CN101441413A - Green coloring composition for filter and filter - Google Patents

Green coloring composition for filter and filter Download PDF

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Publication number
CN101441413A
CN101441413A CNA2008101821611A CN200810182161A CN101441413A CN 101441413 A CN101441413 A CN 101441413A CN A2008101821611 A CNA2008101821611 A CN A2008101821611A CN 200810182161 A CN200810182161 A CN 200810182161A CN 101441413 A CN101441413 A CN 101441413A
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methyl
pigment
color filter
resin
mentioned
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CNA2008101821611A
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CN101441413B (en
Inventor
宫泽由昌
中村高士
吉泽俊启
西田充志
有吉泰
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Toyo Ink Mfg Co Ltd
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Toyo Ink Mfg Co Ltd
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Priority to CN201310349447.5A priority Critical patent/CN103529646B/en
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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 a green colored composition for color filter and color filter. The invention discloses a green colored composition for color filter comprising: (A) a dye component containing at least ZnPc halogenide dye, and (B) a dye carrier containing resin, its precursor and mixture of them, the composition also contains (a) alkalescent resin disperser selected from amine value of 35-100mg KOH/g, (b) pigment derivative with alkalescent substituent and (c) at least one of mixed organic solvents, the mixed organic solvents contains organic solvent (c1) with solubility parameter (SP value) of 8.0-10.0 (cal/cm3)1/2 and boilling point of 140-159 at 760mmHg; and organic solvent (c2) with solubility parameter (SP value) of 8.0-10.0 (cal/cm3)1/2 and boilling point of 160-200 at 760mmHg.

Description

Color filter green coloring composition and color filter
Technical field
The present invention relates to use green coloring composition and use the color filter of its formation at the color filter that the preparation of the color filter that is used for color liquid crystal display arrangement, colour pick-up tube element etc. is used.
Background technology
Liquid crystal indicator be by be clipped in 2 liquid crystal layers controls between polaroid see through the 1st polaroid the polarisation of light degree, and control see through the display device that the light quantity of the 2nd polaroid shows, used the type of twisted-nematic (TN) type liquid crystal just becoming the main flow type.Liquid crystal indicator can carry out colour and show by between 2 polaroids color filter being set, in recent years, owing to begin color filter is applied to TV or personal computer monitor etc., the requirement of its high contrast ratio, high lightnessization is improved.
Color filter is included on the surface of transparency carriers such as glass the color filter joint color filter that (Off イ Le セ グ メ Application ト) is parallel or cross-over configuration forms with fine band (striped) shape of different form and aspect more than 2 kinds, and color filter joint that perhaps will be fine disposes the color filter that forms with certain in length and breadth arrangement mode.Color filter joint is fine like this and being that the mode that regulation is arranged fitly disposes to every kind of form and aspect with several microns～hundreds of microns.
Usually, in color liquid crystal display arrangement, on color filter, form by evaporation or sputter, and then be formed for making the alignment films of liquid crystal thereon in the certain orientation orientation by the transparency electrode that is used to drive liquid crystal.In order fully to obtain the performance of these transparency electrodes and alignment films, its formation need general more than 200 ℃, carry out under the preferred high temperature more than 230 ℃.Therefore, at present as the preparation method of color filter, become the method for main flow as the method that is referred to as the pigment dispersing method of colorant with the pigment of photostability, excellent heat resistance.
But the color filter that has generally disperseed pigment is because the light scattering that causes because of pigment etc., and the problem of the polarization degree disorder that makes liquid crystal control is arranged.That is, when essential shield light (OFF state), light leaks, and sees through the light time (ON state) essential, and therefore the transmitted light decay produces the low problem of ratio (contrast ratio) of brightness on the display device of ON state and OFF state.
For the high brightnessization that realizes color filter, high contrast ratio, be that the pigment that will contain in the color filter joint carries out the miniaturization processing up to now.But, even (will be the particle that is referred to as semifinished product (Network Le-De) of 10～100 μ m with pigment merely by the particle diameter of chemical reaction preparation, handle pigment by pigmentation until the potpourri that becomes the offspring that primary particle and its cohesion form) utilize various miniaturization disposal routes to carry out miniaturization, carry out the generally also cohesion easily of pigment of the miniaturization of primary particle or offspring, also formed the pigment solid content of huge bulk when too carrying out miniaturization.And then, for the pigment that has carried out miniaturization,, and make the offspring of pigment approach primary particle as much as possible and make its stabilization once more even it is dispersed in the pigment carrier that contains resin etc., obtain stable coloured composition and also be unusual difficulty.
To carry out coloured composition that the pigment dispersing of miniaturization forms in pigment carrier the cohesion etc. of pigment particles will often have taken place along with the time, thereby cause high viscosityization, manifest thixotropy.The viscosity of this coloured composition raises, poor flow quality causes the problem on the preparation manipulation or cause variety of issue on value of the product.For example, the color filter joint of color filter generally forms by coloured composition is spin-coated on the glass substrate, described coloured composition forms pigment dispersing in the pigment carrier that contains monomer and resin, if use the coloured composition of high viscosity, poor flow quality, then bad owing to spin coating, levelling is bad etc. causes obtaining filming of uniform film thickness, from rather than preferred.
Color filter is by dry with color composition for color filter (below be also referred to as be coating fluid) coating on transparency carrier, and forming thickness is that about 0.2～5 filming of μ m prepares like this.Coating method has spin-coating method or mouthful mould rubbing method etc., can suitably use according to its feature.
Spin-coating method is to be widely used in film forming method on less substrate, this coating process makes transparency carrier with certain rotation number rotation on one side, drip coating fluid at the transparency carrier central part on one side, utilize centrifugal force that coating fluid is launched thinly, be suitable for the rotation number of transparency carrier of this coating fluid or rotational time etc. by control, and form filming of expectation thickness on the surface of transparency carrier.But, come from the centrifugal force that utilization causes by rotation and the such principle of very thin expansion of will filming has the rotation center part of transparency carrier to compare the too shortcoming of thickening with the intermediate portion with the coating film thickness of peripheral part.In patent documentation 1, recorded and narrated the composition that will contain above boiling point of 50 weight % or the solvent of vapor pressure in particular range and made the coating fluid that the spin coating mode of the surface smoothing excellence of filming is used.
When the size of substrate is big, big for the load of device in the such mode that makes the substrate rotation of spin-coating method, therefore adopt a mouthful mould rubbing method.Mouth mould coating method is to discharge coating fluid from slit, will expect that on substrate filming of thickness is formed at the coating process on the surface of transparency carrier while move this slit.But, for this structure, with respect to the working direction of slit, be easy to produce the bar shaped inequality of vertical direction, in addition, in slit opening portion, coating fluid is exposed in the atmosphere and dry solidification takes place, and produces condensation product thus, and the bar shaped inequality of coating working direction takes place, this condensation product is sneaked in the coating thing, forms the shortcoming of filming.And then the peripheral part of filming protuberance is compared with portion of substrate center, and the problem of the thickening of filming is arranged.
In order to eliminate the problem of this unevenness of filming in mouth mould rubbing method, carry out the trial of in following patent documentation, recording and narrating.
In patent documentation 2 and 3, disclose by containing high boiling solvent, prevent the coating fluid dry solidification, and do not produce the method for condensation product.
[patent documentation 1] spy opens flat 6-3521 communique
[patent documentation 2] spy opens the 2003-55566 communique
[patent documentation 3] spy opens the 2004-346218 communique
On the other hand,, not only require high contrast ratio, also require high lightness for above-mentioned color filter.Be generally and obtained high lightness, in pigment carrier the time, made it approach primary particle pigment dispersing, improved the transparency of dispersion, made dispersion in spectrophotometric spectra, have high-transmission rate, obtained high lightness thus.
But, (red bluish-green as 3 kinds of primary colors of filter substrate; RGB) a kind of green general copper halide phthalocyanine color (for example C.I. pigment green 36 or C.I. pigment Green 7) that uses in is as body pigment, but as long as use copper halide phthalocyanine just is difficult to take into account high contrast ratio and high lightness.
In order to address these problems, bring into use the zinc halide phthalocyanine color that from existing copper halide phthalocyanine color, central metal is replaced to zinc, be used as bringing into play distinct color harmony color viewing area and look material widely with high colouring power.
[patent documentation 4] spy opens flat 10-130547 communique
[patent documentation 5] spy opens the 2001-141922 communique
[patent documentation 6] spy opens the 2007-204658 communique
But the zinc halide phthalocyanine green pigment is compared the acidity height with the copper halide phthalocyanine green pigment.Therefore, the zinc halide phthalocyanine green pigment is difficult to disperse than copper halide phthalocyanine green pigment.Disperse bad coloured composition that the cohesion etc. of pigment particles often takes place in time, thereby cause high viscosityization, manifest thixotropy.The viscosity of this coloured composition raises, poor flow quality causes the problem on the preparation manipulation or cause variety of issue on value of the product.For example, the color filter joint of color filter generally forms by coloured composition is spin-coated on the glass substrate, described coloured composition dispersed color in the pigment carrier that contains monomer and resin forms, if use the coloured composition of high viscosity, poor flow quality, then bad owing to spin coating, levelling is bad etc. causes obtaining filming of uniform film thickness, from rather than preferred.
In addition, known zinc halide phthalocyanine color is different with the chemical property of existing copper halide phthalocyanine color, and the pigment that is difficult to disperse.Therefore, only use to be suitable for existing copper halide phthalocyanine color or other dispersing of pigments agent, be difficult to the zinc halide phthalocyanine color is stably disperseed under the state of keeping its excellent color characteristics.
On the other hand, in order to obtain the zinc halide phthalocyanine color dispersion of high fluidity, use brings the spreading agent of more bad influence can for each patience in a large number, in order to keep high pigment levels, have to reduce the amount of the pigment carrier composition of keeping each patience, the result is difficult to take into account each patience, flowability and color characteristics.
And then, the zinc halide phthalocyanine color is different with existing copper halide phthalocyanine color, the solubleness of its pigment itself is different, therefore for the solvent of the most suitable dispersion copper halide phthalocyanine color, zinc halide phthalocyanine color and its compatibility are too good, when these solvents were used to disperse the zinc phthalocyanine color, itself was dissolved in solvent pigment, and the problem of the dispersion that can not obtain having high contrast ratio and high lightness is arranged.
And then, coloured composition (patent documentation 1～3) for the zinc halide phthalocyanine color that has used solvent used in the dispersion of copper halide phthalocyanine color to disperse, since the proterties of coating method that aforesaid spin coating mode or mouth mould coating method are such and the coating fluid that uses therein, and the shortcoming that produces thickness inequality or bar shaped inequality is arranged.
Here, the thickness inequality is meant that the homogeneity of thickness is insufficient, can be divided into " film thickness uniformity (end) ", be the film thickness uniformity of end face portion and " film thickness uniformity (beyond the end) ", i.e. these 2 kinds of homogeneitys here from substrate center to end face.In addition, the bar shaped inequality can be divided into 2 kinds: " horizontal stripe shape inequality ", promptly in mouth mould coating method, in the inequality of the strip that produces on the direction vertical and " taeniae shape inequality ", promptly in mouth mould coating method, come from the inequality of the strip on the slit working direction of the condensation product of slit opening portion with the working direction of slit.
Summary of the invention
Therefore, the object of the present invention is to provide the stable color filter green coloring composition of mobile and each patience excellence, and the lightness and the high color filter of contrast ratio that use it.
In addition, the object of the present invention is to provide color filter green coloring composition (green anticorrosive additive material), with color filter with the color filter joint that uses its formation, described color filter can reduce viewed shortcoming in the filming of the coating thing that utilizes spin coating mode and mouthful mould rubbing method to form with green coloring composition, and then can form lightness and the high color filter of contrast ratio.
Above-mentioned problem can solve with green coloring composition by color filter, and described color filter contains with green coloring composition:
(A) contain at least the zinc halide phthalocyanine color pigment composition and
(B) comprise the pigment carrier of resin, its precursor or their potpourri, and contain and be selected from:
(a) amine value be 35～100mg KOH/g basic resin type spreading agent,
(b) have alkali subtituent pigment derivative and
(c) at least 1 of mixed organic solvents kind forms, and it is 8.0～10.0 (cal/cm that described mixed organic solvents contains solubility parameters (SP value) 3) 1/2, the boiling point under the 760mmHg is 140～159 ℃ organic solvent (c1); And solubility parameters (SP value) is 8.0～10.0 (cal/cm 3) 1/2, the boiling point under the 760mmHg is 160～200 ℃ organic solvent (c2).
Use in the preferred version of green coloring composition at color filter of the present invention, when acid value note is made X (mg KOH/g), when the weight-average molecular weight note is made Y, the resin that constitutes above-mentioned pigment carrier (B) is the resin that all satisfies following formula (F), (G) and condition (H) simultaneously:
(F)Y>-750X+51000
(G)Y>940X-79000
(H)Y>8000。
Use in the preferred version of green coloring composition at color filter of the present invention, when being benchmark with the general assembly (TW) of the above-mentioned pigment composition (A) that contains the zinc halide phthalocyanine color [below the situation that only is called pigment composition (A) is arranged], the content of above-mentioned basic resin type spreading agent (a) is 0.001～50 weight %.
Use in the preferred version of green coloring composition at color filter of the present invention, above-mentioned basic resin type spreading agent (a) is the block copolymer resin that comprises alkaline copolymer block (a1) and pigment carrier compatibility copolymer block (a2), the block copolymer resin that for example utilizes living polymerization to obtain.
With in the preferred version of green coloring composition, 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 weight % at color filter of the present invention.
With in the preferred version of green coloring composition, above-mentioned organic solvent (c1) is the solvent more than at least a kind that is selected from propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, ethylene glycol monomethyl ether acetate and ethylene glycol monomethyl ether acetate at color filter of the present invention.
With in the preferred version of green coloring composition, above-mentioned organic solvent (c2) is the solvent more than at least a kind that is selected from cyclohexyl acetate, propylene-glycol diacetate, diethylene glycol diethyl ether and 3-ethoxyl ethyl propionate at color filter of the present invention.
With in the preferred version of green coloring composition, when being benchmark with the total amount of above-mentioned mixed organic solvents (c), above-mentioned organic solvent (c1) is 50 weight %～95 weight % at color filter of the present invention, and above-mentioned organic solvent (c2) is 5 weight %～50 weight %.
Use in the preferred version of green coloring composition at color filter of the present invention, and then contain Photoepolymerizationinitiater initiater.
With in the preferred version of green coloring composition, contain above-mentioned basic resin type spreading agent (a) and above-mentioned pigment derivative (b) at color filter of the present invention.
With in the preferred version of green coloring composition, contain above-mentioned basic resin type spreading agent (a) and above-mentioned mixed organic solvents (c) at color filter of the present invention.
With in the preferred version of green coloring composition, contain above-mentioned pigment derivative (b) and above-mentioned mixed organic solvents (c) at color filter of the present invention.
With in the preferred version of green coloring composition, contain above-mentioned basic resin type spreading agent (a), above-mentioned pigment derivative (b) and above-mentioned mixed organic solvents (c) at color filter of the present invention.
In addition, the present invention relates to color filter, it is characterized in that, have the green color filter joint (Green look Off イ Le セ グ メ Application ト that forms with green coloring composition by above-mentioned color filter).
Color filter of the present invention with green coloring composition by containing the pigment composition that (A) contains the zinc halide phthalocyanine color at least; (B) comprise the pigment carrier of resin, its precursor or their potpourri, and then contain at least a kind that is selected from above-mentioned basic resin type spreading agent (a), above-mentioned pigment derivative (b) and above-mentioned mixed organic solvents (c), thereby can form high flowing and stable pigment dispersion, by using said composition, can form the color filter of high lightness and high contrast ratio.In addition, can be formed in that viewed existing shortcoming reduces the color filter that contrast ratio and lightness are high in coating the filming of thing.
Especially, when above-mentioned basic resin type spreading agent (a) is when comprising the block copolymer resin of alkaline 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) and have the pigment derivative (b) of alkali subtituent, initial contrast ratio uprises, and ageing stability is also good.
Description of drawings
[Fig. 1] is used to measure 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
At first, enumerating embodiment preferred is described in detail with green coloring composition for color filter of the present invention.
