula (3),
Q is hydroxyl, alkoxy, the substituting group as shown in above-mentioned general formula (2) or the substituting group Ru shown in above-mentioned general formula (3).〕
Such as dimethylamine can be enumerated for the formation of the such as substituent amine component shown in general formula (2) ~ (4), diethylamine, methyl ethyl-amine, N, N-ethyl isopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methyl tert-butyl amine, N, N-butyl ethamine, N, N-tert-butyl group ethamine, diisopropylamine, di-n-propylamine, N, N-sec-butyl propylamine, dibutylamine, di-sec-butylamine, di-iso-butylmanice, N, N-isobutyl sec-butylamine, diamylamine, di-iso-amylamine, dihexylamine, dicyclohexyl amine, two (2-ethylhexyl) amine, dioctylamine, N, N-methyl octadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethyl propylamine, N, N-tuaminoheptane, two oil base amine, distearyl amine, N, N-dimethylamino methylamine, N, N-dimethylamino ethamine, N, N-dimethylamino amylamine, N, N-dimethylaminobutylamine, N, N-diethylamino ethamine, N, N-diethyl amino propylamine, N, N-diethylamino hexylamine, N, N-diethylamino butylamine, N, N-diethylamino amylamine, N, N-dipropylamino butylamine, N, N-dibutyl amino propyl amine, N, N-dibutylamino ethamine, N, N-dibutylamino butylamine, N, N-diisobutylamino amylamine, N, N-methyl-lauryl amino propylamine, N, N-ethyl hexyl aminoethyl, N, N-distearyl aminoethyl, N, N-bis-oil base aminoethyl, the amino butylamine of N, N-distearyl, piperidines, pipecoline, 3-methyl piperidine, 4-methyl piperidine, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidine carbinols, nipecotic acid, isonipecotic acid, isonipecotic acid methyl esters, ethyl isonipecotate, 2-piperidine ethanol, pyrrolidine, 3-hydroxyl pyrrolidine, N-aminoethylpiperidine, N-amino-ethyl-4-methyl piperidine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-pipecoline, N-aminopropyl-4-methyl piperidine, APM, N methyl piperazine, N-butyl piperazine, N-methyl height piperidines, 1-cyclopentyl-based piperazine, 1-amino-4-methyl piperazine, 1-cyclopentyl-based piperazine etc.
The pigment derivative with alkali subtituent, anthraquinone derivative and the acridone derivatives that use in 2nd embodiment of the present invention can synthesize by various synthetic route.Such as can by introducing such as formula after the substituting group shown in (5) ~ (8) in organic pigment, anthraquinone or acridone, making can with above-mentioned substitution reaction and the substituent above-mentioned amine component formed as shown in general formula (2) ~ (4) carries out reaction to obtain, described amine component such as has N, N-dimethylamino propylamine, N methyl piperazine, diethylamine or 4-[4-hydroxyl-6-[3-(dibutylamino) propylcarbamic]-1,3,5-triazine-2-is amino] aniline etc.
Formula (5) :-SO 2cl
Formula (6) :-COCl
Formula (7) :-CH 2nHCOCH 2cl
Formula (8) :-CH 2cl
When substituting group in formula (5) ~ (8) and above-mentioned amine component react, the substituent part hydrolysis of formula (5) ~ (8), thus also can mix and there is chlorine and be replaced to the material of hydroxyl.Now, formula (5) and formula (6) become sulfonic group and carboxylic acid group respectively, and they can keep the state of free acid, or also can be the salt formed with the metal of 1 ~ 3 valency or above-mentioned monoamine.
In addition, when organic pigment is azo system pigment, the substituting group shown in general formula (2) ~ (4) is incorporated in diazo component or coupling components in advance, carries out coupling reaction afterwards, also can manufacture azo pigment derivant thus.
The pyrrolotriazine derivatives with basic group used in 2nd embodiment of the present invention can synthesize by various synthetic routes.It is such as initiation material with cyanuric chloride, by making substituent amine component, the such as N shown in formation general formula (2) ~ (4), N-dimethylaminopropylamine or N methyl piperazine etc. react with at least 1 chlorine of cyanuric chloride, then make remaining chlorine of cyanuric chloride and various amine or alcohol etc. carry out reaction to obtain.
In color compositions of the present invention, there is the use level of the pigment derivative of alkali subtituent relative to pigment composition (A) 100 weight portion, be preferably 1 ~ 50 weight portion, and then preferably 3 ~ 30 weight portions, most preferably 5 ~ 25 weight portions.When relative to pigment 100 weight portion, when alkaline derivant is less than 1 weight portion, there is dispersed situation about being deteriorated, when more than 50 weight portion, have the situation that thermotolerance, photostability are deteriorated.The compound wherein in alkali subtituent with triazine structure is preferred in dispersion stabilization.
[organic solvent (c)]
In the 3rd embodiment of green coloring composition of the present invention, in order to pigment composition (A) is dispersed in pigment carrier (B) fully, and the mode being easily 0.2 ~ 5 μm with dry film thickness on the substrate of glass substrate etc. carries out coating to form color filter joint, and containing organic solvent (c).
It is 8.0 ~ 10.0 (cal/cm that organic solvent (c) uses containing solubility parameters (SP value) 3) 1/2, and boiling point under 760mmHg is the organic solvent (c1) of 140 ~ 159 DEG C; Be 8.0 ~ 10.0 (cal/cm with solubility parameters (SP value) 3) 1/2, and boiling point under 760mmHg is the mixed organic solvents of the organic solvent (c2) of 160 ~ 200 DEG C.
In this manual, solubility parameters (SP value) refers to the value of being tried to achieve by the physical quantity of organic solvent (heat of evaporation etc.), and it is the value recorded in various document.
More preferably organic solvent (c) is 8.0 ~ 10.0 (cal/cm containing solubility parameters (SP value) 3) 1/2, and boiling point under 760mmHg is the organic solvent (c1) of 144 ~ 157 DEG C; Be 8.0 ~ 10.0 (cal/cm with solubility parameters (SP value) 3) 1/2, and boiling point under 760mmHg is the mixed organic solvents of the organic solvent (c2) of 164 ~ 192 DEG C.
Here, organic solvent (c1) is preferably such as selected from the solvent of propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate more than a kind, in addition, organic solvent (c2) is preferably such as selected from the solvent of cyclohexyl acetate, propylene-glycol diacetate, diethylene glycol diethyl ether and 3-ethoxyl ethyl propionate more than a kind.Further, cyclohexyl acetate is also called adnoral acetate.
The color filter green coloring composition of the 3rd embodiment of the present invention has the solubility parameters (SP value) of particular range and the organic solvent (c1) of boiling point and organic solvent (c2), so have high contrast ratio and high brightness owing to coordinating with special ratios.In addition, for the film being coated with this coloured composition, thickness is uneven and strip is uneven reduces, and uniform film thickness, has excellent performance.
When solubility parameter (SP value) is than 8.0 (cal/cm 3) 1/2hour, the dispersion of zinc halide phthalocyanine color is deteriorated, when than 10.0 (cal/cm 3) 1/2time large, zinc halide phthalocyanine color dissolves in organic solvent, produces the reduction of lightness and contrast ratio.
When the boiling point of the solvent used as organic solvent (c1) is less than 140 DEG C, generation thickness is uneven or strip is uneven, is never preferred.In addition, when the boiling point of the solvent used as organic solvent (c2) is larger than 200 DEG C, remain cohesive (タ Star Network), from instead of preferred.
When being benchmark with the total amount of above-mentioned pigment composition (A), mixed organic solvents (c) can use 800 ~ 4, the amount of 000 % by weight.In addition for the cooperation of mixed organic solvents (c), in its total amount, preferred organic solvent (c1) is 50 ~ 95 % by weight, and organic solvent (c2) is 5 ~ 50 % by weight.More preferably organic solvent (c1) is 65 ~ 95 % by weight, and organic solvent (c2) is 5 ~ 35 % by weight.If the ratio of organic solvent (c1) exceeds the scope of 50 ~ 95%, then coating fluid has the problem that generation thickness is uneven or strip is uneven.Like this, in order to carry out the preferred dispersion of zinc halide phthalocyanine color, the cooperation of organic solvent (c1) and organic solvent (c2) is important.
Described above in addition, the organic solvent (c1) used when disperseing zinc halide phthalocyanine color and the organic solvent (c2) added in order to the unfavorable condition improved in the film being coated with color filter green coloring composition of the present invention are not limited to specific solvent, in order to easily make coloured composition be formed as color filter joint, following organic solvent can be added as secondary solvent.
1,2,3-trichloropropane, 1,3-butanediol (1,3-Block タ Application ジ オ mono-Le), 1,3-BDO (1,3-Block チ レ Application グ リ コ mono-Le), 1,3-BDO diacetate esters, Isosorbide-5-Nitrae-two can be used alkane, 2-HEPTANONE, 2-methyl isophthalic acid, ammediol, 3,5,5-trimethyl-2-cyclohexane-1-ketone, 3,3,5-trimethylcyclohexanone, 3-methyl isophthalic acid, 3-butanediol, MMB, 3-methoxyl-3-Methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetic acid esters, 4-heptanone, m-xylene, between diethylbenzene, m-dichlorobenzene, DMA, DMF, normal butyl alcohol, n-butylbenzene, n-propyl acetate, 1-METHYLPYRROLIDONE, o-xylene, ortho-chlorotolu'ene, adjacent diethylbenzene, o-dichlorobenzene, parachlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl benzene, gamma-butyrolacton, isobutyl alcohol, isophorone, ethylene glycol bisthioglycolate ethylether, ethylene glycol bisthioglycolate butyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetic acid esters, ethylene glycol list propyl ether, ethylene glycol mono hexyl ether, ethylene glycol monomethyl ether, diisobutyl ketone, diethylene glycol dimethyl ether, diglycol monotertiary isopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ehter, diethylene glycol monobutyl ehter acetic acid esters, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methylether acetate, dipropylene glycol monoethyl ether, dipropylene glycol single-butyl ether, dipropylene glycol list propyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, glycerol triacetate, tripropylene glycol monobutyl base ether, tripropylene glycol monomethyl ether, propylene glycol phenyl ether, propylene glycol monoethyl, glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether propionic ester, benzylalcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, or dibasic acid ester etc.