And; in instructions; when being expressed as " (methyl) acryloyl ((メ ) ア Network リ ロ イ Le) "; " (methyl) acryloyl group ((メ ) ア Network リ Le) "; " (methyl) acrylic acid "; " (methyl) acrylate "; when " (methyl) acryloxy "; if not explanation especially, then expression " 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 of the present invention contains the pigment composition that (A) contains the zinc halide phthalocyanine color at least with green coloring composition; (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 35～100mg KOH/g;
In the 2nd embodiment, contain above-mentioned basic resin type spreading agent (a) and/or (b) have the pigment derivative of alkali subtituent;
In the 3rd embodiment, containing above-mentioned basic resin type spreading agent (a) and/or above-mentioned pigment derivative (b) and/or (c) containing solubility parameters (SP value) is 8.0～10.0 (cal/cm 3) 1/2, the boiling point under the 760mmHg is 140～159 ℃ organic solvent (c1); And solubility parameters (SP value) is 8.0～10.0 (cal/cm 3) 1/2, the boiling point under the 760mmHg is the mixed organic solvents of 160～200 ℃ organic solvent (c2).
That is, can contain above-mentioned basic resin type spreading agent (a), above-mentioned pigment derivative (b) and above-mentioned mixed organic solvents (c) any 2 kinds simultaneously, perhaps whole 3 kinds.
[pigment composition (A)]
Color filter of the present invention is characterised in that with green coloring composition, has used and has contained the pigment composition (A) of zinc halide phthalocyanine color as body pigment at least.
When representing typical zinc halide phthalocyanine color with color index (C.I) number, can enumerate C.I. naphthol green 58 etc.By using the zinc halide phthalocyanine color, can obtain the high lightness that can not obtain with other viridine greens as body pigment.And then, can use the pigment that obtains by known manufacture method.Especially, can use following such pigment, promptly, when utilizing the look material, 67[9], the method for recording and narrating among the 547-554 (1994), and when using n-hexylamine to measure as alkaline matter, the acidic functionality amount of this surface of pigments is preferably more than the 100 μ mol/g, and then more than the preferred 200 μ mol/g.
In pigment composition (A), not only contain zinc halide phthalocyanine as body pigment, for the purpose of color adaptation or complementary color can also and with other viridine green or yellow uitramarine.
As can and other viridine green of usefulness, can enumerate C.I. pigment Green 7,10,36,37 etc. viridine green.In addition, as can and the yellow uitramarine of usefulness, can enumerate 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.
Wherein, consider the preferred C.I. pigment yellow 13 8,139,150,185 etc. of also using from the angle that can enlarge chroma areas.
In whole nonvolatile component of coloured composition of the present invention, consider that from the angle that obtains sufficient color reproducibility the concentration of preferred pigment composition (A) is 10～90 weight %, more preferably 15～80 weight %, most preferably 20～70 weight %.When the concentration of pigment composition (A) during less than 10 weight %, can not obtain sufficient color reproducibility, when surpassing 90 weight %, the concentration step-down of pigment carrier, the bad stability of coloured composition.
As the ratio of particularly preferred pigment, when for example being benchmark with the general assembly (TW) of pigment composition (A), the zinc halide phthalocyanine color is 50～100 weight %, and the copper halide phthalocyanine color is 0～50 weight %, and yellow uitramarine is 0～50 weight %.
Be benchmark with pigment composition (A) more preferably, the zinc halide phthalocyanine color is 50～90 weight %, and the copper halide phthalocyanine color is 5～45 weight %, and yellow uitramarine is 5～45 weight %.Utilize the composition of this pigment, can enlarge chroma areas.
For the green coloring composition of the present invention that has used the zinc halide phthalocyanine color, when it being coated on glass substrate etc., to form with the green coloring composition that has used the copper halide phthalocyanine is identical colourity, and when measuring the transmissivity film, near the 450nm to being shown as the transmissivity higher near the 530nm than filming of the coloured composition that has used copper phthalocyanine.For the peak value of transmissivity, be shown as about about 50% high transmissivities especially, be about 90% value.Therefore, by combined with the general backlight that uses in color liquid crystal display arrangement, can obtain with the coloured composition that used copper phthalocyanines such as C.I. pigment green 36 or C.I. pigment Green 7 the high lightness that can not obtain.
[miniaturization of pigment]
The pigment that in green coloring composition of the present invention, uses can carry out the salt milled processed and with miniaturization form use, preferably use miniaturization pigment.
The salt milled processed is meant the mixing roll that uses kneader, two roller mills, three-roll mill, bowl mill, vertical ball mill or sand mill etc., with the potpourri of pigment and water-soluble inorganic salt and water-miscible organic solvent while heat carry out mechanically milling after, the processing of removing water-soluble inorganic salt and water-miscible organic solvent by washing.Water-soluble inorganic salt plays a role as broken auxiliary agent, and salt utilizes the high rigidity of inorganic salts to come broken pigment when grinding, produce active face thus, carries out crystalline growth.Therefore, the fragmentation of pigment and crystalline growth carry out simultaneously when mixing, and according to mixing condition, the primary particle size of the pigment that obtains is different.
In order to promote crystalline growth by heating, preferred heating-up temperature is 40～150 ℃.When heating-up temperature during less than 40 ℃, crystalline growth can not fully take place, the shape of pigment particles approaches amorphous, is not preferred therefore.On the other hand, when heating-up temperature surpassed 150 ℃, crystalline growth too carried out, and it is big that the primary particle size of pigment becomes, and therefore the colouring material 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 the size-grade distribution of the primary particle of salt milled processed pigment and the required expense of salt milled processed, is preferably 2～24 hours.
Condition optimization by will carry out the salt milled processed to pigment the time, it is very fine to obtain 1 particle diameter, the narrow range of Fen Buing in addition, the pigment with narrow size-grade distribution.
The primary particle size that the viridine green that uses 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 than 20nm hour, it is difficult that the dispersion in organic solvent becomes.When bigger, can not obtain sufficient contrast ratio in addition than 100nm.Particularly preferred scope is the scope of 25～85nm.
As the water-soluble inorganic salt that in the salt milled processed, uses, can use sodium chloride, barium chloride, potassium chloride or sodium sulphate etc., consider the preferred sodium chloride (salt) that uses from the angle of price.Consider that from this two aspect of treatment effeciency and production efficiency during as benchmark, the use amount of water-soluble inorganic salt is preferably 50～2000 weight %, most preferably 300～1000 weight % with the general assembly (TW) of pigment composition (A).
Water-miscible organic solvent has the function of moistening pigment and water-soluble inorganic salt, itself so long as in water dissolving (mixings) and the solvent that do not dissolve the inorganic salts of use substantially get final product qualification especially.But temperature raises when grinding owing to salt, and solvent is in the state that is easy to evaporate, so consider from the angle of security, preferred boiling point is the high boiling solvent more than 120 ℃.For example can use 2-methyl cellosolve, butoxy ethanol, 2-(isoamoxy) ethanol, 2-(own oxygen base) ethanol, diglycol, carbiphene, diglycol monotertiary butyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyglycol, 1-methoxyl-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, perhaps Ye Tai polypropylene glycol etc.During as benchmark, water-miscible organic solvent preferably uses the amount of 5～1000 weight %, most preferably uses the amount of 50～500 weight % with the general assembly (TW) of pigment composition (A).
When carrying out the salt milled processed, also can add resin as required.The kind of the resin that uses limits especially, can use natural resin, modified natural resin, synthetic resin or the synthetic resin that forms with the natural resin modification etc.The resin that uses at room temperature is solid, is preferably water-insoluble, and and then preferably can be partially dissolved in above-mentioned organic solvent.During as benchmark, the use amount of resin is preferably the scope of 5～200 weight % with the general assembly (TW) of pigment composition (A).
[pigment carrier (B)]
In green coloring composition of the present invention, except pigment composition (A), also contain the pigment carrier (B) that comprises resin, its precursor or their potpourri.
The pigment carrier that uses in green coloring composition of the present invention (B) is that the long regional spectral transmission of all-wave at 400～700nm of visible region is preferably more than 80%, the more preferably resin more than 95%, its precursor or their potpourri.Resin contains thermoplastic resin, heat-curing resin or active energy ray-curable resin, its precursor comprises monomer or the oligomer that utilizes active energy beam irradiation to be cured and generate transparent resin, can be with them separately or mix more than 2 kinds and use.During as benchmark, pigment carrier (B) can use the amount of 30～500 weight % with the general assembly (TW) of pigment composition (A).When less than 30 weight %, film forming and each patience deficiency, when than 500 weight % for a long time, pigment concentration is low, can not the apparent color characteristic.
When acid value note is made X (mg KOH/g), when the weight-average molecular weight note is made Y, the resin that preferably constitutes above-mentioned pigment carrier (B) is the resin that all satisfies following formula (F), (G) and condition (H) simultaneously:
(F)Y>-750X+51000
(G)Y>940X-79000
(H)Y>8000。
When the resin that constitutes above-mentioned pigment carrier (B) satisfies following formula (F), (G) and full terms (H), owing to have good acid value scope, so the resin type spreading agent and the above-mentioned resin that are adsorbed on the pigment can be kept suitable interaction, in addition because good molecular weight ranges, so can moderately bring into play function as the steric hindrance of vector resin, thereby can keep good disperse state, be preferred therefore.Especially, the pigment derivative (b) that uses in the basic resin type spreading agent (a) that uses in following the 1st embodiment of the present invention and/or following the 2nd embodiment of the present invention is adsorbed on the surface of pigments well.On the contrary, when the resin that constitutes above-mentioned pigment carrier (B) does not satisfy the condition of following formula (F), be adsorbed on a little less than the interaction too of above-mentioned basic resin type spreading agent (a) and above-mentioned resin on the surface of pigments, therefore because pigment cohesion etc. former thereby can not keep good disperse state.When not satisfying the condition of following formula (G), above-mentioned interaction is too strong, and the resin type spreading agent that therefore is adsorbed on the pigment is stripped from, and because pigment cohesion etc. former thereby can not keep good disperse state.In addition, when not satisfying the condition of following formula (H), because molecular weight is too little, so above-mentioned resin can not be brought into play the effect as steric hindrance, thereby because the former thereby formation of pigment cohesion etc. disperses bad.In addition, preferred Y≤60000, and then preferred Y≤50000.If Y surpasses 60000, when using as the painted resist of following alkali developable the development condition of poor appears then, and or not preferred therefore.
Thermoplastic resin for example can enumerate butyral resin, styrene-maleic acid copolymer, haloflex, chlorinated polypropylene, Polyvinylchloride, vinyl chloride-vinyl-acetic ester multipolymer, polyvinyl acetate base ester, polyurethane series resin, vibrin, acrylic resin, alkyd resin, polystyrene resin, polyamide, rubber be resin, thermoprene be resin, cellulose family, tygon (HDPE, LDPE), polybutadiene, polyimide resin etc.
In addition, heat-curing resin can be enumerated for example 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, the alkali soluble resins with acidic-group of preferred use (methyl) acrylic copolymer resin (alkaline soluble acrylic resin) etc.In order to disperse the zinc halide phthalocyanine color well, the weight-average molecular weight of alkali soluble resins (Mw) is preferably 10,000～100,000 scope, more preferably 30,000～80,000 scope.Number-average molecular weight (Mn) is preferably 5,000～50,000 scope in addition, and the value of preferred Mw/Mn is below 10.
And in the present invention, the molecular weight distribution of resin [weight-average molecular weight (Mw), number-average molecular weight (Mn)] utilizes GPC to measure with following condition.
Device: GPC-150C (ウ オ--ズ society)
Pillar: GMH-HT30cm 2 connects (eastern ソ-society's system)
Temperature: 135 ℃
Solvent: o-dichlorobenzene (adding 0.1%2,6-di-tert-butyl-4-methy phenol (ア イ オ ノ-Le))
Flow velocity: 1.0ml/min
Sample: the sample that injects 0.4ml 0.15%
Measure with above condition, when the molecular weight of calculation sample, use the molecular weight calibration curve that utilizes the monodisperse polystyrene standard model to make.And then, use the conversion formula of deriving to convert and calculate by tygon by Mark-Houwink viscosity formula.
The active energy ray-curable resin can use following resin; its make 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 and react, form thereby in this wire macromolecule, introduce photocrosslinking reaction groups such as (methyl) acryloyl group or styryl.In addition, can also use following such resin, the wire macromolecule that (methyl) acyclic compound that its utilization (methyl) acrylic acid hydroxyalkyl acrylate etc. has a hydroxyl contains acid anhydrides with styrene-maleic anhydride copolymer or alpha-olefin-copolymer-maleic anhydride etc. carries out half esterization and forms.
Monomer and oligomer as resin precursor for example can be enumerated, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid isopentyl ester, (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, the perhaps straight chain or side chain (methyl) alkyl acrylate of (methyl) acrylic acid iso stearyl ester etc.;
(methyl) acrylic acid cycloalkyl ester class of (methyl) cyclohexyl acrylate, (methyl) acrylic acid tert-butyl group cyclohexyl, (methyl) acrylic acid two ring pentyl esters, (methyl) acrylic acid two cyclopentyloxy ethyl esters, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid two cyclopentene oxygen base ethyl esters or (methyl) isobornyl acrylate etc.;
(methyl) acrylic acid fluoroalkyl ester class of (methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid perfluoro 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 of (methyl) acrylic acid tetrahydro furfuryl ester or (methyl) acrylic acid-3-methyl-3-oxetanyl ester etc. with heterocycle;
(methyl) benzyl acrylate, (methyl) acrylic acid phenoxy ethyl, phenoxy group polyglycol (methyl) acrylate, (methyl) acrylic acid are to the cumyl phenoxy ethyl, to (methyl) esters of acrylic acids with aromatic ring of cumyl phenoxy group polyglycol (methyl) acrylate or Nonylphenoxy polyglycol (methyl) acrylate etc.;
(methyl) acrylic acid-2-methoxyl ethyl ester, (methyl) acrylic acid-2-ethoxy ethyl ester, (methyl) acrylic acid-3-methoxyl butyl ester, (methyl) acrylic acid-2-methoxyl propyl ester, diglycol monotertiary methyl ether (methyl) acrylate, carbiphene (methyl) acrylate, triethylene glycol monomethyl ether (methyl) acrylate, triethylene glycol list ethylether (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, perhaps (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) acryloxy ethyl ester, phthalic acid-2-(methyl) acryloxy propyl ester, hexahydro-phthalic acid-2-(methyl) acryloxy ethyl ester, hexahydro-phthalic acid-2-(methyl) acryloxy propyl ester, oxirane modification succinic acid (methyl) acrylate, (methyl) senecioate-carboxyl ethyl ester, perhaps (methyl) esters of acrylic acid with carboxyl of ω-carboxyl 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-acryloxy ethyl-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, perhaps (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-butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, perhaps 2-ethyl, (gathering) aklylene glycol two (methyl) esters of acrylic acid of 2-butyl propylene glycol two (methyl) acrylate etc.;
Dihydroxymethyl two cyclopentane two (methyl) acrylate, hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylate, stearic acid modified pentaerythrite two (methyl) acrylate, oxirane modified bisphenol A two (methyl) acrylate, epoxy pronane modification bisphenol-A two (methyl) acrylate, tetrahydrofuran modified bisphenol A two (methyl) acrylate, oxirane modified bisphenol F two (methyl) acrylate, epoxy pronane modification Bisphenol F two (methyl) acrylate, tetrahydrofuran modified bisphenol F two (methyl) acrylate, dizinc acrylate resin, oxirane modified phosphate triacrylate, perhaps two (methyl) esters of acrylic acid of glycerine two (methyl) acrylate etc.;
(methyl) esters of acrylic acid of (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid lignocaine ethyl ester, (methyl) acrylic acid dimethylamino propyl ester or (methyl) acrylic acid lignocaine propyl ester etc. with uncle's amino;
Multitube energy (methyl) acrylate that the 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. is above;
Glycerine triglycidyl ether-(methyl) acrylic acid addition product, glycerine diglycidyl ether-(methyl) acrylic acid addition product, polyglycereol polyglycidyl ether-(methyl) acrylic acid addition product, 1,6-butanediol diglycidyl ether-(methyl) acrylic acid addition product, alkyl glycidyl ether-(methyl) acrylic acid addition product, allyl glycidyl ether-(methyl) acrylic acid addition product, phenyl glycidyl ether-(methyl) acrylic acid addition product, styrene oxide-(methyl) acrylic acid addition product, bisphenol A diglycidyl ether-(methyl) acrylic acid addition product, epoxy pronane modification bisphenol A diglycidyl ether-(methyl) acrylic acid addition product, Bisphenol F diglycidyl ether-(methyl) acrylic acid addition product, chloropropylene oxide modification phthalic acid-(methyl) acrylic acid addition product, chloropropylene oxide modification hexahydrophthalic acid-(methyl) acrylic acid addition product, ethylene glycol diglycidylether-(methyl) acrylic acid addition product, polyethyleneglycol diglycidylether-(methyl) acrylic acid addition product, propylene glycol diglycidylether-(methyl) acrylic acid addition product, polyethyleneglycol diglycidylether-(methyl) acrylic acid addition product, phenol novolac-type epoxy resin (Off エ ノ-Le ノ ボ ラ Star Network type エ Port キ シ Trees fat)-(methyl) acrylic acid addition product, cresols novolac-type epoxy resin (Network レ ゾ-Le ノ ボ ラ Star Network type エ Port キ シ Trees fat)-(methyl) acrylic acid addition product, perhaps epoxy (methyl) esters of acrylic acid of other epoxy resin-(methyl) acrylic acid addition product 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-Jia Jibenyixi, vinyl-acetic ester, (methyl) acrylic acid vinyl esters or (methyl) allyl acrylate etc.;
The vinyl ethers of hydroxyethyl vinyl ether, ethylene glycol bisthioglycolate vinyl ether or pentaerythrite trivinyl ether etc.;
The amide-type of (methyl) acrylamide, N-methylol (methyl) acrylamide or N-vinyl formamide etc.; Perhaps
Vinyl cyanide etc.These compounds can use separately, perhaps use mixing more than 2 kinds, but it are not limited to these compounds.
[basic resin type spreading agent (a)]
Green coloring composition of the present invention is characterised in that, the zinc halide phthalocyanine that uses central metal to have zinc is used as the main pigment of pigment composition (A), above-mentioned zinc halide phthalocyanine is compared with the copper halide phthalocyanine color that generally uses 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, the basic resin type spreading agent (a) that has a high like this amine value of 35～100mg KOH/g by use is as the resin type spreading agent that uses when the pigment dispersing, its absorption to acid pigment is become fully, and dispersion can access sufficient flowability.
The number-average molecular weight of the basic resin type spreading agent (a) that the present invention uses is preferably 500～50000 usually, especially, and then preferred 3000～30000.When above-mentioned number-average molecular weight less than 500 the time, the steric repulsion effect that causes by the 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 prevent the cohesion of pigment, the viscosity of dispersion raises.In addition, when number-average molecular weight surpasses 50000, disperse the addition of needed resin to increase, the reduction of the pigment concentration in causing filming.
In the 1st embodiment of the present invention, using amine value is the basic resin type spreading agent (a) of 35～100mg KOH/g.The amine value of basic resin type spreading agent (a) and then be preferably 50～75mgKOH/g.When amine value during less than 35mg KOH/g, can not be adsorbed on fully on the pigment and form disperse bad, when surpassing 100mg KOH/g, because for the absorption or the reaction of the acid ingredient in the pigment carrier, and make adsorption efficiency variation for the zinc halide phthalocyanine color, form disperse bad.
Amine value is that the basic resin type spreading agent (a) of 35～100mg KOH/g can use ethene base system, carbamate system, polyester system, polyethers system or various types of resin system such as polyamide-based, but the preferred resin design is easy, the ethene base system monomer copolymer type of each patience excellence, specifically, preferably contain N, the copolymer resin of the vinyl monomer unit of N-disubstituted amido and (methyl) alkyl acrylate monomer units and other ethene base system monomeric unit.
Contain 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 the high zinc halide phthalocyanine color of acidity as containing the monomeric unit of basic group.
(methyl) alkyl acrylate monomer units can be enumerated (methyl) esters of acrylic acid etc. that the unsaturated monocarboxylic of (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid 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 (methyl) lauryl acrylate etc. and carbon number are 1～18 alkylol reaction gained, but it is not limited to these compounds.These monomeric units play a role as the pigment carrier affinity groups.
Other ethene base system monomeric unit can be enumerated the ethene base system monomer class that (methyl) vinyl cyanide etc. contains itrile group, styrene, α-Jia Jibenyixi, the perhaps ethene base system aromatic monomer class of (methyl) benzyl acrylate etc., (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid hydroxy propyl ester, perhaps polyglycol (methyl) acrylate etc. contains the ethene base system monomer class of hydroxyl, (methyl) acrylamide, N, the N-DMAA, the N-N-isopropylacrylamide, perhaps diacetone acrylamide etc. contains the ethene base system monomer class of amide group, the ethene base system monomer class of N-methylol (methyl) acrylamide or dihydroxymethyl (methyl) acrylamide etc., N-methoxyl methyl (methyl) acrylamide or N-fourth oxygen methyl (methyl) acrylamide etc. contain the ethene base system monomer class of alkoxyl-methyl, ethene, propylene, the perhaps 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, the perhaps vinyl ethers of IVE etc., the fatty acid vinyl ester class of vinyl-acetic ester or vinyl propionate base ester etc. etc., can suitably use above-claimed cpd according to purpose, but be not limited to these compounds.
Can also enumerate and to have allylamine etc. with vibrin, acryl resin or polyether resin etc. and contain the polymkeric substance of monomeric unit of primary amino radical or the comb shape basic resin type spreading agent that modifications such as polyethyleneimine, polyethylene polyamine, poly-(hydroxyl propylene) 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 form.
The commercially available product of this basic resin type spreading agent can be enumerated for example BYK-161,163,164,167,174,184,2000,2050 of PVC ッ Network ケ ミ-ジ ヤ パ Application society, the SOLSPERSE-34750,56000 of perhaps Japanese Le-Block リ ゾ-Le society, the EFKA4300,4330,4046,4060 of チ バ ジ ヤ パ Application society, 4080 etc.
As the basic resin type spreading agent (a) of color filter of the present invention, especially preferably comprise the block copolymer resin of alkaline copolymer block (a1) and pigment carrier compatibility copolymer block (a2) with green coloring composition.Below, describe for basic resin type spreading agent.
(basic resin type spreading agent)
Color filter of the present invention have the position (being designated hereinafter simply as the adsorption section) that is adsorbed on the pigment with the basic resin type spreading agent of green coloring composition and bring the cohesion that prevents between the pigment, improve dispersed effect, for the high position of the compatibility of pigment carrier (being designated hereinafter simply as compatibility portion).The zinc halide phthalocyanine is because the acidity height, so when compatibility portion and adsorption section random arrangement, the absorption of pigment is become not enough, it is bad to form dispersion.In the 1st embodiment of the present invention, by following block copolymer resin is used as resin type spreading agent (a), but the green coloring composition that does not damage its look characteristic, fine and low viscosity and stable dispersion for the zinc halide phthalocyanine color can be provided, and described block copolymer resin is as separately existing on a part for the alkaline copolymer block (a1) of the adsorption section of zinc halide phthalocyanine color with as the pigment carrier compatibility copolymer block (a2) for the compatibility portion of pigment carrier.
The alkaline copolymer block (a1) and the pigment carrier compatibility copolymer block (a2) that constitute block copolymer resin can be selected various resin system respectively, and preferred resin designs easily and the vinyl based copolymer of each patience excellence.
Below each copolymer block is described.
＜alkaline copolymer block (a1) 〉
The object lesson of alkalescence copolymer block (a1) can be enumerated has (methyl) acrylic acid-N, the N-dimethylaminoethyl, (methyl) acrylic acid-N, the 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, perhaps N, N-diethyllaminoethyl (methyl) acrylamide etc. contains N, the multipolymer of the ethene base system monomeric unit of N-disubstituted amido, have allylamine etc. and contain the polymkeric substance of the monomeric unit of primary amino radical, perhaps polyethyleneimine, polyethylene polyamine, Parylene gathers (hydroxyl propylene) polyamine, perhaps gather (aminomethylation) epoxy resin etc., but it is not limited to these compounds.
Wherein, the resin design of special preferred block copolymer easily and each patience excellence, have a N of containing, the multipolymer of the ethene base system monomeric unit of N-disubstituted amido, what contained this moment in alkaline copolymer block (a1) contains N, the ethene base system monomeric unit of N-disubstituted amido is preferably 60～100 weight %, and then preferred 80～100 weight %, contain N as removing, ethene base system monomeric unit beyond the ethene base system monomeric unit of N-disubstituted amido, preferably the ethene base system monomeric unit of explanation in pigment carrier compatibility copolymer block (a2).
＜pigment carrier compatibility copolymer block (a2) 〉
Pigment carrier compatibility copolymer block (a2) be segmented copolymer resin design easily and the ethene base system monomer copolymer of each patience excellence, and then ethene base system monomeric unit preferably contains (methyl) alkyl acrylate, especially in pigment carrier compatibility copolymer block (a2), preferably contain 60～100 weight %, and then preferred 80～100 weight %.(methyl) alkyl acrylate for example can be enumerated (methyl) esters of acrylic acid etc. that the unsaturated monocarboxylic of (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid 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 (methyl) lauryl acrylate etc. and carbon number are 1～18 alkylol reaction gained, but it is not limited to these compounds.
In pigment carrier compatibility copolymer block (a2), contain amino ethene base system monomeric unit and be preferably 0 weight %, but also can contain amount less than 10 weight %.
As other ethene base system monomeric unit that also can in alkaline copolymer block (a1) and pigment carrier compatibility copolymer block (a2), contain, can enumerate the ethene base system monomer class that (methyl) vinyl cyanide etc. for example contains itrile group, styrene, α-Jia Jibenyixi, the perhaps ethene base system aromatic monomer class of (methyl) benzyl acrylate etc., (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid hydroxy propyl ester, perhaps polyglycol (methyl) acrylate etc. contains the ethene base system monomer class of hydroxyl, (methyl) acrylamide, N, the N-DMAA, the N-N-isopropylacrylamide, perhaps diacetone acrylamide etc. contains the ethene base system monomer class of amide group, the ethene base system monomer class of N-methylol (methyl) acrylamide or dihydroxymethyl (methyl) acrylamide etc., N-methoxyl methyl (methyl) acrylamide or N-fourth oxygen methyl (methyl) acrylamide etc. contain the ethene base system monomer class of alkoxyl-methyl, ethene, propylene, the perhaps 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 of vinyl-acetic ester or vinyl propionate base ester etc. etc., but it is not limited to these compounds.
＜block copolymer resin 〉
The above-mentioned resin type spreading agent (a) that uses in the 1st embodiment of the present invention can use known method to prepare, especially, preferably (1) uses the method for living polymerization, and perhaps (2) make the polymkeric substance coupling method of the precursor (a11) of the alkaline copolymer block (a1) that has functional group endways and precursor (a21) reaction of the pigment carrier compatibility copolymer block (a2) that has functional group endways.Wherein, preferred especially (1) uses the method for living polymerization.
(1) living polymerization method
The living polymerization method can be suppressed at the subsidiary reaction that takes place in the general free radical polymerization, and then owing to can carry out the growth of polymerization equably, so the resin of block polymer synthesis or molecular weight unanimity easily.Wherein, consider from the monomer that goes for wide region and the angle that can adopt the polymerization temperature that can be suitable for existing equipment, preferably with organohalogen compounds or sulfonyl halogen compound as initiating agent, with the atom freedom of movement base polymerization of transition metal complex compound as catalyzer.Atom freedom of movement base polymerization can use the method for recording and narrating in following list of references 1～8 grade to 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) Macromolecules 1995,28,7901, Science, 1996,272,866
(list of references 5) international pamphlet that discloses No. 96/30421
(list of references 6) international pamphlet that discloses No. 97/18247
(list of references 7) spy opens flat 9-208616 communique
(list of references 8) spy opens flat 8-41117 communique
In atom freedom of movement base polymerization, use the transition metal complex compound of copper, ruthenium, iron or nickel etc. to carry out as redox catalyst.The object lesson of transition metal complex compound can be enumerated the halogenation transition metal of cupric chloride (I) or copper bromide low atomicitys such as (I), but, also can in polymerization system, add the transition metal of cupric chloride (II) or the contour atomicity of copper bromide (II) according to known method in order to control polymerization speed.
In above-mentioned metal complex, can use organic ligand.In order to have, and use organic ligand for the solubility of polymer solvent and the reversible variation of redox conjugation coordination compound.The coordination atom of metal can be used nitrogen-atoms, oxygen atom, phosphorus atoms or sulphur atom etc., preferred nitrogen atom or phosphorus atoms.The object lesson of organic ligand can be enumerated sparteine or 2,2 '-bipyridine and derivant, 1 thereof, 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, copper halide and butanediamine be used in combination carry out polymerization, this angle from the control of polymerization speed, block molecular resin amount considers it is preferred.
Above-mentioned transition metal and organic coordination compounds can add respectively and generate metal complex in polymkeric substance, also can synthesize metal complex in advance and add in the polymerization system.Especially, when the transition metal is copper, preferred the former method, when the transition metal is ruthenium, iron or nickel, the preferred latter's method.The object lesson of He Cheng ruthenium, iron or nickel coordination compound can be enumerated three (triphenylphosphine) ruthenous chloride (Ru (Cl) in advance 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 that uses in atom freedom of movement base polymerization can use known compound, mainly can use the organohalogen compounds with reactive high carbon-halogen bond, perhaps sulfonyl halogen compound etc.Specifically can enumerate isobutyl ethyl bromide, bromo ethyl butyrate, chloro ethyl isobutyrate, chloro ethyl butyrate, paratoluensulfonyl chloride, bromo ethyl phenenyl or chloroethyl benzene etc.These compounds can use separately or and use.
In the polymerization of above-mentioned atom freedom of movement base, the initiating agent of atom freedom of movement base polymerization can suitably be selected according to the molecular weight of synthetic resin, with respect to the free radical polymerization monomer total amount, preferably with 0.001～10 mole of %, more preferably the ratio of 0.01～1 mole of % is used.In addition, the use amount of transition metal, as the form of halogenide etc., with respect to 1 mole of initiating agent, preferably with 0.03～3 mole, more preferably 0.1～2 mole ratio is used.And then its part is with respect to 1 mole of above-mentioned transition metal (forms of halogenide etc.), uses with 1～5 mole, preferred 1.2～3 moles ratio usually.When initiating agent, transition metal and the part of the polymerization of above-mentioned atom freedom of movement base use with such ratio, be preferred at the reactivity of active free radical polymerization, the aspects such as molecular weight of generation polymkeric substance.
In addition, on the characteristic of atom freedom of movement base polymerization, have acticarbon-halogen bond, can functional group be introduced in its modification with known method at the termination end of gained resin.In addition, can utilize polymerization initiator to carry out polymerization, introduce functional group and be used for various reactions at the resin end with functional group.
Even the polymerization of atom freedom of movement base also can be carried out under solvent-free state, perhaps also can under the state that has butyl acetate, toluene, dimethylbenzene, anisole, methyl ethyl ketone or cyclohexanone equal solvent, carry out.Consider preferred ketone series solvent, special preferable methyl ethyl ketone especially from the angle of polymerization speed.When using solvent, in order to prevent the reduction of polymerization speed, preferably its use amount is that to make the solvent strength after polymerization finishes be the following amounts of 50 weight %.Even for situation solvent-free or a small amount of solvent amount, do not have especially the relevant safety issues such as control with heat of polymerization yet, thereby reduce solvent, also be preferred at aspects such as economy or environmental cures thus.
As polymerizing condition, consider from the angle of the inactivation of polymerization speed or catalyzer, carry out with 60～130 ℃ polymerization temperatures, though polymerization time also depends on final molecular weight or polymerization temperature, as long as in about 1～100 hour scope.In addition, when polyreaction, the inactivation for the polymerization catalyst that prevents to be caused by oxygen preferably carries out under the atmosphere of inert gases of nitrogen or argon etc.
In addition, after polyreaction finishes, with polymerization reaction system be cooled to preferred below 0 ℃, more preferably-78 ℃ about, and make reaction terminating, according to known method, can carry out the removing of residual monomer and/or solvent, the washing and the drying of the filtration of precipitation polymers, polymkeric substance are carried out in the centrifuging that precipitates, utilizes in appropriate solvent.After utilizing known method to remove to contain in the polymerization system transition metal etc.,, can obtain the block resin that the present invention uses as required by making the volatile ingredient evaporation.The organic solvent diluting reaction mixture of the useful tetrahydrofuran of the method for removing, toluene or methyl ethyl ketone etc. and washings such as water watery hydrochloric acid or ammonia spirit, the method that resin solution is contacted with Zeo-karb or huge legendary turtle resin, the method of passing through in the pillar of aluminium oxide silicon dioxide or clay or filler (パ Star De) is added the method that filters centrifuging behind the adsorbent of reductive agent or hydrotalcite etc. etc.Consider from the angle of the simplicity handled, preferably in dilute resin solution, add the sour adsorbent etc. of Zeo-karb and hydrotalcite etc. and stir, ion exchange resin and sour adsorbent are filtered obtain resin solution.