In order to obtain the preferred green coloring composition of the present invention, in whole mixed organic solvents (c), preferred organic solvent (c1) and organic solvent (c2) add up to more than 70 % by weight.More preferably it adds up to 80 % by weight in addition.Particularly preferably add up to more than 85 % by weight.When secondary solvent beyond organic solvent (c1) and organic solvent (c2) is added in a large number, bring bad impact to the coating of the stability of zinc halide phthalocyanine color dispersion and the film that is coated with this coloured composition, from instead of preferred.
[dispersion]
Green coloring composition of the present invention can use the various dispersion means of above-mentioned three-roll mill, two roller mills, sand mill, kneader or vertical ball mill etc., by the pigment composition (A) at least containing zinc halide phthalocyanine color, is dispersed in imperceptibly in above-mentioned pigment carrier (B) is prepared together with above-mentioned basic resin type spreading agent (a) or above-mentioned basic resin type spreading agent (a) and the above-mentioned pigment derivative (b) with alkali subtituent.In addition, green coloring composition of the present invention also can disperse the material of several pigment to carry out mixing preparing by pigment carrier (B) respectively.
Green coloring composition of the present invention and then can add Photoepolymerizationinitiater initiater etc., modulates with the form of solvent developable or the green resist of alkali developable.When modulating with the form of the painted resist of alkali developable, in a part for pigment carrier, use the alkali-soluble material with acidic-group.
[Photoepolymerizationinitiater initiater]
For color filter green coloring composition of the present invention, utilizing Ultraviolet radiation said composition to be solidified, or when utilizing photoetching process to form color filter joint, can Photoepolymerizationinitiater initiater etc. added.Using use level during Photoepolymerizationinitiater initiater when being benchmark with the general assembly (TW) of pigment composition (A), being preferably 5 ~ 200 % by weight, considering from the angle of photo-curable, developability, more preferably 10 ~ 150 % by weight.
Photoepolymerizationinitiater initiater can use 4-phenoxydichloroacetophenone, 4-tert-butyl group dichloroacetophenone, diethoxy acetophenone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone, or the acetophenone system Photoepolymerizationinitiater initiater of 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone etc., benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or the benzoin system Photoepolymerizationinitiater initiater of benzyl dimethyl ketal etc., benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenyl benzophenone, dihydroxy benaophenonel, polyacryl benzophenone, or the benzophenone system Photoepolymerizationinitiater initiater of 4-benzoyl-4 '-methyldiphenyl sulfide etc., thioxanthones, CTX, 2-methyl thioxanthones, isopropyl thioxanthone, or the thioxanthones system Photoepolymerizationinitiater initiater of 2,4-diisopropylthioxanthone etc., 2,4,6-trichloto-s-triazine, 2-phenyl-4,6-bis-(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis-(trichloromethyl)-s-triazine, 2-(p-methylphenyl)-4,6-bis-(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis-(trichloromethyl)-s-triazine, 2,4-bis-(trichloromethyl)-6-styryl-s-triazine, 2-(naphthalene-1-base)-4,6-bis-(trichloromethyl)-s-triazine, 2-(4-methoxyl-naphthalene-1-base)-4,6-bis-(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or the triazine system Photoepolymerizationinitiater initiater of 2,4-trichloromethyl (4 '-methoxyl-styrene)-6-triazine etc., borate (ボ レ mono-ト) is Photoepolymerizationinitiater initiater, carbazole system Photoepolymerizationinitiater initiater, or imidazoles system Photoepolymerizationinitiater initiater etc., but it is not limited to these compounds.
Above-mentioned Photoepolymerizationinitiater initiater can be used alone or two or more is used in combination; can also as sensitizer; and with such as α-acyl-oxygen ester (α-ア シ ロ キ シ エ ス テ Le), acylphosphine oxide, glyoxalic acid methyl phenyl ester, dibenzoyl, 9; 10-phenanthrenequione, camphorquinone (カ Application Off ア mono-キ ノ Application), EAQ, 4; 4 '-diethyl isophthalic diformyl-benzenes, 3; 3 '; 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone or 4; the compound of 4 '-diethylamino benzophenone etc., but it is not limited to these compounds.
During using the cooperation weight of the Photoepolymerizationinitiater initiater contained in coloured composition as benchmark, use use level during sensitizer to be preferably 3 ~ 60 % by weight, consider from the angle of photo-curable, developability, more preferably 5 ~ 50 % by weight.
[dispersing aid]
When being dispersed in by pigment in pigment carrier (B), the dispersing aid of other resin-bonded pigment spreading agent or the surfactant etc. different from above-mentioned basic resin type spreading agent (a) suitably can be used.Dispersing aid makes the dispersion of pigment excellent, there is the larger effect re-united preventing from disperseing rear pigment, therefore, when using following green coloring composition, can obtain the color filter that spectral transmission is high, described green coloring composition uses dispersing aid to be dispersed in by pigment in pigment carrier (B) and forms.
Other resin-bonded pigment spreading agent different from above-mentioned basic resin type spreading agent (a) also has pigment compatibility position and has the position of compatibility with pigment carrier, described pigment compatibility position has the character be adsorbed on pigment, and this dispersant adsorption plays the function making the decentralized stabilization of pigment in pigment carrier (B) on pigment.As resin-bonded pigment spreading agent, other known resin type pigment dispersing agent different from above-mentioned basic resin type spreading agent (a) specifically, can use polyurethane, or the polycarboxylate of polyacrylate etc., unsaturated polyester acid amides, poly carboxylic acid, poly carboxylic acid (part) amine salt, poly carboxylic acid ammonium salt, poly carboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, polycarboxylate containing hydroxyl, or their modifier, the oiliness spreading agent of the acid amides that utilization poly-(rudimentary alkyleneimines) is carried out reacting with the polyester with free carboxy and formed or its salt etc., (methyl) acrylic-styrene copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol (PVA), or the water soluble resin of polyvinylpyrrolidone etc. or water-soluble high-molecular compound, Polyester, modified polyacrylate system, ethylene oxide/propylene oxide additive compound, or phosphate systems etc., these compounds can be used alone, or two or more is used in combination.
Surfactant can enumerate the anionic surfactant of monoethanolamine, polyoxyethylene alkyl ether phosphate etc. of NaLS, polyoxyethylene alkyl ether sulfate salt, neopelex, the alkali metal salt of Styrene-acrylic copolymer, odium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl base ether sodium disulfonate, lauryl sulfate monoethanolamine, triethanolamine lauryl sulfate, Texapon Special, stearic acid monoethanolamine, Styrene-acrylic copolymer; The nonionic surfactant of polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, ethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitol monostearate, polyethyleneglycol lauryl etc.; The cationic surfactant of alkyl quaternary ammonium salts or their ethylene oxide adduct etc.; The amphoteric surfactant of the alkyl betaine, alkyl imidazoline etc. of alkyl dimethyl oxyneurine etc., these compounds can be used alone or two or more is used in combination, but are not limited to these compounds.
And then, in color filter green coloring composition of the present invention, in order to pigment being dispersed in fully in pigment carrier (B), and the mode being easily 0.2 ~ 5 μm with dry film thickness on the transparency carrier of glass substrate etc. carries out coating to form color filter joint, and containing solvent, can use in the mode of " green ink " or " green resist ink ".
Above-mentioned solvent uses above-mentioned mixed organic solvents (c) in the present invention the 3rd embodiment, but in the of the present invention 1st and the 2nd embodiment, can from organic solvent (c1), organic solvent (c2) and secondary solvent choice for use.
Viscosity (at 25 DEG C, rotation number is the viscosity of 60rpm) after green coloring composition of the present invention preferably just disperses is 2 ~ 100mPas, thixotropic index (at 25 DEG C, rotation number is the ratio of the viscosity of 6rpm and the viscosity of 60rpm) after firm dispersion is less than 1.4, preserve under the condition of 10 DEG C after 3 months through time rate of viscosity increase (when the viscosity being 60rpm with rotation number at 25 DEG C after just disperseing is for benchmark, save under the condition of 10 DEG C after dispersion 3 months, at 25 DEG C rotation number be the rate of viscosity increase of 60rpm) be less than 20%.When the viscosity after just dispersion be less than 2mPas or more than 100mPas time, or when the thixotropic index just after dispersion is more than 1.4, or through time rate of viscosity increase be more than 20% time, can not coating homogeneity be ensured, the color filter with homogeneous film thickness as object can not be obtained.Further, viscosity and thixotropic index such as can use E type viscosity meter (Dong Ji industry society system " ELD type viscosity meter ") to measure.
[storage stabilizer]
In addition, in order to make composition through time viscosity stabilization, green coloring composition of the present invention can contain storage stabilizer.
Storage stabilizer can enumerate the aliquat class of such as benzyltrimethylammonium chloride or diethylhydroxylamine etc.;
The organic acid of lactic acid or oxalic acid etc.;
Above-mentioned organic acid methyl esters class;
The pyrocatechol of tert-butyl pyrocatechol etc.;
The organic phosphine class of triphenylphosphine, tetraethyl phosphine or tetraphenyl phosphine etc.; Or
Phosphorous acid salt etc.