When in resin solution, sneaking into moisture by refinement treatment, the situation that hinders the block resin that uses among the present invention and hardening agent reaction is arranged, preferably the solvent that mixes with water by interpolation in resin solution and carry out the processing of azeotropic dehydration etc. and moisture is removed from resin solution.
For the atom freedom of movement base polymerization of using among the present invention, owing to can be suppressed at the subsidiary reaction that takes place in the general free radical polymerization, thereby the initiating agent of the atom freedom of movement base polymerization of adding when utilizing polymerization and the ratio of packing into of free radical polymerization monomer can freely be controlled the ratio of molecular weight or the alkaline copolymer block (a1) or the pigment carrier compatibility copolymer block (a2) of resin.
(2) polymkeric substance coupling method
As the functional group of the end of the precursor (a21) of the precursor (a11) of the alkaline copolymer block (a1) of polymkeric substance coupling method and 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 precursor (a11) that functional end-group is incorporated into alkaline copolymer block (a1) and pigment carrier compatibility copolymer block (a2), the preferred chain-transferring agent that has the above-mentioned functional group of enumerating and have sulfydryl, the method for carrying out free radical polymerization used.Chain-transferring agent with carboxyl can be enumerated mercaptopropionic acid, chain-transferring agent with primary amino radical can be enumerated cysteamine, chain-transferring agent with hydroxyl can be enumerated mercaptoethanol, and the chain-transferring agent with alkoxysilyl can be enumerated 3-sulfydryl propyl group methyl methoxy base silane or 3-sulfydryl propyl trimethoxy silicane.
Precursor (a11) for example can be the known reactions of carrying out with the combination of following table 1 with the reaction of precursor (a21).
[table 1]
Precursor (a11) terminal groups Precursor (a21) terminal groups Bond Reaction
Hydroxyl Hydroxyl Polyisocyanate compound Addition polymerization
Amino Amino The polyisocyanate compound polyepoxides Addition polymerization
Carboxyl Carboxyl Polyepoxides Addition polymerization
The hydroxyl primary amino radical Carboxyl Dehydrating condensation
Carboxyl The hydroxyl primary amino radical Dehydrating condensation
Alkoxysilyl Alkoxysilyl (water) Hydrolysis and dealcoholysis condensation
The polyisocyanate compound of bond can be enumerated aromatic polyisocyanate, aliphatic polyisocyante, aromatic-aliphatic polyisocyanates or alicyclic polyisocyanates etc.Aromatic polyisocyanate for example can enumerate 1,3-phenylene diisocyanate, 4,4 '-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, 2,4-benzal diisocyanate, 2,6-benzal 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 triisocyanate etc.Aliphatic polyisocyante can be enumerated for example trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, two isocyanic acid pentylidene esters, two isocyanic acids-1, the inferior propyl ester of 2-, two isocyanic acids-2,3-Aden ester, two isocyanic acids-1,3-Aden ester, two isocyanic acids, 12 methylene esters or two isocyanic acids-2,4, the inferior own ester of 4-trimethyl etc.The aromatic-aliphatic polyisocyanates can be enumerated for example ω, ω '-diisocyanate-1,3-dimethyl benzene, ω, ω '-diisocyanate-1,4-dimethyl benzene, ω, ω '-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylene diisocyanate or 1,3-tetramethylxylene diisocyanate etc.Alicyclic polyisocyanates can be enumerated for example 3-isocyanatomethyl (イ ソ シ ア ネ-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-two (isocyanatomethyl) cyclohexane or 1,4-two (isocyanatomethyl) cyclohexane etc., but be not limited to these compounds.In addition, the biuret thing that also can and react with the trimethylolpropane adduct of a part of above-mentioned polyisocyanates, with water, have the tripolymer of isocyanurate ring etc.
The polyepoxides of bond preferably has the polyepoxides of at least 2 glycidyls.Specifically, can enumerate ethylene glycol diglycidylether, propylene glycol diglycidylether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, the trimethylolethane trimethacrylate glycidol ether, sorbitol polyglycidylether, the perhaps aliphatic poly epoxy compound of pentaerythrite polyglycidyl ether etc., the aromatics polyepoxides of bisphenol-A or Bisphenol F type, the four glycidyl group aminophenyl methane, triglycidyl isocyanurate, perhaps 1,3-two (N, N-glycidyl-amino methyl) the glycidyl group 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 that uses in the 1st embodiment of the present invention is preferably 500～50000 usually, and then preferred 3000～30000.But above-mentioned number-average molecular weight was less than 500 o'clock, the steric repulsion effect that causes 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 prevent the cohesion of pigment, the viscosity of dispersion raises.In addition, when number-average molecular weight surpasses 50000, disperse the addition of needed resin to increase, the reduction of the pigment concentration in causing filming.
In addition, the amine value of the segmented copolymer type basic resin type spreading agent that uses in the 1st embodiment of the present invention is 35～100mg KOH/g, and then preferred 50～75mg KOH/g.When amine value during less than 35mg KOH/g, can not be adsorbed on fully on the pigment and form disperse bad, when surpassing 100mg KOH/g, because for the absorption or the reaction of the acid ingredient in the pigment carrier, and make adsorption efficiency variation for pigment, form disperse bad.
The formation part by weight of alkalescence copolymer block (a1) or pigment carrier compatibility copolymer block (a2) and separately the number-average molecular weight of block preferably can at random design so that the number-average molecular weight of resin type spreading agent integral body and amine value are in above-mentioned preferred range.
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 weight %, and then preferred 0.1～30 weight %, most preferably 0.5～25 weight %.If the use level of the resin type spreading agent (a) when being benchmark with the general assembly (TW) of pigment composition (A) then has the situation of dispersed variation less than 0.001 weight %,, the situation of thermotolerance, photostability variation is arranged then if surpass 40 weight %.
[pigment derivative (b)] with alkali subtituent
Green coloring composition of the present invention is characterised in that, the zinc halide phthalocyanine that uses central metal to have zinc is used as the main pigment of pigment composition (A), above-mentioned zinc halide phthalocyanine is compared with the copper halide phthalocyanine color that generally uses 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, become fully for the absorption of acid pigment, this pigment dispersion can be found sufficient flowability and color characteristics.In the 2nd embodiment of the present invention, the pigment derivative (b) that has alkali subtituent by use can obtain preferred pigment dispersion as spreading agent.
As mentioned above, in the 2nd embodiment of color composition for color filter of the present invention,, can use pigment derivative (b) for the purpose of improving dispersing of pigments.Pigment derivative can be set forth in to be introduced alkali subtituent, acid substituting group or also can have the compound that substituent phthalimide methyl forms in organic pigment, anthraquinone, acridone or the triazine.
In the present invention, wherein preferred especially alkaline derivant, alkaline derivant is the compound shown in following general formula (1), and it is the derivant with specific precursor skeleton, and described specific precursor skeleton has basic group.Get final product so long as have the pigment derivative of basic group, do not limit especially, the preferred pigment derivative that uses with triazine ring skeleton, described triazine ring skeleton has the basic group shown in following general formula (4).
General formula (1):
P-Lm
(wherein, in the general formula (1),
P is organic pigment residue, anthraquinone skeleton, acridone skeleton, triazine skeleton of m valency etc.,
M is 1～4 integer,
L is for being selected from the substituting group in the group shown in general formula (2), (3) and (4).)
General formula (2):
Figure A200810182161D00281
General formula (3):
Figure A200810182161D00291
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 1～10 integer,
Y 1Be-NH-,-NR 58-Z-NR 59-or Direct Bonding,
R 58And R 59Represent hydrogen atom respectively independently, also can have that substituent carbon number is 1～36 alkyl, also can to have substituent carbon number be 2～36 thiazolinyl or also can have substituent phenyl,
Z represents also can have substituent alkylidene or also can have substituent arlydene,
R 50, R 51Representing hydrogen atom respectively independently, also can have substituent carbon number to be 1～30 alkyl, also can having substituent carbon number is 2～30 thiazolinyl or R 50With R 51What form one and then contain nitrogen, oxygen or sulphur atom also can have substituent heterocycle.
R 52, R 53, R 54And R 55Representing hydrogen atom respectively independently, also can have substituent carbon number to be 1～20 alkyl, also can have substituent carbon number to be 2～20 thiazolinyl, also can having substituent carbon number is 6～20 arlydene,
R 56Be hydrogen atom, also can to have substituent carbon number be 1～20 alkyl, also can have substituent carbon number is 2～20 thiazolinyl,
R 57Be substituting group or the substituting group shown in general formula (3) shown in general formula (2),
Q is hydroxyl, alkoxy, the substituting group shown in above-mentioned general formula (2) or the substituting group shown in above-mentioned general formula (3).〕
The substituent amine component that is used to form shown in general formula (2)～(4) can be enumerated for example dimethylamine, diethylamine, methyl ethyl-amine, N, N-ethyl isopropylamine, N, N-ethyl propylamine, N, the N-methylbutylamine, N, N-methyl isobutyl 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, the 2-dimethyl propylamine, N, the N-tuaminoheptane, two oil base amine, distearyl amine, N, N-dimethylamino methylamine, N, N-dimethylamino ethamine, N, N-dimethylamino amylamine, N, N-dimethylamino butylamine, N, N-diethylamino ethamine, N, the N-diethyl amino propylamine, N, N-diethylamino hexylamine, N, N-diethylamino butylamine, N, N-diethylamino amylamine, N, the amino butylamine of N-dipropyl, N, the N-dibutyl amino propyl amine, N, N-dibutylamino ethamine, N, N-dibutylamino butylamine, N, the amino amylamine of N-diisobutyl, N, the amino propylamine of N-methyl-lauryl, N, N-ethyl-hexyl aminoethyl, N, N-distearyl aminoethyl, N, N-two oil base aminoethyl, N, the amino butylamine of N-distearyl, piperidines, pipecoline, the 3-methyl piperidine, the 4-methyl piperidine, 2, the 4-lupetidine, 2, the 6-lupetidine, 3, the 5-lupetidine, the 3-piperidine carbinols, nipecotic acid, isonipecotic acid, the isonipecotic acid methyl esters, ethyl isonipecotate, 2-piperidines ethanol, pyrrolidine, the 3-hydroxyl pyrrolidine, N-amino-ethyl piperidines, N-amino-ethyl-4-methyl piperidine, N-amino-ethyl morpholine, N-aminopropyl piperidines, N-aminopropyl-pipecoline, N-aminopropyl-4-methyl piperidine, N-aminopropyl morpholine, N methyl piperazine, N-butyl piperazine, the high piperidines of N-methyl, the 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 uses in the 2nd embodiment of the present invention can synthesize with various synthetic routes.For example can be by in organic pigment, anthraquinone or acridone, introducing suc as formula behind the substituting group shown in (5)～(8), the substituent above-mentioned amine component that can form with above-mentioned substitution reaction shown in general formula (2)～(4) is reacted to be obtained, described amine component for example has N, N-dimethylamino propylamine, N methyl piperazine, diethylamine or 4-[4-hydroxyl-6-[3-(dibutylamino) propyl group amino]-1,3,5-triazine-2-amino] aniline etc.
Formula (5) :-SO 2Cl
Formula (6) :-COCl
Formula (7) :-CH 2NHCOCH 2Cl
Formula (8) :-CH 2Cl
When the substituting group of formula (5)～(8) and the reaction of above-mentioned amine component, substituent a part of hydrolysis of formula (5)～(8), thus also can mix the material that exists chlorine to be replaced to hydroxyl.At this moment, formula (5) and formula (6) become sulfonic group and carboxylic acid group respectively, and they can keep the state of free acid, perhaps also can be and the metal of 1～3 valency or the salt of above-mentioned monoamine formation.
In addition,, the substituting group shown in general formula (2)～(4) is incorporated in diazonium composition or the coupling composition in advance, carries out coupling reaction afterwards, also can make the azo pigment derivant thus when organic pigment is an azo when being pigment.
The pyrrolotriazine derivatives with basic group that uses in the 2nd embodiment of the present invention can synthesize with various synthetic routes.It for example is initiation material with the cyanuric chloride, form substituent amine component, for example N shown in general formula (2)～(4) by making, at least 1 chlorine reaction of N-dimethylaminopropylamine or N methyl piperazine etc. and cyanuric chloride then makes remaining chlorine of cyanuric chloride and various amine or alcohol etc. react and obtains.
In color compositions of the present invention, the use level of pigment derivative with alkali subtituent is preferably 1～50 weight portion with respect to pigment composition (A) 100 weight portions, and then preferred 3～30 weight portions, most preferably 5～25 weight portions.When with respect to pigment 100 weight portions, alkaline derivant has the situation of dispersed variation during less than 1 weight portion, when surpassing 50 weight portions, the situation of thermotolerance, photostability variation is arranged.The compound that wherein has triazine structure in alkali subtituent is preferred aspect dispersion stabilization.
[organic solvent (c)]
In the 3rd embodiment of green coloring composition of the present invention, for pigment composition (A) is dispersed in the pigment carrier (B) fully, and on the substrate of glass substrate etc., be that the mode of 0.2～5 μ m is coated with and forms the color filter joint with dry film thickness easily, and contain organic solvent (c).
It is 8.0～10.0 (cal/cm that organic solvent (c) use contains solubility parameters (SP value) 3) 1/2, and 760mmHg under boiling point be 140～159 ℃ organic solvent (c1); And solubility parameters (SP value) is 8.0～10.0 (cal/cm 3) 1/2, and 760mmHg under boiling point be the mixed organic solvents of 160～200 ℃ organic solvent (c2).
In this manual, solubility parameters (SP value) is meant the value of being tried to achieve by the physical quantity (heat of evaporation etc.) of organic solvent, and it is the value of putting down in writing in various documents.
More preferably organic solvent (c) is that to contain solubility parameters (SP value) be 8.0～10.0 (cal/cm 3) 1/2, and 760mmHg under boiling point be 144～157 ℃ organic solvent (c1); And solubility parameters (SP value) is 8.0～10.0 (cal/cm 3) 1/2, and 760mmHg under boiling point be the mixed organic solvents of 164～192 ℃ organic solvent (c2).
Here, organic solvent (c1) preferably for example is selected from the solvent more than a kind of propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, in addition, organic solvent (c2) preferably for example is selected from the solvent more than a kind of cyclohexyl acetate, propylene-glycol diacetate, diethylene glycol diethyl ether and 3-ethoxyl ethyl propionate.And cyclohexyl acetate also is called adnoral acetate.
The color filter of the 3rd embodiment of the present invention has the solubility parameters (SP value) of particular range and the organic solvent (c1) and the organic solvent (c2) of boiling point with green coloring composition owing to cooperating with special ratios, so have high contrast ratio and high lightness.In addition, for being coated with filming of this coloured composition, thickness is uneven and strip is uneven reduces, and uniform film thickness has excellent performance.
When solubility parameter (SP value) than 8.0 (cal/cm 3) 1/2Hour, the dispersion variation of zinc halide phthalocyanine color is when than 10.0 (cal/cm 3) 1/2When big, the zinc halide phthalocyanine color dissolves in organic solvent, produces the reduction of lightness and contrast ratio.
When the boiling point of the solvent that uses as organic solvent (c1) than 140 ℃ hours, generation thickness inequality or strip inequality never are preferred.In addition, when the boiling point of the solvent that uses as organic solvent (c2) was big than 200 ℃, residual had a cohesive ( ッ Network), from rather than preferably.
When being benchmark with the total amount of above-mentioned pigment composition (A), mixed organic solvents (c) can use the amount of 800～4,000 weight %.For the cooperation of mixed organic solvents (c), preferred organic solvent (c1) is 50～95 weight % in its total amount in addition, and organic solvent (c2) is 5～50 weight %.More preferably organic solvent (c1) is 65～95 weight %, and organic solvent (c2) is 5～35 weight %.If the ratio of organic solvent (c1) exceeds 50～95% scope, then coating fluid has the problem that produces thickness inequality or strip inequality.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.