[removing of oversize grain or dust]
For green coloring composition of the present invention, the means preferably by centrifuging, sintered filter or membrane filter etc. remove oversize grain, the preferably oversize grain of more than 1 μm and then the preferably oversize grain of more than 0.5 μm and the dust that is mixed into of more than 5 μm.When there is oversize grain, in color filter, remaining impurity, not only producing problem in practical use, and in painting process, impurity is blocked in pipeline or nozzle, produce the significant problem in preparation.This green coloring composition is preferably substantially devoid of the particle of more than 0.5 μm.More preferably the particle contained in green coloring composition is less than 0.3 μm (utilizing the particle diameter that SEM records).
In addition, in order to improve lightness or contrast ratio, average mark shot footpath is preferably 0.05 ~ 0.2 μm, when for 0.06 ~ 0.15 μm, owing to and then can improve lightness or contrast ratio, so be preferred.
[preparation of color filter]
Color filter of the present invention can be prepared by print process or photoetching process.
The formation that make use of the color filter joint of print process due to only repeatedly carry out as the coloured composition of printing-ink modulation printing and dry just can be graphical, so as the preparation method of color filter, carry out with low cost mass-produced in excellence.And then, utilize the development of printing technology can carry out the printing of the Micropicture with high dimensional accuracy and smoothness.In order to print, to be preferably formed in galley or moist at superficial layer (Block ラ Application ケ Star ト) curing ink, solidify such composition.In addition, the control of the mobility of the ink on printing machine is also important, and spreading agent or filler pigment also can be utilized to carry out the adjustment of ink viscosity.
When utilizing photoetching process to form color filter joint, by the coating process of spraying process or spin-coating method, slot coated method or rolling method etc., the coloured composition as above-mentioned solvent developable or the painted resist modulation of alkali developable can be coated with on the transparent substrate in the mode that dry film thickness is 0.2 ~ 5 μm.As required, dried film is passed through to carry out ultraviolet exposure with the mask with compulsory figure contacted with this film or contactless state is arranged.Flood in solvent or alkaline developer afterwards or utilize the spray development liquid such as sprayer to form the figure of expectation to remove uncured portion, then can repeatedly carry out same operation to prepare color filter for other color.And then, in order to promote the polymerization of painted resist, heating also can be implemented as required.According to photoetching process, the high color filter of precision can be prepared by above-mentioned print process.
When developing, alkaline developer can use the aqueous solution of sodium carbonate or NaOH etc., also can use the organic base of dimethyl benzyl amine or triethanolamine etc.In addition, in developer solution, also can add defoamer or surfactant.
And, in order to improve ultraviolet exposure sensitivity, also can after the dry above-mentioned painted resist of coating, by water-soluble or buck soluble resin, it is dry that such as polyvinyl alcohol (PVA) or water soluble acrylic resin etc. carry out coating, and form the film of the polymerization obstruction preventing from being caused by oxygen, then carry out ultraviolet exposure.
Color filter of the present invention can be prepared by the electrodeposition process beyond said method or transfer printing etc., and coloured composition of the present invention can use in any one method.Further, electrodeposition process utilizes the nesa coating formed on substrate, forms shades of colour color filter joint, prepare the method for color filter thus by the electrophoresis of colloidal particle at nesa coating substrates.
In addition, transfer printing is pre-formed color filter joint, and make this color filter save the method be transferred on the substrate of expectation.
[color filter]
Then, color filter of the present invention is described.Color filter of the present invention has the red color filter joint of at least 1, the blue color filter of at least 1 saves and the green color filter of at least 1 saves, and the green color filter joint of above-mentioned at least 1 uses color composition for color filter of the present invention to be formed.
Red color filter joint can use common red colored composition to be formed.Can use in red colored composition such as C.I. paratonere 7,14,41,48:1,48:2,48:3,48:4,57:1,81,81:1,81:2,81:3,81:4,122,146,168,177,178,184,185,187,200,202,208,210,246,254,255,264,270,272, the red pigment of 279 etc.
C.I. pigment orange 43 is can be used together in red colored composition, 71, the orange pigment of 73 grades and/or C.I. pigment yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, the yellow uitramarine of 214 grades.
In addition, blue color filter joint can use common blue colored composition to be formed.Can use in blue colored composition C.I. pigment blue 15,15:1,15:2,15:3,15:4,15:6,16,22,60, the blue pigment of 64 etc.In addition in purple coloured composition, can be used together C.I. pigment violet 1,19,23,27,29,30,32,37,40,42, the violet pigment of 50 etc.
[embodiment]
Below, based on embodiment, the present invention is described, but the present invention is not limited to these embodiments.Further, in embodiment and comparative example, " part " expression " weight portion ".In addition, Mn and Mw represents number-average molecular weight and weight-average molecular weight respectively.
(1) mean molecular weight of basic resin type spreading agent (a)
In following embodiment and comparative example, the number-average molecular weight (Mn) of basic resin type spreading agent and weight-average molecular weight (Mw) use HLC-8320GPC (eastern ソ mono-Co., Ltd. system) as device, use SUPER-AW3000 as pillar, and number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polystyrene conversion measured is carried out using the DMF of 30mM triethylamine and 10mMLiBr as eluant.
(2) amine value
The amine value of basic resin type spreading agent is the method according to ASTMD2074, and the total amine value (mgKOH/g) measured is carried out solid constituent conversion and the value that obtains.
(3) mean molecular weight of the resin of pigment carrier (B)
The number-average molecular weight (Mn) of the acryl resin used as the resin of pigment carrier (B) and weight-average molecular weight (Mw) use TSKgel pillar (eastern ソ mono-society system), to be equipped with the GPC (eastern ソ mono-society system, HLC-8120GPC) of RI detecting device, and in developing solvent, THF is used to carry out number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polystyrene conversion measured.
(4) acid value of the resin of pigment carrier (B)
The acid value of the acryl resin used as the resin of pigment carrier (B) is the potential difference titration according to JISK0070, the acid value (mgKOH/g) measured is carried out solid constituent conversion and the value that obtains.
(the 1st embodiment)
For containing the green coloring composition of above-mentioned basic resin type spreading agent (a) as essential component, embodiment (example I series) and comparative example (Comparative Example I series) is utilized to be described.
First, the resin type spreading agent, its solution, commercial resins type dispersant solution, acryl resin and its solution that use in example I series and Comparative Example I series are described.
Synthesis example I-1: the synthesis of resin type spreading agent I-1 and the modulation of its solution
In four mouthfuls of removable flasks with thermometer, stirring machine, distillation cascade and refrigeratory, add methyl ethyl ketone 70 parts, n-butyl acrylate 76.0 parts, sparteine 2.8 parts and isobutyl ethyl bromide 1.9 parts, be warming up to 40 DEG C under nitrogen flowing.Add stannous chloride 1.1 parts, be warming up to 75 DEG C of initiated polymerizations.After polymerization in 3 hours, polymeric solution is sampled, confirm that polymerization yield is more than 95% by the solid constituent be polymerized, add methacrylic acid-N, N-dimethylaminoethyl 24.0 parts and MEK30.0 part, and then be polymerized.Confirm that polymerization yield is more than 97% by the solid constituent of the polymeric solution after 2 hours, be cooled to room temperature and stop polymerization.The resin solution 100 parts methyl ethyl ketone 100 parts obtained is diluted, add Zeo-karb " ダ イ ア イ オ Application PK228LH (Mitsubishi Chemical's (strain) system) " 60 parts and at room temperature stir 1 hour, and then interpolation 10 parts of hydrotalcites (キ ヨ mono-ワ mono-De 500SN: consonance chemical industry (strain) system), as neutralizing agent, carry out the stirring of 30 minutes.Utilized and filtered Zeo-karb and adsorbent, removed the residue of polymerization catalyst thus.And then resin solution is concentrated, be substituted by ethylene glycol monomethyl ether acetic acid ester, obtain the solution that nonvolatile component is the resin type spreading agent I-1 (Mn=10200, Mw=12200, amine value 86mgKOH/g) of 40 % by weight.
Synthesis example I-2: the synthesis of resin type spreading agent I-2 and the modulation of its solution
Add methyl ethyl ketone 70 parts, n-butyl acrylate 75.0 parts, methyl methacrylate 10.0 parts, sparteine 2.3 parts and isobutyl ethyl bromide 1.6 parts by the method same with above-mentioned synthesis example I-1, and add stannous chloride 0.9 part of initiated polymerization.After polymerization in 3 hours, add methacrylic acid-N, N-dimethylaminoethyl 15.0 parts and MEK30.0 part, and then carry out the polymerization of 2 hours.Afterwards, carry out the operation that the residue of polymerization catalyst removed same with above-mentioned synthesis example I-1, obtain the solution that nonvolatile component is the resin type spreading agent I-2 (Mn=11900, Mw=13200, amine value 54mgKOH/g) of 40 % by weight.
Synthesis example I-3: the synthesis of resin type spreading agent I-3 and the modulation of its solution
Add methyl ethyl ketone 70 parts, ethyl acrylate 45.0 parts, methyl methacrylate 43.0 parts, sparteine 3.3 parts and isobutyl ethyl bromide 2.8 parts by the method same with above-mentioned synthesis example I-1, and add stannous chloride 1.4 parts of initiated polymerizations.After polymerization in 3 hours, add methacrylic acid-N, N-dimethylaminoethyl 12.0 parts and MEK30.0 part, and then carry out the polymerization of 2 hours.Afterwards, carry out the operation that the residue of polymerization catalyst removed same with above-mentioned synthesis example I-1, obtain the solution that nonvolatile component is the resin type spreading agent I-3 (Mn=7000, Mw=8500, amine value 43mgKOH/g) of 40 % by weight.