In addition as mentioned above, the organic solvent (c1) that when disperseing the zinc halide phthalocyanine color, uses and be coated with the organic solvent (c2) that color filter of the present invention adds with the unfavorable condition in the filming of green coloring composition and be not limited to specific solvent in order to improve, in order easily to make coloured composition form the color filter joint, can add following organic solvent as secondary solvent.
Can use 1,2, the 3-trichloropropane, 1,3-butanediol (1,3-Block Application ジ オ-Le), 1,3-butylene glycol (1,3-Block チ レ Application グ リ コ-Le), 1,3-butylene glycol diacetate esters, 1, the 4-diox, the 2-heptanone, the 2-methyl isophthalic acid, ammediol, 3,5,5-trimethyl-2-cyclohexane-1-ketone, 3,3, the 5-trimethylcyclohexanone, the 3-methyl isophthalic acid, the 3-butanediol, 3-methoxyl-3-methyl isophthalic acid-butanols, 3-methoxyl-3-methyl butyl acetic acid esters, the 3-methoxybutanol, 3-methoxyl butylacetic acid ester, the 4-heptanone, m-xylene, between diethylbenzene, m-dichlorobenzene, N, the N-dimethyl acetamide, N, dinethylformamide, normal butyl alcohol, n-butylbenzene, n-propyl acetate, N-Methyl pyrrolidone, o-xylene, ortho-chlorotolu'ene, adjacent diethylbenzene, o-dichlorobenzene, parachlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl benzene, the Y-butyrolactone, isobutyl alcohol, isophorone, the ethylene glycol bisthioglycolate ethylether, the ethylene glycol bisthioglycolate butyl ether, the glycol monomethyl isopropyl ether, ethylene glycol monomethyl ether, the glycol monomethyl tertbutyl ether, ethylene glycol monobutyl ether, the ethylene glycol monobutyl ether acetic acid esters, the glycol monomethyl propyl ether, ethylene glycol mono hexyl ether, the glycol monomethyl methyl ether, diisobutyl ketone, diethylene glycol dimethyl ether, the diglycol monotertiary isopropyl ether, diethylene glycol monoethyl ether acetate, the diglycol monotertiary butyl ether, diglycol monotertiary butyl ether acetic acid esters, the diglycol monotertiary methyl ether, cyclohexanol, cyclohexanone, the dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetic acid esters, dipropylene glycol list ethylether, the dipropylene glycol single-butyl ether, dipropylene glycol list propyl ether, the dipropylene glycol monomethyl ether, diacetone alcohol, glycerol triacetate, the tripropylene glycol single-butyl ether, the tripropylene glycol monomethyl ether, propylene glycol phenyl ether, propylene glycol list ethylether, the propylene glycol single-butyl ether, propylene glycol list propyl ether, propylene glycol monomethyl ether, the propylene glycol monomethyl ether propionic ester, benzylalcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, perhaps dibasic acid ester etc.
In order to obtain the preferred green coloring composition of the present invention, in whole mixed organic solvents (c), preferably organic solvent (c1) and organic solvent (c2) adds up to more than the 70 weight %.More preferably it adds up to 80 weight % in addition.Especially preferably add up to more than the 85 weight %.When organic solvent (c1) and organic solvent (c2) secondary solvent were in addition added in a large number, the coating of filming of giving the stability of zinc halide phthalocyanine color dispersion and being coated with this coloured composition brought bad influence, from rather than 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., will contain the pigment composition (A) of zinc halide phthalocyanine color at least, be dispersed in imperceptibly in the above-mentioned pigment carrier (B) with above-mentioned basic resin type spreading agent (a) or above-mentioned basic resin type spreading agent (a) and above-mentioned pigment derivative (b) with alkali subtituent and be prepared.In addition, green coloring composition of the present invention also can mix the material that disperses several pigment to form respectively and prepares in pigment carrier (B).
Green coloring composition of the present invention can and then add Photoepolymerizationinitiater initiater etc., modulates with the form of solvent develop type or the green resist of alkali developable.When modulating, in the part of pigment carrier, use alkali-soluble material with acidic-group with the form of the painted resist of alkali developable.
[Photoepolymerizationinitiater initiater]
For color filter green coloring composition of the present invention, utilizing the ultraviolet ray irradiation that said composition is solidified, when perhaps utilizing photoetching process to form the color filter joint, can add Photoepolymerizationinitiater initiater etc.Use level when using Photoepolymerizationinitiater initiater is considered from the angle of photo-curable, development, more preferably 10～150 weight % during as benchmark, being preferably 5～200 weight % with the general assembly (TW) of pigment composition (A).
Photoepolymerizationinitiater initiater can use 4-phenoxy group dichloroacetophenone; 4-tert-butyl group dichloroacetophenone; diethoxy acetophenone; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone; the 1-hydroxycyclohexylphenylketone; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone; perhaps the acetophenone of 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone etc. is a Photoepolymerizationinitiater initiater; benzoin; benzoin methyl ether; the benzoin ethylether; the benzoin isopropyl ether; perhaps the benzoin of benzyl dimethyl ketal etc. is a Photoepolymerizationinitiater initiater; benzophenone; benzoylbenzoic acid; the benzoylbenzoic acid methyl esters; the 4-phenyl benzophenone; dihydroxy benaophenonel; the acryloyl group benzophenone; perhaps 4-benzoyl-4 '-benzophenone of methyldiphenyl base sulfide etc. is a Photoepolymerizationinitiater initiater; thioxanthones; the 2-clopenthixal ketone; 2-methyl thioxanthones; isopropyl thioxanthone; perhaps 2; the thioxanthones of 4-diisopropyl thioxanthones etc. is a Photoepolymerizationinitiater initiater; 2; 4; 6-three chloro-s-triazines; 2-phenyl-4; 6-two (trichloromethyl)-s-triazine; 2-(p-methoxyphenyl)-4; 6-two (trichloromethyl)-s-triazine; 2-(p-methylphenyl)-4; 6-two (trichloromethyl)-s-triazine; 2-piperonyl-4; 6-two (trichloromethyl)-s-triazine; 2; 4-two (trichloromethyl)-6-styryl-s-triazine; 2-(naphthalene-1-yl)-4; 6-two (trichloromethyl)-s-triazine; 2-(4-methoxyl-naphthalene-1-yl)-4; 6-two (trichloromethyl)-s-triazine; 2; 4-trichloromethyl-(piperonyl)-6-triazine; perhaps 2; the triazine of 4-trichloromethyl (4 '-methoxyl-styrene)-6-triazine etc. is a Photoepolymerizationinitiater initiater; (ボ レ-ト) is a Photoepolymerizationinitiater initiater to borate; carbazole is a Photoepolymerizationinitiater initiater; perhaps imidazoles is a Photoepolymerizationinitiater initiater etc., but it is not limited to these compounds.
Above-mentioned Photoepolymerizationinitiater initiater can be used alone or two or more kinds mixed; can also be as sensitizer; and with for example 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-キ ノ Application), EAQ, 4; 4 '-diethyl between phenyl-diformyl base benzene, 3; 3 '; 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone or 4; 4 '-compound of diethylamino benzophenone etc., but it is not limited to these compounds.
During as benchmark, the use level when using sensitizer is preferably 3～60 weight %, considers from the angle of photo-curable, development, more preferably 5～50 weight % with the cooperation weight of the Photoepolymerizationinitiater initiater that contains in coloured composition.
[dispersing aid]
Pigment dispersing in pigment carrier (B) time, can suitably used the dispersing aid of other resin type pigment dispersing agent different with above-mentioned basic resin type spreading agent (a) or surfactant etc.Dispersing aid makes the dispersing of pigments excellence, has the effect of cohesion again that bigger preventing disperses back pigment, therefore, when using following green coloring composition, can obtain the high color filter of spectral transmission, described green coloring composition uses dispersing aid that pigment dispersing is formed in pigment carrier (B).
Other resin type pigment dispersing agent different with above-mentioned basic resin type spreading agent (a) also has pigment compatibility position and with pigment carrier the position of compatibility arranged, described pigment compatibility position has the character that is adsorbed on the pigment, and this dispersant adsorption is on the pigment and performance makes the function of the decentralized stabilization of pigment in pigment carrier (B).As the resin type pigment dispersing agent, other known resin type pigment dispersing agents different with above-mentioned basic resin type spreading agent (a) specifically, can use polyurethane, the perhaps polycarboxylate of polyacrylate etc., the unsaturated polyester acid amides, poly carboxylic acid, poly carboxylic acid (part) amine salt, the poly carboxylic acid ammonium salt, the poly carboxylic acid alkylamine salt, polysiloxane, the long-chain polyaminoamide phosphate, the polycarboxylate that contains hydroxyl, or their modifier, the oiliness spreading agent of the acid amides that utilizes poly-(rudimentary alkyleneimines) and polyester to react and form or its salt etc. with free carboxy, (methyl) acrylic acid-styrol copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol (PVA), the perhaps water soluble resin or the water-soluble high-molecular compound of polyvinylpyrrolidone etc., polyester system, modified polyacrylate system, the ethylene oxide/propylene oxide additive compound, perhaps phosphate system etc., these compounds can use separately, perhaps use mixing more than 2 kinds.
Surfactant can be enumerated the anionic surfactant of monoethanolamine, polyoxyethylene alkyl ether phosphate of alkali metal salt, odium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl base ether sodium disulfonate, lauryl sulfate monoethanolamine, triethanolamine lauryl sulfate, Texapon Special, stearic acid monoethanolamine, the styrene-propene acid copolymer of NaLS, polyoxyethylene alkyl ether sulfate salt, neopelex, styrene-propene acid copolymer etc.; The nonionic surfactant of polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylplenyl 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 of alkyl dimethyl aminoacetic acid betaine etc., alkyl imidazoline etc., these compounds can be used alone or two or more kinds mixed, but are not limited to these compounds.
And then, use in the green coloring composition at color filter of the present invention, for pigment being dispersed in fully in the pigment carrier (B), and on the transparency carrier of glass substrate etc., be that the mode of 0.2～5 μ m is coated with and forms the color filter joint easily with dry film thickness, and contain solvent, can use in the mode of " green ink " or " green resist printing ink ".
Above-mentioned solvent uses above-mentioned mixed organic solvents (c) in the present invention's the 3rd embodiment, but in the of the present invention the 1st and the 2nd embodiment, can select to use from organic solvent (c1), organic solvent (c2) and secondary solvent.
Viscosity (25 ℃ of following rotation numbers are the viscosity of 60rpm) after the preferred dispersion just of green coloring composition of the present invention is 2～100mPas, thixotropic index after just having disperseed (ratio of viscosity that 25 ℃ of following rotation numbers are 6rpm and the viscosity of 60rpm) is below 1.4, preserve under 10 ℃ the condition after 3 months through the time viscosity increment rate (when being benchmark with the viscosity that is 60rpm of 25 ℃ of following rotation numbers after the firm dispersion, disperse the back under 10 ℃ condition, preserved 3 months, 25 ℃ of viscosity increment rates that following rotation number is 60rpm) less than 20%.When the viscosity after the firm dispersion less than 2mPas or when surpassing 100mPas, thixotropic index after perhaps just having disperseed was above 1.4 o'clock, perhaps through the time viscosity increment rate be 20% when above, can not guarantee to be coated with homogeneity, can not obtain color filter with homogeneous film thickness as purpose.And viscosity and thixotropic index for example can use E type viscosity meter (eastern machine industry society's system " ELD type viscosity meter ") to measure.
[stable storage agent]
In addition, for make composition through the time viscosity stabilization, green coloring composition of the present invention can contain the stable storage agent.
The stable storage agent can be enumerated for example aliquat class of benzyltrimethylammonium chloride or diethyl hydramine 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.; Perhaps
Phosphorous acid salt etc.
[removing of oversize grain or dust]
For green coloring composition of the present invention, preferably remove the oversize grain more than the 5 μ m, oversize grain and then oversize grain more than the preferred 0.5 μ m and the dust of sneaking into more than the preferred 1 μ m by the means of centrifuging, sintered filter or membrane filter etc.When having oversize grain, residual in color filter have impurity, not only produce the problem in the practicality, and in painting process, impurity is blocked in pipeline or the nozzle, produces the significant problem in the preparation.This green coloring composition preferably is substantially devoid of the above particle of 0.5 μ m.The particle that more preferably contains in green coloring composition is (particle diameter that utilizes SEM to record) below the 0.3 μ m.
In addition, in order to improve lightness or contrast ratio, the average mark shot directly is preferably 0.05～0.2 μ m, when being 0.06～0.15 μ m, owing to can and then improve lightness or contrast ratio, so be preferred.
[preparation of color filter]
Color filter of the present invention can prepare by print process or photoetching process.
Utilized print process color filter joint formation since only carry out repeatedly as the printing of the coloured composition of printing-ink modulation and dry just can be graphical, so as the preparation method of color filter, carry out with low cost mass-produced aspect excellence.And then, utilize the development of printing technology can have the printing of the Micropicture of high dimensional accuracy and smoothness.In order to print, to be preferably formed on the galley or and to go up the composition that printing ink is moist, curing is such at superficial layer (Block ラ Application ケ ッ ト).In addition, the control of the flowability of the printing ink on the printing machine also is important, also can utilize spreading agent or filler pigment to carry out the adjusting of ink viscosity.
When utilizing photoetching process to form the color filter joint, can be by the coating process of spraying process or spin-coating method, slot coated method or rolling method etc., will be that the mode of 0.2～5 μ m is coated on the transparency carrier with dry film thickness as the coloured composition of above-mentioned solvent develop type or the painted resist modulation of alkali developable.As required, for dried film by to contact with this film or the mask with compulsory figure of contactless state setting carries out ultraviolet exposure.Dipping or utilize spray development liquid such as sprayer to form the figure of expectation to remove uncured portion in solvent or alkaline developer can carry out same operation repeatedly for other color then and prepare color filter afterwards.And then, in order to promote the polymerization of painted resist, also can implement heating as required.According to photoetching process, can prepare the high color filter of precision 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 be behind the dry above-mentioned painted resist of coating, with water-soluble or buck soluble resin, for example polyvinyl alcohol (PVA) or water soluble acrylic resin etc. are coated with drying, and form the film that the polymerization prevent to be caused by oxygen hinders, carry out ultraviolet exposure then.
Color filter of the present invention can wait by electrodeposition process beyond the said method or transfer printing and prepare, and coloured composition of the present invention can use in any method.And electrodeposition process is to utilize the nesa coating that forms on substrate, and electro-deposition forms shades of colour color filter joint on nesa coating by the electrophoresis of colloidal particle, prepares the method for color filter thus.
In addition, transfer printing is to be pre-formed color filter joint on the surface of the transfer printing substrate of fissility, and makes this color filter joint be transferred to method on the substrate of expectation.
[color filter]
Then, describe for color filter of the present invention.Color filter of the present invention has at least 1 red color filter joint, at least 1 blue color filter joint and at least 1 green color filter joint, and above-mentioned at least 1 green color filter joint uses color composition for color filter of the present invention to form.
The red color filter joint can use common red colored composition to form.In red colored composition, can use C.I. paratonere 7,14,41 for example, 48:1,48:2,48:3,48:4,57:1,81,81:1,81:2,81:3,81:4,122,146,168,177,178,184,185,187,200,202,208,210,246,254,255,264,270,272,279 etc. red pigment.
In red colored composition, can and use C.I. pigment orange 43,71, 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, the blue color filter joint can use common blue colored composition to form.In blue colored composition, can use C.I. pigment blue 15,15:1,15:2,15:3,15:4,15:6,16,22,60,64 etc. blue pigment.In addition in the purple coloured composition, can and with C.I. pigment violet 1,19,23,27,29,30,32,37,40,42,50 etc. violet pigment.
[embodiment]
Below, based on embodiment the present invention is described, but the present invention is not limited to these embodiment.And, in embodiment and comparative example, " part " expression " weight portion ".In addition, Mn and Mw represent 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) are to use HLC-8320GPC (eastern ソ-Co., Ltd.'s system) as device, use SUPER-AW3000 as pillar, and with the N of 30mM triethylamine and 10mM LiBr, the number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polystyrene conversion that dinethylformamide is measured as eluant.
(2) amine value
The amine value of basic resin type spreading agent is the method according to ASTM D 2074, total amine value (mgKOH/g) of measuring is carried out that solid constituent converts and value.
(3) mean molecular weight of the resin of pigment carrier (B)
The number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the acryl resin that uses as the resin of pigment carrier (B) are to use TSKgel pillar (eastern ソ-society's system), with the GPC (eastern ソ-society's system, HLC-8120GPC) that has equipped the RI detecting device, and the number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polystyrene conversion that use THF measures in launching solvent.