Synthesis example I-4: the synthesis of resin type spreading agent I-4 and the modulation of its solution
Add methyl ethyl ketone 70 parts, n-butyl acrylate 71.0 parts, sparteine 2.8 parts and isobutyl ethyl bromide 1.9 parts by the method same with above-mentioned synthesis example I-1, and add stannous chloride 1.4 parts of initiated polymerizations.After polymerization in 3 hours, add methacrylic acid-N, N-dimethylaminoethyl 29.0 parts and MEK30.0 part, and then carry out the polymerization of 2 hours.Afterwards, carry out the operation that the residue of polymerization catalyst removed same with above-mentioned synthesis example I-1, obtain the solution that nonvolatile component is the resin type spreading agent I-4 (Mn=10000, Mw=12000, amine value 105mgKOH/g) of 40 % by weight.
Synthesis example I-5: the synthesis of resin type spreading agent I-5 and the modulation of its solution
Add methyl ethyl ketone 70 parts, n-butyl acrylate 66.0 parts, sparteine 2.8 parts and isobutyl ethyl bromide 1.9 parts by the method same with above-mentioned synthesis example I-1, and add stannous chloride 1.4 parts of initiated polymerizations.After polymerization in 3 hours, add methacrylic acid-N, N-dimethylaminoethyl 34.0 parts and MEK30.0 part, and then carry out the polymerization of 2 hours.Afterwards, carry out the operation that the residue of polymerization catalyst removed same with above-mentioned synthesis example I-1, obtain the solution that nonvolatile component is the resin type spreading agent I-5 (Mn=9800, Mw=12000, amine value 121mgKOH/g) of 40 % by weight.
Synthesis example I-6: the modulation of commercial resins type dispersant solution
Using as commercial resins type spreading agent PVC Star Network ケ ミ mono-ジ ヤ パ Application society BYK-161,163,164,167,174,184,2000,2050, Japanese Le one Block リ ゾ mono-Le society SOLSPERSE-34750,56000, チ バ ジ ヤ パ Application society EFKA4330,4046,4060,4080 is less than 40% for nonvolatile component respectively, nonvolatile component is made to be more than 60% by drying under reduced pressure, then use ethylene glycol monomethyl ether acetic acid ester to be modulated into the solution that nonvolatile component is 40 % by weight, the solution as commercial resins type spreading agent uses.
Synthesis example I-A: the synthesis of acryl resin I-A and the modulation of its solution
Cyclohexanone 800 parts is added in reaction vessel, while to nitrogen injection in container while be heated to 100 DEG C, at the same temperature, styrene 80.0 parts, methacrylic acid 40.0 parts, methacrylic acid-N is dripped with 1 hour, the potpourri of N-methyl esters 85.0 parts, n-BMA 95.0 parts and azoisobutyronitrile 10.0 parts, carries out polyreaction.
After dropping, and then after the reaction carrying out 3 hours at 100 DEG C, interpolation cyclohexanone 50 parts dissolves the solution of azoisobutyronitrile 2.0 parts, and then continue reactions 1 hour at 100 DEG C, obtain the cyclohexanone solution that weight-average molecular weight is about 30000, acid value is the acryl resin I-A of 87mgKOH/g.
After being cooled to room temperature, to sample the resin solution of about 2g, at 180 DEG C, carry out the heat drying of 20 minutes, measure nonvolatile component, in the resin solution of previously synthesis, add ethylene glycol monomethyl ether acetic acid ester to make nonvolatile component is 20 % by weight solution preparing acryl resin I-A like this.
The synthesis of synthesis example I-B ~ I-P: acryl resin I-B ~ I-P and the modulation of their solution
Use monomer composition, amount of initiator (azoisobutyronitrile amount) as shown in table 2 below, the synthesis of carrying out acryl resin I-B ~ I-P same with the synthetic method of aforesaid propylene acid resin I-A, and modulate their solution.In addition, the acid value of the resin of synthesis, weight-average molecular weight are shown in table 2.
[table 2]
The explanation be called for short in table 2
Styrene (weight portion)
MA: methacrylic acid (weight portion)
MMA: methyl methacrylate (weight portion)
NBMA: n-BMA (weight portion)
AIBN: azoisobutyronitrile (weight portion)
Acid value (mgKOH/g)
Molecular weight: weight-average molecular weight
(F) formula: Y >-750X+51000
(G) formula: Y > 940X-79000
(H) formula: Y > 8000
X: the acid value (mgKOH/g) of resin
Y: the weight-average molecular weight of resin
[example I-1]
By zinc halide phthalocyanine viridine green (C.I. naphthol green 58) 11.0 parts, the solution 2.5 parts of the SOLSPERSE-56000 modulated according to the modulator approach of the solution of above-mentioned resin dispersion type spreading agent, the solution of aforesaid propylene acid resin I-A 40.0 parts, and after the potpourri uniform stirring mixing of ethylene glycol monomethyl ether acetic acid ester 46.5 parts, use the zirconia bead that diameter is 0.5mm, in Chinese mugwort lattice grinding machine (ア イ ガ mono-ミ Le) (ア イ ガ mono-ジ ヤ パ Application society system " ミ ニ モ デ Le M-250MKII "), dispersion is after 5 hours, filter with the filtrators of 5.0 μm and prepare viridine green dispersion.
Then, be uniformly mixed, to make above-mentioned viridine green dispersion 60.0 parts, the solution of aforesaid propylene acid resin I-A 11.0 parts, trimethylolpropane triacrylate (Xin Zhong village chemistry society's system " NK エ ス テ Le ATMPT ") 4.2 parts, Photoepolymerizationinitiater initiater (チ バ ジ ヤ パ Application society system " イ Le ガ キ ユ ア 1 ") 1.2 parts, sensitizer (soil conservation ケ paddy chemistry society's system " EAB-F ") 0.4 part, be formed uniformly with the potpourri of ethylene glycol monomethyl ether acetic acid ester 23.2 parts, then filter with the filtrator of 1.0 μm, obtain the green anticorrosive additive material I-1 of alkali developable.
[example I-2 ~ I-24]
Use the solution of the solution of above-mentioned resin type spreading agent as shown in table 3, above-mentioned pigment derivative and aforesaid propylene acid resin, obtain alkali developable anticorrosive additive material I-2 ~ I-24 equally with the method shown in example I-1.Table 4 illustrates the type (block type or non-block type any one) of resin type spreading agent.
[table 3]
[table 4]
[example I-25]
Resin solution (nonvolatile component is 40 % by weight) 2.5 parts, following formula I-9 by zinc halide phthalocyanine viridine green (C.I. naphthol green 58) 10.0 parts, SOLSPERSE-56000:
After the potpourri of the shown pigment derivative with basic functionality 1.0 parts, the solution 40.0 parts of aforesaid propylene acid resin I-A and ethylene glycol monomethyl ether acetic acid ester 46.5 parts carries out uniform stirring mixing, use the zirconia bead that diameter is 0.5mm, in Chinese mugwort lattice grinding machine (ア イ ガ mono-ジ ヤ パ Application society system " ミ ニ モ デ Le M-250MKII "), dispersion is after 5 hours, filters prepare viridine green dispersion with the filtrators of 5.0 μm.
Then, be uniformly mixed, to make above-mentioned viridine green dispersion 60.0 parts, the solution of aforesaid propylene acid resin I-A 11.0 parts, trimethylolpropane triacrylate (Xin Zhong village chemistry society's system " NK エ ス テ Le ATMPT ") 4.2 parts, Photoepolymerizationinitiater initiater (チ バ ジ ヤ パ Application society system " イ Le ガ キ ユ ア 1 ") 1.2 parts, sensitizer (soil conservation ケ paddy chemistry society's system " EAB-F ") 0.4 part, be formed uniformly with the potpourri of ethylene glycol monomethyl ether acetic acid ester 23.2 parts, then filter with the filtrator of 1.0 μm, obtain the green anticorrosive additive material I-25 of alkali developable.
[example I-26 ~ I-48]
Use the solution of the solution of above-mentioned resin type spreading agent as shown in table 5, above-mentioned pigment derivative and aforesaid propylene acid resin, obtain alkali developable anticorrosive additive material I-26 ~ I-48 equally with the method shown in example I-25.
[table 5]
[example I-49]
By zinc halide phthalocyanine viridine green (C.I. naphthol green 58) 10.0 parts, SOLSPERSE-56000 solution (nonvolatile component is 40 % by weight) 2.5 parts, following formula I-10:
Shown possess have after pigment derivative 1.0 parts, the solution 40.0 parts of aforesaid propylene acid resin I-A and the potpourri of ethylene glycol monomethyl ether acetic acid ester 46.5 parts that anchor portion (ア Application カ mono-) is the triazine ring skeleton of the basic functionality of benzimidazolone be uniformly mixed equably, use the zirconia bead that diameter is 0.5mm, in Chinese mugwort lattice grinding machine (ア イ ガ mono-ジ ヤ パ Application society system " ミ ニ モ デ Le M-250MKII "), dispersion is after 5 hours, prepares viridine green dispersion with the metre filter of 5.0 μm.
Then, be uniformly mixed, to make above-mentioned viridine green dispersion 60.0 parts, the solution of aforesaid propylene acid resin I-A 11.0 parts, trimethylolpropane triacrylate (Xin Zhong village chemistry society's system " NK エ ス テ Le ATMPT ") 4.2 parts, Photoepolymerizationinitiater initiater (チ バ ジ ヤ パ Application society system " イ Le ガ キ ユ ア 1 ") 1.2 parts, sensitizer (soil conservation ケ paddy chemistry society's system " EAB-F ") 0.4 part, be formed uniformly with the potpourri of ethylene glycol monomethyl ether acetic acid ester 23.2 parts, then the metre filter of 1.0 μm is used, obtain the green anticorrosive additive material I-49 of alkali developable.
[example I-50 ~ I-72]
As shown in table 6, use the solution of the solution of above-mentioned resin type spreading agent, above-mentioned pigment derivative and aforesaid propylene acid resin, obtain alkali developable anticorrosive additive material I-50 ~ I-72 equally with the method shown in example I-49.
[table 6]
[Comparative Example I-1 ~ I-15]
Replace except the SOLSPERSE-56000 solution that uses in example I-1 except using the solution (nonvolatile component is 40 % by weight) of the spreading agent shown in table 7, other is identical with example I-1 obtains alkali developable anticorrosive additive material I-73 ~ I-87.
[table 7]
[Comparative Example I-16]
Except using halogenated copper phthalocyanine viridine green (C.I. pigment green 36) to replace except zinc halide phthalocyanine viridine green (C.I. naphthol green 58), other is same with example I-3 obtains alkali developable anticorrosive additive material I-88.
(evaluation method)
Use the alkali developable anticorrosive additive material I-1 ~ I-88 obtained, with following method, viscosity characteristics is measured for evaluating mobility, measure lightness and contrast ratio for carrying out the evaluation of lightness and contrast ratio (CR), for evaluate stability measure through time contrast ratio rate of change and through time rate of viscosity increase.
(1) assay method of viscosity characteristics
The viscosity when viscosity of gained alkali developable anticorrosive additive material uses E type viscosity meter (Dong Ji industry society system " ELD type viscosity meter ") mensuration rotation number to be 20rpm obtains.And then try to achieve the ratio (be referred to as thixotropic index, this value is larger, and thixotropy is higher) of viscosity when rotation number is 6rpm and 60rpm, carry out thixotropic evaluation.
(2) through time rate of viscosity increase assay method
Use E type viscosity meter (Dong Ji industry society system " ELD type viscosity meter "), 25 DEG C, under rotation number is the condition of 20rpm, measure by the gained alkali developable anticorrosive additive material modulation initial viscosity of latter second day and place 1 week at 40 DEG C and carried out through time promotion through time viscosity.By the initial viscosity that measures like this and through time viscosity substitute into following formula, measure through time rate of viscosity increase.
[through time rate of viscosity increase]=(through time viscosity/initial viscosity) × 100
(3) assay method of lightness
Gained alkali developable anticorrosive additive material being utilized spinner and changes rotation number to prepare 3 coated substrates, is 0.62,0.6,0.58 to make the chromaticity y of dry film thickness in cie color system.Be coated with the drying 30 points at 80 DEG C of rear hot-air oven, then measure thickness respectively, obtain lightness when chromaticity y is 0.6 by the data separate linear correlation method methods of 3.Colourity uses microspectrophotometer (オ リ Application パ ス optics society's system " OSP-SP100 ") to measure.
(4) assay method of the contrast ratio of film
By the substrate used in lightness mensuration, obtain contrast ratio when chromaticity y is 0.6 by the data separate linear correlation methods of 3.Colourity uses microspectrophotometer (オ リ Application パ ス optics society's system " OSP-SP100 ") to measure.
For the determinator of the contrast ratio of film and the calculation method of numerical value, following Fig. 1 is used to be described.
Polarization is there is in the light sent from liquid crystal display back light unit (7) by polaroid (6), by being coated on the dry coating (4) of the coloured composition on glass substrate (5), arrive polaroid (3).If polaroid (6) is parallel with the plane of polarization of polaroid (3), then light transmission polaroid (3), but when plane of polarization is vertical, light is polarized sheet (3) blocking.But, if when dry coating (4) that caused the light of polarization by coloured composition by polaroid (6), there is the scattering etc. caused by pigment particles, and produce dislocation in a part for plane of polarization, then reduce through the light quantity of polaroid (3) when polaroid is parallel, when polaroid is vertical, a part of light transmission polaroid (3).Measure this through light as the brightness on polaroid, calculate polaroid parallel time the ratio (contrast ratio) of brightness and brightness time vertical.
(contrast ratio)=(brightness time parallel)/(brightness time vertical)
Therefore, if there is the scattering that caused by the pigment of the dry coating (4) of coloured composition, then brightness time parallel reduces, and brightness time vertical increases, therefore contrast ratio step-down.
Further, nitometer (1) uses color luminance meter (ト プ コ Application society's system " BM-5A "), and polaroid uses polaroid (Dong electrician society system " NPF-G1220DUN ").Further, in order to cover unwanted light during mensuration, putting and opening in mensuration part the mask (2) that the length of side is the black of four square holes of 1cm.
(5) assay method of the rheological parameters' change with time rate of contrast ratio
Gained alkali developable anticorrosive additive material is left standstill seven days at 40 DEG C, is obtained the rate of change of the CR (contrast ratio) after seven days leave standstill relative to initial CR (contrast ratio) by following formula.
Through time CR rate of change=(CR after seven days leave standstill)/(initial CR)
If this through time contrast ratio rate of change be more than 90%, then can reach realistic scale.Be preferably more than 95%.When exceeding this scope, storage stability is poor, can not become color filter green coloring composition.
As the thixotropic index of resist obtained above, viscosity, through time rate of viscosity increase, contrast ratio (CR), contrast ratio (CR) through time be shown in table 8 ~ 11 than the result of rate of change, lightness.
[table 8]
CR: contrast ratio
[table 9]
CR: contrast ratio
[table 10]
CR: contrast ratio
[table 11]
CR: contrast ratio
As shown in example I series, when using amine value to be the basic resin type spreading agent of 35 ~ 100mgKOH/g, can good fluidity be obtained, through time excellent storage stability, and achieve the green coloring composition of high brightness, high contrast ratio.
When above-mentioned resin type spreading agent is the block copolymer resin comprising alkaline copolymerized block (a1) and pigment carrier compatibility copolymerized block (a2), high contrast ratio and then can be formed.
And then when the pigment derivative and above-mentioned resin type spreading agent with basic functionality being share, initial contrast ratio uprises, and viscosity characteristics, ageing stability are also roughly good.And, and then when share with following such resin, green coloring composition the most excellent can be obtained, described resin be using X as acid value, Y as mean molecular weight time, with (F) Y >-750X+51000 and (G) Y > 940X-79000 and the resin of the Range Representation of (H) Y > 8000.
Relative to instead, in Comparative Example I-1 ~ I-15, form mobility, storage stability is all poor, the green coloring composition that contrast ratio is low.In addition, in Comparative Example I-16, green owing to employing halogenated copper phthalocyanine, so form the green coloring composition of lightness difference.
(the 2nd embodiment)
Then, for containing the green coloring composition of above-mentioned pigment derivative (b) as essential component, embodiment (example II series) and comparative example (Comparative Example I I series) is utilized to be described.
First, the acrylic resin soln used in example II series and Comparative Example I I series is described.
Synthesis example II-A: the synthesis of acryl resin II-A and the modulation of its solution
Cyclohexanone 800 parts is added in reaction vessel, while to nitrogen injection in container while be heated to 100 DEG C, at the same temperature, drip the potpourri of styrene 80.0 parts, methacrylic acid 40.0 parts, methyl methacrylate 85.0 parts, n-BMA 95.0 parts and azoisobutyronitrile 2.0 parts with 1 hour, carry out polyreaction.
After dropping, and then react at 100 DEG C after 3 hours, interpolation cyclohexanone 50 parts dissolves the solution of azoisobutyronitrile 2.0 parts, and then continues reactions 1 hour at 100 DEG C, obtains the cyclohexanone solution that weight-average molecular weight is about 30000, acid value is the acryl resin II-A of 87mgKOH/g.
After being cooled to room temperature, to sample the resin solution of about 2g, at 180 DEG C, carry out the heat drying of 20 minutes, measure nonvolatile component, in the resin solution of previously synthesis, add ethylene glycol monomethyl ether acetic acid ester to make nonvolatile component is 20 % by weight solution preparing acryl resin II-A like this.
The synthesis of synthesis example II-B ~ II-P: acryl resin II-B ~ II-P and the modulation of their solution
Use monomer composition, amount of initiator (azoisobutyronitrile amount) as shown in table 12 below, the synthesis of carrying out acryl resin II-B ~ II-P same with the synthetic method of aforesaid propylene acid resin II-A, and modulate their solution.In addition, the acid value of the resin of synthesis, weight-average molecular weight are shown in table 12.
[table 12]
The explanation be called for short in table 12
Styrene (weight portion)
MA: methacrylic acid (weight portion)
MMA: methyl methacrylate (weight portion)
NBMA: n-BMA (weight portion)
AIBN: azoisobutyronitrile (weight portion)
Acid value (mgKOH/g)
Molecular weight: weight-average molecular weight
(F) formula: Y >-750X+51000
(G) formula: Y > 940X-79000
(H) formula: Y > 8000
X: the acid value (mgKOH/g) of resin
Y: the weight-average molecular weight of resin
[example II-1]
By zinc halide phthalocyanine viridine green (C.I. naphthol green 58) 11.0 parts, following formula II-9:
Shown possess have that anchor portion is the pigment derivative 1.0 parts of the triazine ring skeleton of the basic functionality of benzimidazolone, after the potpourri of the solution 40.0 parts of acryl resin II-A and ethylene glycol monomethyl ether acetic acid ester 48.0 parts is uniformly mixed equably, use the zirconia bead that diameter is 0.5mm, in Chinese mugwort lattice grinding machine (ア イ ガ mono-ジ ヤ パ Application society system " ミ ニ モ デ Le M-250MKII "), dispersion is after 5 hours, prepares viridine green dispersion with the metre filter of 5.0 μm.