(4) acid value of the resin of pigment carrier (B)
The acid value of the acryl resin that uses as the resin of pigment carrier (B) is the potential difference titration according to JIS K0070, the acid value of measuring (mgKOH/g) is carried out that solid constituent converts and value.
(the 1st embodiment)
For containing the green coloring composition of above-mentioned basic resin type spreading agent (a), utilize embodiment (example I series) and comparative example (Comparative Example I series) to describe as necessary composition.
At first, describe for the resin type spreading agent, its solution, commercial resins type dispersant solution, acryl resin and its solution that in example I series and Comparative Example I series, use.Synthesis example I-1: the modulation of synthetic and its solution of resin type spreading agent I-1
In the removable flask of the four-hole with thermometer, stirring machine, distillation cascade and refrigeratory, add 1.9 parts of 70 parts of methyl ethyl ketones, 76.0 parts of n-butyl acrylates, 2.8 parts of sparteine and isobutyl ethyl bromides, flow down at nitrogen and be warming up to 40 ℃.Add 1.1 parts of stannous chlorides, be warming up to 75 ℃ of initiated polymerizations.After the polymerization in 3 hours, polymeric solution is sampled, confirm that by the solid constituent of polymerization the polymerization yield is more than 95%, add methacrylic acid-N, 30.0 parts of 24.0 parts of N-dimethylaminoethyls and MEK, and then carry out polymerization.Confirm that by the solid constituent of the polymeric solution after 2 hours the polymerization yield is more than 97%, be cooled to room temperature and end polymerization.100 parts of the resin solutions that obtain are diluted for 100 parts with methyl ethyl ketone, adding Zeo-karb " ダ イ ア イ オ Application PK228LH (Mitsubishi Chemical's (strain) system) " also at room temperature stirred 1 hour for 60 parts, and then add 10 parts of hydrotalcites (キ ョ-ワ-De 500SN: consonance chemical industry (strain) is made) and, carry out 30 minutes stirring as neutralizing agent.Utilization removes by filter Zeo-karb and adsorbent, removes the residue of polymerization catalyst thus.And then resin solution is concentrated, be substituted by the ethylene glycol monomethyl ether acetate, obtaining nonvolatile component is the solution of the resin type spreading agent I-1 (Mn=10200, Mw=12200, amine value 86mgKOH/g) of 40 weight %.
Synthesis example I-2: the modulation of synthetic and its solution of resin type spreading agent I-2
With adding 1.6 parts of 70 parts of methyl ethyl ketones, 75.0 parts of n-butyl acrylates, 10.0 parts of methyl methacrylates, 2.3 parts of sparteine and isobutyl ethyl bromides, and add 0.9 part of initiated polymerization of stannous chloride with the same method of above-mentioned synthesis example I-1.After the polymerization in 3 hours, add methacrylic acid-N, 30.0 parts of 15.0 parts of N-dimethylaminoethyls and MEK, and then carry out 2 hours polymerization.Afterwards, carry out the operation of removing with the same residue with polymerization catalyst of above-mentioned synthesis example I-1, obtaining nonvolatile component is the solution of the resin type spreading agent I-2 (Mn=11900, Mw=13200, amine value 54mgKOH/g) of 40 weight %.
Synthesis example I-3: the modulation of synthetic and its solution of resin type spreading agent I-3
With adding 2.8 parts of 70 parts of methyl ethyl ketones, 45.0 parts of ethyl acrylates, 43.0 parts of methyl methacrylates, 3.3 parts of sparteine and isobutyl ethyl bromides, and add 1.4 parts of initiated polymerizations of stannous chloride with the same method of above-mentioned synthesis example I-1.After the polymerization in 3 hours, add methacrylic acid-N, 30.0 parts of 12.0 parts of N-dimethylaminoethyls and MEK, and then carry out 2 hours polymerization.Afterwards, carry out the operation of removing with the same residue with polymerization catalyst of above-mentioned synthesis example I-1, obtaining nonvolatile component is the solution of the resin type spreading agent I-3 (Mn=7000, Mw=8500, amine value 43mgKOH/g) of 40 weight %.
Synthesis example I-4: the modulation of synthetic and its solution of resin type spreading agent I-4
With adding 1.9 parts of 70 parts of methyl ethyl ketones, 71.0 parts of n-butyl acrylates, 2.8 parts of sparteine and isobutyl ethyl bromides, and add 1.4 parts of initiated polymerizations of stannous chloride with the same method of above-mentioned synthesis example I-1.After the polymerization in 3 hours, add methacrylic acid-N, 30.0 parts of 29.0 parts of N-dimethylaminoethyls and MEK, and then carry out 2 hours polymerization.Afterwards, carry out the operation of removing with the same residue with polymerization catalyst of above-mentioned synthesis example I-1, obtaining nonvolatile component is the solution of the resin type spreading agent I-4 (Mn=10000, Mw=12000, amine value 105mgKOH/g) of 40 weight %.
Synthesis example I-5: the modulation of synthetic and its solution of resin type spreading agent I-5
With adding 1.9 parts of 70 parts of methyl ethyl ketones, 66.0 parts of n-butyl acrylates, 2.8 parts of sparteine and isobutyl ethyl bromides, and add 1.4 parts of initiated polymerizations of stannous chloride with the same method of above-mentioned synthesis example I-1.After the polymerization in 3 hours, add methacrylic acid-N, 30.0 parts of 34.0 parts of N-dimethylaminoethyls and MEK, and then carry out 2 hours polymerization.Afterwards, carry out the operation of removing with the same residue with polymerization catalyst of above-mentioned synthesis example I-1, obtaining nonvolatile component is the solution of the resin type spreading agent I-5 (Mn=9800, Mw=12000, amine value 121mgKOH/g) of 40 weight %.
Synthesis example I-6: the modulation of commercial resins type dispersant solution
Will be as the PVC ッ Network ケ ミ of commercial resins type spreading agent-system BYK-161,163,164,167,174,184,2000,2050 of ジ ヤ パ Application society, the Japanese Le-Block リ ゾ-system SOLSPERSE-34750,56000 of Le society, the system EFKA4330,4046,4060,4080 of チ バ ジ ヤ パ Application society respectively for nonvolatile component less than 40%, making nonvolatile component by drying under reduced pressure is more than 60%, use the ethylene glycol monomethyl ether acetate to be modulated into the solution that nonvolatile component is 40 weight % then, use as the solution of commercial resins type spreading agent.
Synthesis example I-A: the modulation of synthetic and its solution of acryl resin I-A
In reaction vessel, add 800 parts of cyclohexanone, nitrogen injection is heated to 100 ℃ on one side in container on one side, under uniform temp, with 80.0 parts of 1 hour drip styrenes, 40.0 parts of methacrylic acids, methacrylic acid-N, the potpourri that 85.0 parts of N-methyl esters, 95.0 parts of n-BMAs and azoisobutyronitrile are 10.0 parts carries out polyreaction.
After the dropping, and then after carrying out 3 hours reaction under 100 ℃, add with 2.0 parts of solution that form of cyclohexanone 50 parts of dissolvings azoisobutyronitrile, and then continue reaction 1 hour at 100 ℃, obtain that weight-average molecular weight is about 30000, acid value is the cyclohexanone solution of the acryl resin I-A of 87mgKOH/g.
After being cooled to room temperature, the resin solution of the about 2g of sampling, under 180 ℃, carry out 20 minutes heat drying, measure nonvolatile component, formerly add the ethylene glycol monomethyl ether acetate in the He Cheng resin solution so that nonvolatile component is the solution that 20 weight % prepare acryl resin I-A like this.
Synthesis example I-B～I-P: the modulation of acryl resin I-B～I-P synthetic and their solution
Use monomer composition, amount of initiator (azoisobutyronitrile amount) as shown in table 2 below, carry out the synthetic of acryl resin I-B～I-P equally with the synthetic method of aforesaid propylene acid resin I-A, and modulate their solution.In addition, the acid value of He Cheng resin, weight-average molecular weight are shown in table 2.
[table 2]
Acryl resin Styrene MA MMA nBMA AIBN Acid value Molecular weight Formula (F) is (H) (G)
I—A 80.0 40.0 85.0 95.0 2.0 87 30000 In the scope
I—B 80.0 9.7 115.0 95.0 1.5 21 38200 In the scope
I—C 80.0 25.3 100.0 95.0 6.0 55 13900 In the scope
I—D 80.0 35.9 89.0 95.0 1.9 78 32000 In the scope
I—E 80.0 21.6 103.0 95.0 2.5 47 27500 In the scope
I—F 80.0 41.8 87.0 95.0 5.0 91 16300 In the scope
I—G 80.0 31.3 94.0 95.0 8.0 68 10500 In the scope
I—H 80.0 35.4 80.0 95.0 2.2 77 28400 In the scope
I—I 80.0 14.3 59.0 95.0 1.5 31 37000 In the scope
I—J 80.0 7.4 117.6 95.0 1.8 16 33200 Outside the scope
I—K 80.0 56.1 101.0 95.0 3.5 122 21900 Outside the scope
I—L 80.0 61.1 106.0 95.0 1.7 133 35000 Outside the scope
I—M 80.0 16.6 94.0 95.0 3.6 36 21000 Outside the scope
I—N 80.0 22.1 94.0 95.0 7.7 48 11000 Outside the scope
I—O 80.0 35.4 94.0 95.0 8.7 77 8000 Outside the scope
I—P 80.0 47.8 94.0 95.0 7.0 104 12000 Outside the scope
The explanation that is called for short in the 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 of resin (mgKOH/g)
Y: the weight-average molecular weight of resin
[example I-1]
With 11.0 parts of zinc halide phthalocyanine viridine greens (C.I. naphthol green 58), 2.5 parts of the solution of the SOLSPERSE-56000 of the modulator approach modulation of the solution of the above-mentioned resin dispersion type spreading agent of foundation, 40.0 parts of the solution of aforesaid propylene acid resin I-A, and after the potpourri of 46.5 parts of ethylene glycol monomethyl ether acetate evenly mixes, use the zirconia bead of diameter as 0.5mm, dispersion is after 5 hours in Chinese mugwort lattice grinding machines (ア イ ガ-ミ Le) (ア イ ガ-ジ ヤ パ Application society system " ミ ニ モ デ Le M-250MKII "), filters with the filtrator of 5.0 μ m to prepare the viridine green dispersion.
Then, mix, so that 60.0 parts of above-mentioned viridine green dispersions, 11.0 parts of the solution of aforesaid propylene acid resin I-A, 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 ジ ヤ パ Application society system " イ Le ガ キ ュ ア-907 "), 0.4 part of sensitizer (protecting native ケ paddy chemistry society's system " EAB-F "), be formed uniformly with the potpourri of 23.2 parts of ethylene glycol monomethyl ether acetate, filtrator with 1.0 μ m filters then, obtains 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 the example I-1.Table 4 illustrates the type (block type or non-block type any) of resin type spreading agent.
[table 3]
Figure A200810182161D00441
[table 4]
The resin type spreading agent Amine value mgKOH/g Block type or non-block type
SOLSPERSE-56000 38.7 Non-block type
Resin type spreading agent I-1 86.0 Block type
Resin type spreading agent I-2 54.0 Block type
Resin type spreading agent I-3 43.0 Block type
[example I-25]
With 2.5 parts of the resin solutions (nonvolatile component is 40 weight %) of 10.0 parts of zinc halide phthalocyanine viridine greens (C.I. naphthol green 58), SOLSPERSE-56000, following formula I-9:
Figure A200810182161D00451
After the potpourri that 40.0 parts of the solution of 1.0 parts of the shown pigment derivatives with basic functionality, aforesaid propylene acid resin I-A and ethylene glycol monomethyl ether acetate are 46.5 parts evenly mixes, use the zirconia bead of diameter as 0.5mm, dispersion is after 5 hours in Chinese mugwort lattice grinding machines (ア イ ガ-ジ ヤ パ Application society system " ミ ニ モ デ Le M-250 MKII "), filters with the filtrator of 5.0 μ m to prepare the viridine green dispersion.
Then, mix, so that 60.0 parts of above-mentioned viridine green dispersions, 11.0 parts of the solution of aforesaid propylene acid resin I-A, 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 ジ ヤ パ Application society system " イ Le ガ キ ュ ア-907 "), 0.4 part of sensitizer (protecting native ケ paddy chemistry society's system " EAB-F "), be formed uniformly with the potpourri of 23.2 parts of ethylene glycol monomethyl ether acetate, filtrator with 1.0 μ m filters then, obtains 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 the example I-25.
[table 5]
Figure A200810182161D00461
[example I-49]
With 10.0 parts of zinc halide phthalocyanine viridine greens (C.I. naphthol green 58), 2.5 parts of SOLSPERSE-56000 solution (nonvolatile component is 40 weight %), following formula I-10:
Figure A200810182161D00462
Shown possessing have anchor portion (ア Application カ-portion) for after the potpourri of 46.5 parts of 40.0 parts of the solution of 1.0 parts of the pigment derivatives of the triazine ring skeleton of the basic functionality of benzimidazolone, aforesaid propylene acid resin I-A and ethylene glycol monomethyl ether acetate mixes equably, use the zirconia bead of diameter as 0.5mm, dispersion is after 5 hours in Chinese mugwort lattice grinding machines (ア イ ガ-ジ ヤ パ Application society system " ミ ニ モ デ Le M-250 MKII "), filters with the filtrator of 5.0 μ m to prepare the viridine green dispersion.
Then, mix, so that 60.0 parts of above-mentioned viridine green dispersions, 11.0 parts of the solution of aforesaid propylene acid resin I-A, 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 ジ ヤ パ Application society system " イ Le ガ キ ュ ア-907 "), 0.4 part of sensitizer (protecting native ケ paddy chemistry society's system " EAB-F "), be formed uniformly with the potpourri of 23.2 parts of ethylene glycol monomethyl ether acetate, filtrator with 1.0 μ m filters then, obtains 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 the example I-49.
[table 6]
Figure A200810182161D00481
[Comparative Example I-1～I-15]
Except the SOLSPERSE-56000 solution that the solution (nonvolatile component is 40 weight %) that uses the spreading agent shown in the table 7 replaces using in the example I-1, other identical alkali developable anticorrosive additive material I-73～I-87 that obtains with example I-1.
[table 7]
Spreading agent Amine value mgKOH/g Block type or non-block type Anticorrosive additive material
Comparative Example I-1 EFKA4330 28.0 Block type I—73
Comparative Example I-2 SOLSPERSE —34750 15.6 Non-block type I—74
Comparative Example I-3 BYK—174 22.0 Block type I—75
Comparative Example I-4 Resin type spreading agent 4 105.0 Block type I—76
Comparative Example I-5 Resin type spreading agent 5 121.0 Block type I—77
Comparative Example I-6 EFKA4046 19.0 Non-block type I—78
Comparative Example I-7 EFKA4060 8.0 Non-block type I—79
Comparative Example I-8 EFKA4080 4.0 Non-block type I—80
Comparative Example I-9 BYK—161 11.0 Block type I—81
Comparative Example I-10 BYK—163 10.0 Block type I—82
Comparative Example I-11 BYK—164 18.0 Block type I—83
Comparative Example I-12 BYK—167 13.0 Block type I—84
Comparative Example I-13 BYK—184 15.0 Block type I—85
Comparative Example I-14 BYK—2000 4.0 Block type I—86
Comparative Example I-15 BYK—2050 30.0 Non-block type I—87
[Comparative Example I-16]
Except use copper halide phthalocyanine viridine green (C.I. pigment green 36) replaced zinc halide phthalocyanine viridine green (C.I. naphthol green 58), other and example I-3 obtained alkali developable anticorrosive additive material I-88 equally.
(evaluation method)
Alkali developable anticorrosive additive material I-1～I-88 that use obtains, with following method, measure viscosity characteristics for estimating flowability, for lightness and contrast ratio are measured in the evaluation of carrying out lightness and contrast ratio (CR), for estimate stability measure through the time contrast ratio rate of change and through the time viscosity increment rate.
(1) assay method of viscosity characteristics
Viscosity when the viscosity of gained alkali developable anticorrosive additive material uses E type viscosity meter (eastern machine industry society's system " ELD type viscosity meter ") to measure rotation number as 20rpm gets.And then try to achieve the ratio (be referred to as thixotropic index, this value is big more, and thixotropy is high more) of the viscosity of rotation number when being 6rpm and 60rpm, carry out thixotropic evaluation.