Then, be uniformly mixed, to make above-mentioned viridine green dispersion 60.0 parts, the solution of acryl resin II-A 11.0 parts, trimethylolpropane triacrylate (Xin Zhong village chemistry society's system " NK エ ス テ Le ATMPT ") 4.2 parts, Photoepolymerizationinitiater initiater (チ バ ス ペ シ ヤ リ テ イ mono-ケ ミ カ Le ズ society's system " イ Le ガ キ ユ ア 1 ") 1.2 parts, sensitizer (soil conservation ケ paddy chemistry society's system " EAB-F ") 0.4 part, be formed uniformly with the potpourri of ethylene glycol monomethyl ether acetic acid ester 23.2 parts, then the metre filter of 1.0 μm is used, obtain the green anticorrosive additive material II-1 of alkali developable.
[example II-2]
It is 37.0 parts except making the solution of acryl resin II-A, and adding that to add ethylene glycol monomethyl ether acetic acid ester to make nonvolatile component be beyond the solution 3 parts of the 20 % by weight acrylic acid series macromolecule dispersing agents (チ バ ジ ヤ パ Application society's system " EFKA4300; amine value 56mgKOH/g ") of modulation like this, other is same with example II-1 obtains alkali developable anticorrosive additive material II-2.
[example II-3]
It is 37.0 parts except making the solution of acryl resin II-A, and adding that to add ethylene glycol monomethyl ether acetic acid ester to make nonvolatile component be beyond the solution 3 parts of the 20 % by weight carbamate system macromolecule dispersing agents (PVC Star Network ケ ミ mono-society's system " BYK-163; amine value 10mgKOH/g ") of modulation like this, other is same with example II-1 obtains alkali developable anticorrosive additive material II-3.
[example II-4]
Except there is the pigment derivative that anchor portion is the triazine ring skeleton of the alkali subtituent of benzimidazolone by possessing, change over Formula Il-10:
Shown possess have beyond the pigment derivative of triazine ring skeleton that anchor portion is the alkali subtituent of anthraquinone, other is same with example II-1 obtains alkali developable anticorrosive additive material II-4.
[example II-5]
Except zinc halide phthalocyanine viridine green (C.I. naphthol green 58) 11.0 parts being changed over zinc halide phthalocyanine viridine green (C.I. naphthol green 58) 9.0 parts and metal complex system yellow uitramarine (C.I. pigment yellow 150, ラ Application Network セ ス society's system " YellowPigmentE4GN ") beyond 2.0 parts, other is same with example II-1 obtains alkali developable anticorrosive additive material II-5.
[example II-6]
Except there is the pigment derivative 1.0 parts that anchor portion is the triazine ring skeleton of the alkali subtituent of benzimidazolone by possessing, change over following formula II-11:
Shown possess beyond pigment derivative 1.0 parts that anchor portion is the alkali subtituent of benzimidazolone, and other is same with example II-1 obtains alkali developable anticorrosive additive material II-6.
[example II-7]
Except there is the pigment derivative 1.0 parts that anchor portion is the triazine ring skeleton of the alkali subtituent of benzimidazolone by possessing, change over following formula II-12:
Shown possess beyond pigment derivative 1.0 parts that anchor portion is the alkali subtituent of anthraquinone, and other is same with example II-1 obtains alkali developable anticorrosive additive material II-7.
[example II-8 ~ II-15]
Except the solution of acryl resin II-A being changed over the solution of acryl resin II-B, other is same with example II-1 obtains alkali developable anticorrosive additive material II-8.Below, except only the solution of acryl resin II-A being changed over the solution of acryl resin II-C ~ II-I, other is same with example II-1 obtains alkali developable anticorrosive additive material II-9 ~ II-15.
[Comparative Example I I-1]
Except making the solution of acryl resin II-A be 41.0 parts, and remove beyond pigment derivative, other is same with example II-1 obtains alkali developable anticorrosive additive material II-16.
[Comparative Example I I-2]
Except zinc halide phthalocyanine viridine green (C.I. naphthol green 58) 11.0 parts is changed into halogenated copper phthalocyanine viridine green (C.I. pigment green 36, Toyo Ink Manufacturing Co., Ltd.'s system " リ オ ノ mono-Le グ リ mono-Application 6YK ") beyond 11.0 parts, other is same with example II-1 obtains alkali developable anticorrosive additive material II-17.
[Comparative Example I I-3]
Except zinc halide phthalocyanine viridine green (C.I. naphthol green 58) 11.0 parts being changed into halogenated copper phthalocyanine viridine green (C.I. pigment Green 7, Toyo Ink Manufacturing Co., Ltd.'s system " リ オ ノ mono-Le グ リ mono-Application YS-07 ") 11.0 parts, other is same with example II-1 obtains alkali developable anticorrosive additive material II-18.
[example II-16 ~ II-22]
Except the solution of acryl resin II-A being changed over the solution of acryl resin II-J, other is same with example II-1 obtains alkali developable anticorrosive additive material II-19.Below, except only the solution of acryl resin II-A being changed over the solution of acryl resin II-K ~ II-P, other is same with example II-1 obtains alkali developable anticorrosive additive material II-20 ~ II-25.
(evaluation method)
Same with the 1st embodiment evaluate resist obtained above viscosity, thixotropic index, the lightness of film, contrast ratio, the results are shown in table 13.
Table 13
As shown in example II series, if use the pigment derivative with alkali subtituent when being disperseed by zinc halide phthalocyanine color, then can obtain the coloured composition of mobility excellence, forming the film that simultaneously can realize high brightness, high contrast ratio.Especially when use has the pigment derivative of triazine skeleton, lightness, contrast ratio show good numerical value.In addition, and then when share with following such resin solution, good especially, described resin solution be using X as acid value, Y as mean molecular weight time, with Y >-750X+51000 and Y > 940X-79000 and the resin solution of the Range Representation of Y > 8000.In contrast, the anticorrosive additive material employing the coloured composition of Comparative Example I I-1 is compared with the anticorrosive additive material obtained in an embodiment, viscosity increases considerably, and the lightness of film, contrast ratio are also in low level.In addition, for the anticorrosive additive material of coloured composition employing Comparative Example I I-2, II-3, its viscosity and the anticorrosive additive material obtained in embodiment are identical levels, and the contrast ratio of film is also almost in same level, but its lightness is compared with the film obtained in embodiment, it is lower value.
(the 3rd embodiment)
And then, for containing the green coloring composition of above-mentioned mixed organic solvents (c) as essential component, utilize embodiment (EXAMPLE III series) and comparative example (Comparative Example I II series) to be described.
First, for the evaluation method of the coating of resist and in EXAMPLE III series and Comparative Example I II series the acrylic resin soln that uses be described.
(evaluation method of coating)
Evaluation for coating is described.
Use the apparatus for coating of mouth mould coating method and spin coating mode to be coated with respectively, to form the average film thickness of 2.0 μm on the glass substrate of 360mm × 465mm size, the coated substrates obtained is carried out at 70 DEG C the prebake conditions of 20 minutes, obtain dry coating.Below, the method for expressing of assessment item content and result is described.
< only spin coating mode >
(film thickness uniformity)
" film thickness uniformity (end) ": the central portion in the minor face end from coated substrates is along substrate center direction until the length of 5cm measures a thickness every 5mm.Maximum film thickness is denoted as T 1, minimum thickness is denoted as T 2, average film thickness is denoted as T, calculates film thickness uniformity (end) by following formula (A).
" film thickness uniformity (beyond end) ": in the substrate center from coated substrates diagonally until the length of 26cm measures a thickness every 2cm.As described above, film thickness uniformity (beyond end) is calculated by following formula (A).
Film thickness uniformity [%]=((T 1-T 2)/T) × 100 (A)
The numerical value that film thickness uniformity [%] is preferably little, will be less than 4% and be denoted as zero, more than 4% and be less than 10% and be denoted as △, more than 10% to be denoted as ×.
< is mouth mould coating method > only
(taeniae shape is uneven)
" taeniae shape uneven ": for the coated substrates of mouth mould coating, utilizes white transmitted light evaluation as " taeniae shape is uneven " of the strip inequality in slit working direction of condensation product coming from slit opening portion.When not had taeniae shape uneven by range estimation, be denoted as zero, uneven when observing taeniae shape, be denoted as ×.
(maximum transmission rate)
Gained alkali developable anticorrosive additive material being utilized spinner and changes rotation number to prepare 3 coated substrates, is 0.62,0.6,0.58 to make the chromaticity y of dry film thickness in cie color system.Be coated with the drying 30 points at 80 DEG C of rear hot-air oven, then measure thickness respectively, obtain maximum transmission rate when chromaticity y is 0.6 by the data separate linear correlation methods of 3.Colourity uses microspectrophotometer (オ リ Application パ ス optics society's system " OSP-SP100 ") to measure.
Then, the acrylic resin soln used in EXAMPLE III series and Comparative Example I II series and pigment are described.
The modulation of synthesis example III-A: acryl resin III-A solution
Propylene glycol monomethyl ether (being denoted as PGMAC below) 800 parts is added in reaction vessel, while to nitrogen injection in container while be heated to 100 DEG C, at the same temperature, drip the potpourri of styrene 60.0 parts, methacrylic acid 60.0 parts, methyl methacrylate 65.0 parts, butyl methacrylate 65.0 parts and azoisobutyronitrile 10.0 parts with 1 hour, carry out polyreaction.
After dropping, and then react 3 hours at 100 DEG C, then interpolation PGMAC50 part dissolves the solution of azoisobutyronitrile 2.0 parts, and then at 100 DEG C, continue reaction 1 hour, obtain the solution that weight-average molecular weight (Mw) is the acryl resin III-A of 40,000.
After being cooled to room temperature, to sample the resin solution of about 2g, at 180 DEG C, carry out the heat drying of 20 minutes, measure nonvolatile component, in the resin solution of previously synthesis, add PGMAC to make nonvolatile component is 20 % by weight solution preparing acryl resin III-A like this.
pigment modulation example
Then the primary particle size assay method of pigment and the modulator approach of pigment are described.
(primary particle size assay method)
The method that the average primary particle diameter utilization of pigment directly measures the size of primary particle by the electron micrograph of transmission electron microscope (TEM) measures.Specifically, measure minor axis diameter and the major diameter of the primary particle of each pigment, using the particle diameter of mean value as this pigment particles.Then, for 100 pigment particles, the volume (weight) of respective particle is similar to the cube of required particle diameter and tries to achieve, volume average particle size is denoted as average primary particle diameter.
(modulation of viridine green III-1)
Zinc halide phthalocyanine viridine green (C.I. naphthol green 58) 200 parts, 1400 parts, sodium chloride and diglycol 360 parts is added, at 80 DEG C mixing 6 hours in stainless steel 1 gallon of kneader (ガ ロ Application ニ mono-ダ mono-) (aboveground making is made).Then this mixing thing joined in the warm water of 8 liters, be heated to 80 DEG C and stir 2 hours, make pulpous state, repeatedly carry out filtering, wash and after removing sodium chloride and diglycol, dry diel at 85 DEG C, obtains the viridine green III-1 of 190 parts.The primary particle size of being tried to achieve by TEM (transmission electron microscope) is 50nm.
(modulation of viridine green III-2)
Except replacing with except halogenated copper phthalocyanine viridine green (C.I. pigment green 36) by zinc halide phthalocyanine viridine green (C.I. naphthol green 58), other is same with the modulation of viridine green III-1 obtains viridine green III-2.The primary particle size of being tried to achieve by TEM (transmission electron microscope) is 60nm.
(modulation of viridine green III-3)
Except replacing with except halogenated copper phthalocyanine viridine green (C.I. pigment Green 7) by zinc halide phthalocyanine viridine green (C.I. naphthol green 58), other is same with the modulation of viridine green III-1 obtains viridine green III-3.The primary particle size of being tried to achieve by TEM (transmission electron microscope) is 60nm.
(modulation of yellow uitramarine)
Except replacing with except metal complex system yellow uitramarine (C.I. pigment yellow 150) by zinc halide phthalocyanine viridine green (C.I. naphthol green 58), other is same with the modulation of viridine green III-1 obtains yellow uitramarine.The primary particle size of being tried to achieve by TEM (transmission electron microscope) is 70nm.
pigment dispersion modulation example
Then the modulator approach for color filter green coloring composition (viridine green dispersion) is described.
(modulation of viridine green dispersion III-1)
After the potpourri of the solution 40 parts of viridine green III-1 (C.I. naphthol green 58) 11.0 parts, acryl resin III-A, propylene glycol monomethyl ether (PGMAC) 48.0 parts, resin type spreading agent (EFKA4300) 1.0 parts is uniformly mixed equably, use the zirconia bead that diameter is 0.5mm, in Chinese mugwort lattice grinding machine (ア イ ガ mono-ジ ヤ パ Application society system " ミ ニ モ デ Le M-250MKII "), dispersion is after 5 hours, filters prepare viridine green dispersion III-1 with the filtrators of 5.0 μm.
Below, the material shown in use table 14 is same with the modulation of viridine green dispersion III-1 obtains viridine green dispersion III-2 ~ III-8.Further, pigment dispersion III-5 uses these two kinds of pigment of 9 parts of viridine green III-1 and 2 part yellow uitramarines to carry out conditioned pigment dispersion.
[table 14]
(anticorrosive additive material Production Example)
Then the assay method of the dispersion particle diameter of green anticorrosive additive material and modulator approach are described.
(mensuration of dispersion particle diameter)
Use have employed the マ イ Network ロ ト ラ Star Network UPA-EX150 of the Ji Zhuan society of dynamic light scattering method (FFT power spectrum method), and with particle permeability for absorption mode, shape of particle is aspherical, and using D50 as mean diameter.The diluting solvent measured uses the solvent used in dispersions respectively, measures for the sample of ultrasound wave process.
(utilizing the particle diameter that SEM measures)
The particle diameter measured by SEM of pigment is that the method that utilization directly measures the size of maximum particle by the electron micrograph of scanning electron microscope (SEM) carries out measuring.Specifically, in photo, take 50 pigment particles, measure minor axis diameter and the major diameter of the primary particle of each pigment, using the particle diameter of mean value as this pigment particles, represent its maximum particle diameter in the mode retaining 1 position effective digital after radix point.
(green anticorrosive additive material III-1)
60.0 parts of viridine green dispersion III-1
11.0 part acrylic resin soln
Trimethylolpropane triacrylate (Xin Zhong village chemistry society's system " NK エ ス テ Le ATMPT ") 4.2 parts
1.2 parts of Photoepolymerizationinitiater initiaters (チ バ ス ペ シ ヤ リ テ イ mono-ケ ミ カ Le ズ society's system " イ Le ガ キ ユ ア 1 ")
0.4 part of sensitizer (soil conservation ケ paddy chemistry society's system " EAB-F ")
15.0 part PGMAC
8.2 parts of cyclohexyl acetates
Carry out being uniformly mixed said mixture is formed uniformly, then obtain the green anticorrosive additive material III-1 of alkali developable with the metre filter of 1.0 μm.In whole solvent, the match ratio of PGMAC is 89.8%, and the match ratio of cyclohexyl acetate is 10.2%.In addition, the particle diameter measured by SEM of the viridine green particle of dispersion is 0.2 μm.
(green anticorrosive additive material III-2)
60.0 parts of viridine green dispersion III-1
11.0 part acrylic resin soln
4.2 parts of trimethylolpropane triacrylates (Xin Zhong village chemistry society's system " NK エ ス テ Le ATMPT ")
1.2 parts of Photoepolymerizationinitiater initiaters (チ バ ス ペ シ ヤ リ テ イ mono-ケ ミ カ Le ズ society's system " イ Le ガ キ ユ ア 1 ")
0.4 part of sensitizer (soil conservation ケ paddy chemistry society's system " EAB-F ")
23.2 part cyclohexyl acetate
Carry out being uniformly mixed said mixture is formed uniformly, then obtain the green anticorrosive additive material III-2 of alkali developable with the metre filter of 1.0 μm.In whole solvent, the match ratio of PGMAC is 71.0%, and the match ratio of cyclohexyl acetate is 29.0%.In addition, the particle diameter measured by SEM of the viridine green particle of dispersion is 0.2 μm.
Below, the material shown in use table 15 is same with the modulation of green anticorrosive additive material III-1 obtains green anticorrosive additive material III-3 ~ III-11.The particle diameter measured by SEM of each anticorrosive additive material is also illustrated in addition in table 15.
[table 15]
[comparative example]
Use material shown in table 16, modulate green anticorrosive additive material equally with the modulation of green anticorrosive additive material III-1.Further, for green anticorrosive additive material III-12 and III-19, a kind of solvent of 23.2 parts is added.The particle diameter measured by SEM of each anticorrosive additive material is also illustrated in addition in table 16.
In addition, the characteristic value of the organic solvent used in EXAMPLE III series and Comparative Example I II series is shown in table 17.
[table 17]
(evaluation result)
Same with the 1st embodiment evaluate resist obtained above viscosity, thixotropic index, the lightness of film, contrast ratio, its result is shown in table 18 and table 19 with the evaluation result of dispersion particle diameter, maximum transmission rate and coating.
(preparation of red pigment dispersion)
Then, use red anticorrosive additive material and green anticorrosive additive material to make color filter, and evaluate.First, the red anticorrosive additive material used in the making of color filter is described.
After the potpourri of 8.0 parts of C.I. paratoneres 177, acrylic resin soln 40 parts, propylene glycol monomethyl ether (PGMAC) 48.0 parts, resin type spreading agent (EFKA4300) 1.0 parts is uniformly mixed equably, use the zirconia bead that diameter is 0.5mm, in Chinese mugwort lattice grinding machine (ア イ ガ mono-ジ ヤ パ Application society system " ミ ニ モ デ Le M-250MKII "), dispersion is after 5 hours, filters prepare red pigment dispersion with the filtrators of 5.0 μm.
(modulation of red anticorrosive additive material)
Be uniformly mixed, to make red pigment dispersion 60.0 parts, acrylic resin soln 11.0 parts, trimethylolpropane triacrylate (Xin Zhong village chemistry society's system " NK エ ス テ Le ATMPT ") 4.2 parts, Photoepolymerizationinitiater initiater (チ バ ジ ヤ パ Application society system " イ Le ガ キ ユ ア 1 ") 1.2 parts, the potpourri of sensitizer (soil conservation ケ paddy chemistry society's system " EAB-F ") 0.4 part and PGMAC23.2 part is formed uniformly, then filter with the filtrator of 1.0 μm, obtain the red anticorrosive additive material of alkali developable.
(making of color filter)
With the above-mentioned red anticorrosive additive material that spinner coating about 2 μm is thick on the glass substrate of 10cm × 10cm, it is left standstill 15 minutes in the baking oven of 70 DEG C, by dry for remaining solvent removing.Then, exposure device is used to carry out striated pattern exposure.Exposure is 100mJ/cm 2.And then, utilize the developer solution comprising 2% aqueous sodium carbonate to carry out spray developing, remove unexposed portion, then use ion-exchange water washing, this substrate is heated 30 minutes at 230 DEG C, form the red color filter joint that live width is about 50 μm.Then, by same operation, save adjacent place at red color filter and use the green anticorrosive additive material of EXAMPLE III-1 to form color filter joint, thus make the color filter of the color filter joint with 2 looks.