(2) through the time viscosity increment rate assay method
Use E type viscosity meter (eastern machine industry society's system " ELD type viscosity meter "), at 25 ℃, rotation number is under the condition of 20rpm, measure with gained alkali developable anticorrosive additive material modulate back second day initial viscosity and 40 ℃ placed for 1 week down and carried out through the time promote through the time viscosity.With the initial viscosity measured like this and through the time viscosity substitution following formula, measure through the time viscosity increment rate.
[through the time viscosity increment rate]=(through the time viscosity/initial viscosity) * 100
(3) assay method of lightness
Gained alkali developable anticorrosive additive material utilized spinner and changes rotation number prepare 3 coated substrates, so that the chromaticity y of dry film thickness in the cie color system is 0.62,0.6,0.58.Coating back with hot-air oven 80 ℃ dry 30 minutes down, measure thickness then respectively, utilizing linear dependence method method to obtain chromaticity y by 3 data is 0.6 o'clock lightness.Colourity uses microspectrophotometer (オ リ Application パ ス optics society's system " OSP-SP100 ") to measure.
The assay method of the contrast ratio of (4) filming
By the substrate that uses in lightness is measured, utilizing the linear dependence method to obtain chromaticity y by 3 data is 0.6 o'clock contrast ratio.Colourity uses microspectrophotometer (オ リ Application パ ス optics society's system " OSP-SP100 ") to measure.
For the determinator of the contrast ratio of filming and the calculation method of numerical value, use following Fig. 1 to describe.
By polaroid (6) polarization taking place with the light that back light unit (7) sends from LCD, by being coated on the dry coating (4) of the coloured composition on the glass substrate (5), arrives polaroid (3).If polaroid (6) is parallel with the plane of polarization of polaroid (3), light transmission polaroid (3) then, but when plane of polarization was vertical, light was polarized sheet (3) blocking.But, if when the dry coating (4) that causes the light of polarization by coloured composition by polaroid (6), the scattering that generation is caused by pigment particles etc., and produce dislocation in the part of plane of polarization, the light quantity that then sees through polaroid (3) when polaroid is parallel reduces, when polaroid is vertical, a part of light transmission polaroid (3).Measure this and see through light, calculate the ratio (contrast ratio) of the brightness of the brightness of polaroid when parallel when vertical as the brightness on the polaroid.
(contrast ratio)=when parallel (brightness)/when vertical (brightness)
Therefore, if the scattering that the pigment by the dry coating (4) of coloured composition causes takes place, the brightness when then parallel reduces, and the brightness when vertical increases, so the contrast ratio step-down.
And nitometer (1) uses chroma-luminance meter (ト プ コ Application society's system " BM-5A "), and polaroid uses polaroid (day Dong Diangongshe system " NPF-G1220DUN ").And, in order to cover unwanted light, put in mensuration and partially opened the mask (2) of black that the length of side is the cubic hole of 1cm during mensuration.
(5) contrast ratio through the time rate of change assay method
Gained alkali developable anticorrosive additive material was left standstill under 40 ℃ seven days, obtain rate of change with respect to the CR (contrast ratio) after the leaving standstill of initial CR (contrast ratio) through seven days by following formula.
Through the time CR rate of change=(leave standstill through seven days after CR)/(initial CR)
If should through the 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 the color filter green coloring composition.
As the thixotropic index of the above-mentioned resist that obtains, viscosity, through the time viscosity increment rate, contrast ratio (CR), contrast ratio (CR) through the time the results are shown in table 8～11 than rate of change, lightness.
[table 8]
The T.I. of resist The viscosity of resist Through the time viscosity increment rate CR CR through the time rate of change Lightness
Example I-1 1.14 5.8 117％ 4520 92％ 50.2
Example I-2 1.09 6.1 114％ 4700 92％ 50.3
Example I-3 1.06 5.4 104％ 4970 92％ 50.3
Example I-4 1.19 6.2 111％ 4750 91％ 50.3
Example I-5 1.13 7.2 114％ 4480 91％ 50.1
Example I-6 1.13 7.1 112％ 4430 91％ 50.4
Example I-7 1.13 7.3 115％ 4440 91％ 50.4
Example I-8 1.14 7.4 112％ 4430 91％ 50.1
Example I-9 1.20 8.7 120％ 4180 90％ 50.2
Example I-10 1.10 6.1 108％ 4800 94％ 50.2
Example I-11 1.09 6.2 109％ 4780 95％ 50.4
Example I-12 1.08 6.1 108％ 4800 95％ 50.1
Example I-13 1.09 6.2 109％ 4810 96％ 50.4
Example I-14 1.20 7.2 119％ 4589 90％ 50.1
Example I-15 1.09 5.9 109％ 4870 95％ 50.2
Embodiment 1-16 1.08 6.1 108％ 4870 95％ 50.4
Example I-17 1.11 6.1 109％ 4850 96％ 50.1
Example I-18 1.09 5.8 111％ 4850 95％ 50.2
Example I-19 1.17 6.9 116％ 4660 91％ 50.4
Example I-20 1.08 6.3 110％ 4810 94％ 50.1
Example I-21 1.09 6.4 108％ 4810 94％ 50.2
Example I-22 1.08 6.2 109％ 4810 96％ 50.4
Example I-23 1.11 6.3 111％ 4820 93％ 50.1
Example I-24 1.20 6.9 118％ 4570 91％ 50.2
CR: contrast ratio
[table 9]
The T.I. of resist The viscosity of resist Through the time viscosity increment rate CR CR through the time rate of change Lightness
Example I-25 1.04 6.2 114％ 4580 98％ 50.1
Example I-26 1.11 6.3 113％ 4730 98％ 50.3
Example I-27 1.03 6.4 104％ 4980 99％ 50.1
Example I-28 1.08 6.1 110％ 4780 98％ 50.2
Example I-29 1.10 6.9 112％ 4550 93％ 50.1
Example I-30 1.11 6.8 110％ 4510 92％ 50.4
Example I-31 1.12 6.9 111％ 4490 93％ 50.4
Example I-32 1.11 7.1 109％ 4510 92％ 50.1
Example I-33 1.19 8.6 119％ 4240 91％ 50.2
Example I-34 1.06 5.8 105％ 4870 95％ 50.2
Example I-35 1.07 5.8 106％ 4850 97％ 50.4
Example I-36 1.06 5.7 104％ 4870 96％ 50.1
Example I-37 1.06 5.9 106％ 4890 97％ 50.4
Example I-38 1.19 6.9 116％ 4659 92％ 50.1
Example I-39 1.06 5.6 106％ 4930 97％ 50.2
Example I-40 1.06 5.8 105％ 4940 98％ 50.4
Example I-41 1.07 5.7 106％ 4930 97％ 50.1
Example I-42 1.05 5.5 108％ 4920 96％ 50.2
Example I-43 1.16 6.6 113％ 4720 92％ 50.4
Example I-44 1.06 5.9 107％ 4870 96％ 50.1
Example I-45 1.05 6.1 104％ 4870 96％ 50.2
Example I-46 1.06 5.9 106％ 4880 97％ 50.4
Example I-47 1.07 6.1 107％ 4890 95％ 50.1
Example I-48 1.18 6.8 116％ 4630 92％ 50.2
CR: contrast ratio
[table 10]
The T.I. of resist The viscosity of resist Through the time viscosity increment rate CR CR through the time rate of change Lightness
Example I-49 1.21 5.9 115％ 4600 98％ 50.1
Example I-50 1.14 5.8 112％ 4770 99％ 50.4
Example I-51 1.07 6.1 103％ 4990 100％ 50.4
Example I-52 1.12 6.2 110％ 4800 99％ 50.1
Example I-53 1.08 6.4 109％ 4610 94％ 50.4
Example I-54 1.09 6.3 108％ 4580 93％ 50.4
Example I-55 1.1 6.5 108％ 4580 95％ 50.1
Example I-56 1.09 6.6 107％ 4570 94％ 50.2
Example I-57 1.18 8.2 118％ 4320 92％ 50.2
Example I-58 1.04 5.4 102％ 4950 98％ 50.4
Example I-59 1.05 5.4 103％ 4930 99％ 50.1
Example I-60 1.04 5.3 102％ 4930 98％ 50.4
Example I-61 1.04 5.4 103％ 4950 99％ 50.1
Example I-62 1.17 6.5 112％ 4730 94％ 50.2
Example I-63 1.04 5.2 103％ 5000 99％ 50.4
Example I-64 1.04 5.3 102％ 5010 100％ 50.1
Example I-65 1.05 5.3 103％ 4990 99％ 50.2
Example I-66 1.03 5.1 104％ 5010 99％ 50.4
Embodiment 1-67 1.15 6.1 110％ 4800 95％ 50.1
Example I-68 1.04 5.5 103％ 4950 98％ 50.2
Example I-69 1.03 5.6 102％ 4930 98％ 50.4
Example I-70 1.04 5.5 104％ 4930 99％ 50.1
Example I-71 1.05 5.6 103％ 4940 98％ 50.2
Example I-72 1.17 6.4 112％ 4720 94％ 50.2
CR: contrast ratio
[table 11]
The T.I. of resist The viscosity of resist Through the time viscosity increment rate CR CR through the time rate of change Lightness
Comparative Example I-1 2.31 123.2 412％ 3200 87％ 50.1
Comparative Example I-2 2.12 142.2 340％ 2800 88％ 50.4
Comparative Example I-3 2.24 152.1 190％ 1200 88％ 50.1
Comparative Example I-4 1.83 89.2 210％ 3100 85％ 50.2
Comparative Example I-5 1.88 92.1 224％ 3300 84％ 50.4
Comparative Example I-6 2.44 194.1 212％ 1500 81％ 50.4
Comparative Example I-7 2.33 134.2 231％ 1900 88％ 50.2
Comparative Example I-8 2.32 153.2 252％ 1800 81％ 50.4
Comparative Example I-9 2.93 145.3 225％ 1700 83％ 50.3
Comparative Example I-10 2.49 323.3 212％ 2200 78％ 50.2
Comparative Example I-11 3.21 355.3 242％ 2100 81％ 50.4
Comparative Example I-12 2.92 293.3 253％ 2200 80％ 50.3
Comparative Example I-13 2.23 243.2 231％ 2800 81％ 50.1
Comparative Example I-14 2.21 233.1 213％ 1800 82％ 50.2
Comparative Example I-15 2.21 233.1 213％ 1800 82％ 50.2
Comparative Example I-16 1.18 6.2 112％ 4720 88％ 47.1
CR: contrast ratio
Shown in example I series, when using amine value to be the basic resin type spreading agent of 35～100mgKOH/g, can obtain good fluidity, through the time excellent storage stability, and realized the green coloring composition of high lightness, high contrast ratio.
When above-mentioned resin type spreading agent is when comprising the block copolymer resin of alkaline copolymerization block (a1) and pigment carrier compatibility copolymerization block (a2), can and then to form high contrast ratio.
And then when the pigment derivative that will have basic functionality and above-mentioned resin type spreading agent share, initial contrast ratio uprised, and viscosity characteristics, ageing stability are also roughly good.And, and then when share with following such resin, can obtain the best green coloring composition, described resin be with X as acid value, Y during as mean molecular weight, with (F) Y-750X+51000 and (G) Y 940X-79000 and (H) Y the resin represented of 8000 scope.
With respect to instead, in Comparative Example I-1～I-15, formation is mobile, storage stability is all poor, the green coloring composition that contrast ratio is low.In addition, in Comparative Example I-16,, form the green coloring composition of lightness difference owing to used the copper halide phthalocyanine green.
(the 2nd embodiment)
Then, for containing the green coloring composition of above-mentioned pigment derivative (b), utilize embodiment (example II series) and comparative example (Comparative Example I I series) to describe as necessary composition.
At first, describe for the acrylic resin soln that in example II series and Comparative Example I I series, uses.
Synthesis example II-A: the modulation of synthetic and its solution of acryl resin II-A
In reaction vessel, add 800 parts of cyclohexanone, nitrogen injection is heated to 100 ℃ on one side in container on one side, under uniform temp, potpourri with 2.0 parts of 80.0 parts of 1 hour drip styrenes, 40.0 parts of methacrylic acids, 85.0 parts of methyl methacrylates, 95.0 parts of n-BMAs and azoisobutyronitriles carries out polyreaction.
After the dropping, and then after reacting 3 hours under 100 ℃, add with 2.0 parts of solution that form of cyclohexanone 50 parts of dissolvings azoisobutyronitrile, and then continue to react 1 hour, obtain that weight-average molecular weight is about 30000, acid value is the cyclohexanone solution of the acryl resin II-A of 87mgKOH/g at 100 ℃.
After being cooled to room temperature, the resin solution of the about 2g of sampling, under 180 ℃, carry out 20 minutes heat drying, measure nonvolatile component, formerly add the ethylene glycol monomethyl ether acetate in the He Cheng resin solution so that nonvolatile component is the solution that 20 weight % prepare acryl resin II-A like this.
Synthesis example II-B～II-P: the modulation of acryl resin II-B～II-P synthetic and their solution
Use monomer composition, amount of initiator (azoisobutyronitrile amount) as shown in table 12 below, carry out the synthetic of acryl resin II-B～II-P equally with the synthetic method of aforesaid propylene acid resin II-A, and modulate their solution.In addition, the acid value of He Cheng resin, weight-average molecular weight are shown in table 12.
[table 12]
Acryl resin Styrene MA MMA nBMA AIBN Acid value Molecular weight Formula (F) is (H) (G)
II—A 80.0 40.0 85.0 95.0 2.0 87 30000 In the scope
II—B 80.0 9.7 115.0 95.0 1.5 21 38200 In the scope
II—C 80.0 25.3 100.0 95.0 6.0 55 13900 In the scope
II—D 80.0 35.9 89.0 95.0 1.9 78 32000 In the scope
II—E 80.0 21.6 103.0 95.0 2.5 47 27500 In the scope
II—F 80.0 41.8 87.0 95.0 5.0 91 16300 In the scope
II—G 80.0 31.3 94.0 95.0 8.0 68 10500 In the scope
II—H 80.0 35.4 80.0 95.0 2.2 77 28400 In the scope
II—I 80.0 14.3 59.0 95.0 1.5 31 37000 In the scope
II—J 80.0 7.4 117.6 95.0 1.8 16 33200 Outside the scope
II—K 80.0 56.1 101.0 95.0 3.5 122 21900 Outside the scope
II—L 80.0 61.1 106.0 95.0 1.7 133 35000 Outside the scope
II—M 80.0 16.6 94.0 95.0 3.6 36 21000 Outside the scope
II—N 80.0 22.1 94.0 95.0 7.7 48 11000 Outside the scope
II—O 80.0 35.4 94.0 95.0 8.7 77 8000 Outside the scope
II—P 80.0 47.8 94.0 95.0 7.0 104 12000 Outside the scope
The explanation that is called for short in the 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 of resin (mgKOH/g)
Y: the weight-average molecular weight of resin
[example II-1]
With 11.0 parts of zinc halide phthalocyanine viridine greens (C.I. naphthol green 58), following formula II-9:
Figure A200810182161D00581
Shown possess potpourri and mix equably with 48.0 parts of 40.0 parts of the solution of 1.0 parts of pigment derivatives, acryl resin II-A of triazine ring skeleton of basic functionality that anchor portion is a benzimidazolone and ethylene glycol monomethyl ether acetate after, use the zirconia bead of diameter as 0.5mm, dispersion is after 5 hours in Chinese mugwort lattice grinding machines (ア イ ガ-ジ ヤ パ Application society system " ミ ニ モ デ Le M-250MKII "), filters with the filtrator of 5.0 μ m to prepare the viridine green dispersion.
Then, mix, so that 60.0 parts of above-mentioned viridine green dispersions, 11.0 parts of the solution of acryl resin II-A, 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-ケ ミ カ Le ズ society system " イ Le ガ キ ュ ア-907 "), 0.4 part of sensitizer (protecting native ケ paddy chemistry society's system " EAB-F "), be formed uniformly with the potpourri of 23.2 parts of ethylene glycol monomethyl ether acetate, filtrator with 1.0 μ m filters then, obtains the green anticorrosive additive material II-1 of alkali developable.
[example II-2]
Except the solution that makes acryl resin II-A is 37.0 parts, and add adding the ethylene glycol monomethyl ether acetate so that nonvolatile component is 20 weight % like this beyond 3 parts of the solution of the acrylic acid series macromolecule dispersing agent (チ バ ジ ヤ パ Application society's system " EFKA4300; amine value 56mgKOH/g ") that forms of modulation, other and example II-1 obtain alkali developable anticorrosive additive material II-2 equally.