[table 18]
[table 19]
When the green anticorrosive additive material III-1 ~ III-11 as shown in EXAMPLE III series, use solvent (c1) make and employ in the resist of zinc halide phthalocyanine color dispersion, when use at least comprises the mixed organic solvents of solvent (c1) and solvent (c2), the coloured composition of mobility, coating excellence can be obtained, form the film that simultaneously can realize high brightness, high-transmission rate, high contrast ratio.In contrast, for the green anticorrosive additive material III-12 ~ III-21 shown in Comparative Example I II series, the film that simultaneously can meet lightness, contrast ratio, transmissivity, coating can not be obtained.

Claims (15)

1. color filter green coloring composition, it contains:
Pigment composition (A) at least containing zinc halide phthalocyanine color,
(B) comprise resin, its precursor or their potpourri pigment carrier and
(c) mixed organic solvents,
Described mixed organic solvents contains solubility parameters and SP value is 8.0 ~ 10.0(cal/cm 3) 1/2, boiling point under 760mmHg is the organic solvent (c1) of 140 ~ 159 DEG C; Be 8.0 ~ 10.0(cal/cm with solubility parameters and SP value 3) 1/2, boiling point under 760mmHg is the organic solvent (c2) of 160 ~ 200 DEG C, and in whole organic solvent, above-mentioned organic solvent (c1) and above-mentioned organic solvent (c2) add up to more than 85 % by weight.
2. color filter green coloring composition as claimed in claim 1, wherein, when acid value is denoted as X, weight-average molecular weight is when being denoted as Y, and the resin forming above-mentioned pigment carrier (B) is the resin of condition simultaneously all meeting following formula (F), (G) and (H):
（F）Y＞－750X＋51000
（G）Y＞940X－79000
（H）Y＞8000，
The unit of acid value is mgKOH/g.
3. color filter green coloring composition as claimed in claim 1, wherein, as pigment composition, further containing yellow uitramarine.
4. color filter green coloring composition as claimed in claim 3, wherein, as pigment composition, further containing halogenated copper phthalocyanine pigment.
5. color filter green coloring composition as claimed in claim 3, wherein, the content of above-mentioned pigment composition is, with the general assembly (TW) of described pigment composition (A) for benchmark, zinc halide phthalocyanine color is 50 ~ 90 % by weight, and yellow uitramarine is 5 ~ 45 % by weight.
6. color filter green coloring composition as claimed in claim 4, wherein, the content of above-mentioned pigment composition is, with the general assembly (TW) of described pigment composition (A) for benchmark, zinc halide phthalocyanine color is 50 ~ 90 % by weight, and halogenated copper phthalocyanine pigment is 5 ~ 45 % by weight, and yellow uitramarine is 5 ~ 45 % by weight.
7. color filter green coloring composition as claimed in claim 1, wherein, above-mentioned organic solvent (c1) is the solvent of more than a kind being selected from propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, ethylene glycol monomethyl ether acetic acid ester and ethylene glycol monomethyl ether acetate.
8. color filter green coloring composition as claimed in claim 1, wherein, above-mentioned organic solvent (c2) is the solvent of more than a kind being selected from cyclohexyl acetate, propylene-glycol diacetate, diethylene glycol diethyl ether and 3-ethoxyl ethyl propionate.
9. color filter green coloring composition as claimed in claim 1, wherein, when being benchmark with the total amount of above-mentioned mixed organic solvents (c), above-mentioned organic solvent (c1) is 50 % by weight ~ 95 % by weight, and above-mentioned organic solvent (c2) is 5 % by weight ~ 50 % by weight.
10. color filter green coloring composition as claimed in claim 1, is characterized in that, and then containing Photoepolymerizationinitiater initiater.
11. color filter green coloring compositions as claimed in claim 1, wherein, also containing the pigment derivative (b) with alkali subtituent.
12. color filter green coloring compositions as claimed in claim 11, is characterized in that, when being benchmark with the general assembly (TW) of above-mentioned pigment composition (A), the content of above-mentioned pigment derivative (b) is 0.001 ~ 40 % by weight.
13. color filter green coloring compositions as claimed in claim 1, wherein, and then containing basic resin type spreading agent (a).
14. color filter green coloring compositions as claimed in claim 1, average mark shot footpath is 0.05 ~ 0.2 μm.
15. color filters, is characterized in that, have the green color filter joint that the above-mentioned color filter green coloring composition according to any one of claim 1 ~ 14 is formed.
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JP5834379B2 (en) * 2009-06-25 2015-12-24 Jsr株式会社 Coloring composition, color filter and color liquid crystal display element
JP4905547B2 (en) * 2009-12-22 2012-03-28 凸版印刷株式会社 Color filter substrate and liquid crystal display device
JP5919698B2 (en) * 2010-11-08 2016-05-18 Jsr株式会社 Coloring composition for color filter, color filter and display element
JP6159348B2 (en) * 2014-02-14 2017-07-05 富士フイルム株式会社 Coloring composition, cured film, color filter, pattern forming method, color filter manufacturing method, solid-state imaging device, and image display device
JP5666037B1 (en) * 2014-03-13 2015-02-04 株式会社Ｄｎｐファインケミカル Method for producing pigment dispersion, pigment dispersion and colored resin composition for color filter
CN104536196B (en) * 2015-01-19 2017-03-01 京东方科技集团股份有限公司 A kind of preparation method of color membrane substrates, color membrane substrates and display floater
JP6119922B2 (en) * 2015-03-27 2017-04-26 三菱化学株式会社 Colored resin composition, color filter, and image display device
KR102558752B1 (en) * 2015-04-21 2023-07-24 디아이씨 가부시끼가이샤 Green pigment composition for color filters, and color filter
KR20180101392A (en) * 2016-01-14 2018-09-12 토요잉크Sc홀딩스주식회사 Method for manufacturing color filter for thermosetting coloring composition and solid-state imaging device
KR102371945B1 (en) * 2017-11-03 2022-03-08 동우 화인켐 주식회사 Colored Photosensitive Resin Composition, Color Filter and Display Device
KR102397084B1 (en) * 2017-11-21 2022-05-11 동우 화인켐 주식회사 Colored Photosensitive Resin Composition, Color Filter and Display Device
CN110187602B (en) * 2019-05-14 2020-10-13 深圳市华星光电技术有限公司 Color photoresist composition
TWI738310B (en) * 2019-12-09 2021-09-01 日商Ｄｉｃ股份有限公司 Halogenated zinc phthalocyanine pigment for color filters and method for manufacturing thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095379A (en) * 1990-04-13 1992-03-10 International Business Machines Corporation Color filter, liquid crystal display using same and method of repair thereof by using a negative photosensitive resin
CN1460192A (en) * 2001-02-23 2003-12-03 大日本油墨化学工业株式会社 Color filter
CN1492283A (en) * 2002-09-06 2004-04-28 东洋油墨制造株式会社 Light sensitive colouring composition and filter
CN1717598A (en) * 2002-11-29 2006-01-04 大赛璐化学工业株式会社 Colored photosensitive composition for color filters, color filters, and process for the production thereof

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3147423B2 (en) * 1991-09-05 2001-03-19 インターナショナル・ビジネス・マシーンズ・コーポレ−ション Color filter and manufacturing method thereof
JP2001342374A (en) * 2000-03-30 2001-12-14 Dainippon Ink & Chem Inc Halogenized copper phthalocyanine pigment composition for color filter, and color filter
JP2003161823A (en) * 2001-11-28 2003-06-06 Dainippon Ink & Chem Inc Pigment-dispersed resist for color filter, and the color filter
JP2003206414A (en) * 2002-01-11 2003-07-22 Dainippon Ink & Chem Inc Surface-treated fine organic pigment and color filter using the same
JP4195323B2 (en) 2003-03-24 2008-12-10 大日本印刷株式会社 Pigment dispersion for coloring resist, photosensitive coloring composition, and color filter
JP4809006B2 (en) * 2005-07-05 2011-11-02 太陽ホールディングス株式会社 Colored photosensitive resin composition and cured product thereof
JP4983029B2 (en) * 2006-02-03 2012-07-25 東洋インキＳｃホールディングス株式会社 Coloring composition
JP4841980B2 (en) * 2006-03-20 2011-12-21 新日鐵化学株式会社 Resin composition for color filter and color filter
JP4828275B2 (en) * 2006-03-30 2011-11-30 新日鐵化学株式会社 Light-shielding resin composition for color filter and color filter
JP5275548B2 (en) * 2006-03-30 2013-08-28 三菱化学株式会社 Green pigment dispersion, colored resin composition, color filter, and liquid crystal display device
JP5487564B2 (en) * 2007-06-21 2014-05-07 三菱化学株式会社 Colored resin composition, color filter, liquid crystal display device and organic EL display

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095379A (en) * 1990-04-13 1992-03-10 International Business Machines Corporation Color filter, liquid crystal display using same and method of repair thereof by using a negative photosensitive resin
CN1460192A (en) * 2001-02-23 2003-12-03 大日本油墨化学工业株式会社 Color filter
CN1492283A (en) * 2002-09-06 2004-04-28 东洋油墨制造株式会社 Light sensitive colouring composition and filter
CN1717598A (en) * 2002-11-29 2006-01-04 大赛璐化学工业株式会社 Colored photosensitive composition for color filters, color filters, and process for the production thereof

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