[example II-3]
Except the solution that makes acryl resin II-A is 37.0 parts, and add to add the ethylene glycol monomethyl ether acetate so that nonvolatile component be 20 weight % like this carbamate that forms of modulation be that other and example II-1 obtain alkali developable anticorrosive additive material II-3 equally beyond 3 parts of the solution of macromolecule dispersing agent (PVC ッ Network ケ ミ-society's system " BYK-163; amine value 10mgKOH/g ").
[example II-4]
Have the pigment derivative of triazine ring skeleton that anchor portion is the alkali subtituent of benzimidazolone except possessing, change over Formula Il-10:
Figure A200810182161D00591
Shown possess have beyond the pigment derivative of triazine ring skeleton of alkali subtituent that anchor portion is an anthraquinone, other and example II-1 obtain alkali developable anticorrosive additive material II-4 equally.
[example II-5]
Except 11.0 parts of zinc halide phthalocyanine viridine greens (C.I. naphthol green 58) being changed over 9.0 parts of zinc halide phthalocyanine viridine greens (C.I. naphthol green 58) and metal complex is yellow uitramarine (C.I. pigment yellow 150, ラ Application Network セ ス society's system " Yellow Pigment E4GN ") beyond 2.0 parts, other and example II-1 obtain alkali developable anticorrosive additive material II-5 equally.
[example II-6]
Have 1.0 parts of the pigment derivatives of triazine ring skeleton that anchor portion is the alkali subtituent of benzimidazolone except possessing, change over following formula II-11:
Figure A200810182161D00592
Shown possess beyond 1.0 parts of the pigment derivatives of alkali subtituent that anchor portion is a benzimidazolone, and other and example II-1 obtain alkali developable anticorrosive additive material II-6 equally.
[example II-7]
Have 1.0 parts of the pigment derivatives of triazine ring skeleton that anchor portion is the alkali subtituent of benzimidazolone except possessing, change over following formula II-12:
Shown possess beyond 1.0 parts of the pigment derivatives of alkali subtituent that anchor portion is an anthraquinone, and other and example II-1 obtain alkali developable anticorrosive additive material II-7 equally.
[example II-8～II-15]
Except the solution with acryl resin II-A changed over the solution of acryl resin II-B, other and example II-1 obtained alkali developable anticorrosive additive material II-8 equally.Below, except only the solution of acryl resin II-A being changed over the solution of acryl resin II-C～II-I, other and example II-1 obtain alkali developable anticorrosive additive material II-9～II-15 equally.
[Comparative Example I I-1]
Except the solution that makes acryl resin II-A is 41.0 parts, and remove beyond the pigment derivative, other and example II-1 obtain alkali developable anticorrosive additive material II-16 equally.
[Comparative Example I I-2]
Except 11.0 parts of zinc halide phthalocyanine viridine greens (C.I. naphthol green 58) are changed into copper halide phthalocyanine viridine green (C.I. pigment green 36, Toyo Ink Manufacturing Co., Ltd.'s system " リ オ ノ-Le グ リ-Application 6YK ") beyond 11.0 parts, other and example II-1 obtain alkali developable anticorrosive additive material II-17 equally.
[Comparative Example I I-3]
Except 11.0 parts of zinc halide phthalocyanine viridine greens (C.I. naphthol green 58) being changed into 11.0 parts of copper halide phthalocyanine viridine greens (C.I. pigment Green 7, Toyo Ink Manufacturing Co., Ltd.'s system " リ オ ノ-Le グ リ-Application YS-07 "), other and example II-1 obtain alkali developable anticorrosive additive material II-18 equally.
[example II-16～II-22]
Except the solution with acryl resin II-A changed over the solution of acryl resin II-J, other and example II-1 obtained alkali developable anticorrosive additive material II-19 equally.Below, except only the solution of acryl resin II-A being changed over the solution of acryl resin II-K～II-P, other and example II-1 obtain alkali developable anticorrosive additive material II-20～II-25 equally.
(evaluation method)
Estimate viscosity, thixotropic index, the lightness of filming, the contrast ratio of the above-mentioned resist that obtains equally with the 1st embodiment, it the results are shown in table 13.
Table 13
Shown in example II series, if when the zinc halide phthalocyanine color is disperseed, use pigment derivative, then can obtain mobile excellent coloured composition with alkali subtituent, formation can realize filming of high lightness, high contrast ratio simultaneously.Special 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 with X as acid value, Y during as mean molecular weight, with Y-750X+51000 and Y 940X-79000 and Y the resin solution represented of 8000 scope.With respect to this, used the anticorrosive additive material of the coloured composition of Comparative Example I I-1 to compare with the anticorrosive additive material that obtains in an embodiment, viscosity increases considerably, and the lightness of filming, contrast ratio are also in low level.In addition, for the anticorrosive additive material of the coloured composition that has used Comparative Example I I-2, II-3, the anticorrosive additive material that obtains among its viscosity and the embodiment is identical level, and the contrast ratio of filming is also almost in same level, but filming of obtaining among its lightness and the embodiment compared, and is lower value.
(the 3rd embodiment)
And then, for containing the green coloring composition of above-mentioned mixed organic solvents (c), utilize embodiment (EXAMPLE III series) and comparative example (Comparative Example I II series) to describe as necessary composition.
At first, describe for the evaluation method of the coating of resist and the acrylic resin soln that in EXAMPLE III series and Comparative Example I II series, uses.
(evaluation method of coating)
Evaluation for coating describes.
Use the apparatus for coating of mouthful mould coating method and spin coating mode to be coated with respectively, on the glass substrate of 360mm * 465mm size, forming the average film thickness of 2.0 μ m, the coated substrates that obtains is carried out 20 minutes prebake conditions under 70 ℃, obtain dry coating.Below, record and narrate assessment item, content and result's method for expressing.
＜only spin coating mode 〉
(film thickness uniformity)
" film thickness uniformity (end) ": on the length of 5cm, measure a thickness along substrate center's direction every 5mm at central portion from the minor face end of coated substrates.The maximum film thickness note is made T 1, minimum thickness note makes T 2, average film thickness note makes T, calculates film thickness uniformity (end) by following formula (A).
" film thickness uniformity (beyond the end) ": on the length of 26cm, measure a thickness along diagonal every 2cm in substrate center from coated substrates.With above-mentioned same, calculate film thickness uniformity (beyond the end) by following formula (A).
Film thickness uniformity [%]=((T 1-T 2)/T) * 100 (A)
The preferred little numerical value of film thickness uniformity [%] will be made O less than 4% note, make △ more than 4% and less than 10% note, note work more than 10% *.
＜mouthful mould coating method only 〉
(taeniae shape inequality)
" taeniae shape inequality ":, utilize " the taeniae shape inequality " of white transmitted light evaluation as the strip inequality on the slit working direction of the condensation product that comes from slit opening portion for the coated substrates of mouth mould coating.When not having taeniae shape uneven by range estimation, note is made O, when observing taeniae shape inequality, remember to do *.
(maximum transmission rate)
Gained alkali developable anticorrosive additive material utilized spinner and changes rotation number prepare 3 coated substrates, so that the chromaticity y of dry film thickness in the cie color system is 0.62,0.6,0.58.Coating back with hot-air oven 80 ℃ dry 30 minutes down, measure thickness then respectively, utilizing the linear dependence method to obtain chromaticity y by 3 data is 0.6 o'clock maximum transmission rate.Colourity uses microspectrophotometer (オ リ Application パ ス optics society's system " OSP-SP100 ") to measure.
Then, describe for the acrylic resin soln and the pigment that in EXAMPLE III series and Comparative Example I II series, use.
Synthesis example III-A: the modulation of acryl resin III-A solution
In reaction vessel, add 800 parts of propylene glycol monomethyl ether (following note is made PGMAC), nitrogen injection is heated to 100 ℃ on one side in container on one side, under uniform temp, potpourri with 10.0 parts of 60.0 parts of 1 hour drip styrenes, 60.0 parts of methacrylic acids, 65.0 parts of methyl methacrylates, 65.0 parts of butyl methacrylates and azoisobutyronitriles carries out polyreaction.
After the dropping, and then under 100 ℃, reacted 3 hours, add then with 2.0 parts of solution that form of PGMAC50 part dissolving azoisobutyronitrile, and then continuation was reacted 1 hour under 100 ℃, obtain weight-average molecular weight (Mw) and be the solution of 40,000 acryl resin III-A.
After being cooled to room temperature, the resin solution of the about 2g of sampling, under 180 ℃, carry out 20 minutes heat drying, measure nonvolatile component, formerly add PGMAC in the He Cheng resin solution so that nonvolatile component is the solution that 20 weight % prepare acryl resin III-A like this.
Pigment modulation example
Then describe for the primary particle size assay method of pigment and the modulator approach of pigment.
(primary particle size assay method)
The average primary particle diameter utilization of pigment is measured by the method that the electron micrograph of transmission electron microscope (TEM) directly measures the size of primary particle.Specifically, measure the minor axis diameter and the major diameter of the primary particle of each pigment, with the particle diameter of mean value as this pigment particles.Then,, the volume (weight) of separately particle is similar to the cube of the particle diameter of asking and tries to achieve, the volume average particle size note is made average primary particle diameter for 100 pigment particles.
(modulation of viridine green III-1)
In 1 gallon of kneader of stainless steel (ガ ロ Application ニ-ダ-) (aboveground making is made), add 360 parts of 200 parts of zinc halide phthalocyanine viridine greens (C.I. naphthol green 58), 1400 parts in sodium chloride and diglycols, 80 ℃ mixing 6 hours down.Then will this mixing thing join in 8 liters the warm water, stirred 2 hours, make pulpous state, filter repeatedly, wash and after removing sodium chloride and diglycol,, obtain 190 parts viridine green III-1 at 85 ℃ of dry diels down while be heated to 80 ℃.The primary particle size of trying to achieve by TEM (transmission electron microscope) is 50nm.
(modulation of viridine green III-2)
Except zinc halide phthalocyanine viridine green (C.I. naphthol green 58) being replaced with copper halide phthalocyanine viridine green (C.I. pigment green 36), the modulation of other and viridine green III-1 obtains viridine green III-2 equally.The primary particle size of trying to achieve by TEM (transmission electron microscope) is 60nm.
(modulation of viridine green III-3)
Except zinc halide phthalocyanine viridine green (C.I. naphthol green 58) being replaced with copper halide phthalocyanine viridine green (C.I. pigment Green 7), the modulation of other and viridine green III-1 obtains viridine green III-3 equally.The primary particle size of trying to achieve by TEM (transmission electron microscope) is 60nm.
(modulation of yellow uitramarine)
Except zinc halide phthalocyanine viridine green (C.I. naphthol green 58) being replaced with metal complex is the yellow uitramarine (C.I. pigment yellow 150), and the modulation of other and viridine green III-1 obtains yellow uitramarine equally.The primary particle size of trying to achieve by TEM (transmission electron microscope) is 70nm.
Pigment dispersion modulation example
Then describe for the modulator approach of color filter with green coloring composition (viridine green dispersion).
(modulation of viridine green dispersion III-1)
After the potpourri of 1.0 parts of 40 parts of solution, 48.0 parts of propylene glycol monomethyl ether (PGMAC), the resin type spreading agents (EFKA4300) of 11.0 parts of viridine green III-1 (C.I. naphthol green 58), acryl resin III-A mixed equably, use the zirconia bead of diameter as 0.5mm, dispersion is after 5 hours in Chinese mugwort lattice grinding machines (ア イ ガ-ジ ヤ パ Application society system " ミ ニ モ デ Le M-250MKII "), filters with the filtrator of 5.0 μ m to prepare viridine green dispersion III-1.
Below, the modulation of material shown in the use table 14 and viridine green dispersion III-1 obtains viridine green dispersion III-2～III-8 equally.And pigment dispersion III-5 uses 9 parts of viridine green III-1 and 2 parts of these two kinds of pigment of yellow uitramarine to come the conditioned pigment dispersion.
[table 14]
№ Pigment Solvent Primary particle size
1 Viridine green III-1 Propylene glycol monomethyl ether 50nm
2 Viridine green III-1 The ethylene glycol monomethyl ether acetate 50nm
3 Viridine green III-1 The ethylene glycol monomethyl ether acetate 50nm
4 Viridine green III-1 Propylene glycol monomethyl ether 50nm
5 2 parts of yellow uitramarines of 9 parts of viridine green III-1 Propylene glycol monomethyl ether 54nm
6 Viridine green III-1 Cyclohexanone 50nm
7 Viridine green III-2 Propylene glycol monomethyl ether 60nm
8 Viridine green III-3 Propylene glycol monomethyl ether 60nm
(anticorrosive additive material Production Example)
Then assay method and the modulator approach for the dispersion particle diameter of green anticorrosive additive material describes.
(mensuration of disperseing particle diameter)
Use adopted dynamic light scattering method (FFT power spectrum method) day machine dress society マ イ Network ロ ト ラ ッ Network UPA-E X 150, be absorption mode with the particle permeability, shape of particle is non-sphere, and with D50 as mean diameter.The diluting solvent of measuring usefulness uses the solvent that uses respectively in dispersion, measure for the sample of crossing with ultrasonic Treatment.
(particle diameter that utilizes SEM to measure)
The particle diameter of being measured by SEM of pigment is that the method for utilizing electron micrograph by scanning electron microscope (SEM) directly to measure the size of maximum particle is measured.Specifically, take 50 pigment particles in photo, the minor axis diameter and the major diameter of measuring the primary particle of each pigment with the particle diameter of mean value as this pigment particles, are represented the particle diameter that it is maximum in the mode that keeps 1 position effective digital behind the radix point.
(green anticorrosive additive material III-1)
60.0 part 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 part Photoepolymerizationinitiater initiater (チ バ ス ペ シ ヤ リ テ イ-ケ ミ カ Le ズ society system " イ Le ガ キ ュ ア-907 ")
0.4 part sensitizer (protecting native ケ paddy chemistry society's system " EAB-F ")
15.0 part PGMAC
8.2 part cyclohexyl acetate
Mix so that said mixture is formed uniformly, obtain the green anticorrosive additive material III-1 of alkali developable with the filtrator filtration of 1.0 μ m then.All the match ratio of PGMAC is 89.8% in the solvent, and the match ratio of cyclohexyl acetate is 10.2%.In addition, the particle diameter of being measured by SEM of the viridine green particle of dispersion is 0.2 μ m.
(green anticorrosive additive material III-2)
60.0 part viridine green dispersion III-1
11.0 part acrylic resin soln
4.2 part trimethylolpropane triacrylate (Xin Zhong village chemistry society's system " NK エ ス テ Le ATMPT ")
1.2 part Photoepolymerizationinitiater initiater (チ バ ス ペ シ ヤ リ テ イ-ケ ミ カ Le ズ society system " イ Le ガ キ ュ ア-907 ")
0.4 part sensitizer (protecting native ケ paddy chemistry society's system " EAB-F ")
23.2 part cyclohexyl acetate
Mix so that said mixture is formed uniformly, obtain the green anticorrosive additive material III-2 of alkali developable with the filtrator filtration of 1.0 μ m then.All the match ratio of PGMAC is 71.0% in the solvent, and the match ratio of cyclohexyl acetate is 29.0%.In addition, the particle diameter of being measured by SEM of the viridine green particle of dispersion is 0.2 μ m.
Below, the modulation of material shown in the use table 15 and green anticorrosive additive material III-1 obtains green anticorrosive additive material III-3～III-11 equally.The particle diameter of in table 15, also having represented each anticorrosive additive material in addition by SEM mensuration.
[table 15]
Anticorrosive additive material No. Pigment dispersion Organic solvent (C1-1) Organic solvent (C1-2) The C1-1 match ratio The C1-2 match ratio Particle diameter (μ m) by SEM mensuration
III-1 III-1 Propylene glycol monomethyl ether Cyclohexyl acetate 89.8％ 10.2％ 0.2
III-2 III-1 Propylene glycol monomethyl ether Cyclohexyl acetate 71.0％ 29.0％ 0.2
III-3 III-2 Propylene glycol monomethyl ether Cyclohexyl acetate 89.8％ 10.2％ 0.2
III-4 III-1 Propylene glycol monomethyl ether The 3-ethoxyl ethyl propionate 89.8％ 10.2％ 0.2
III-5 III-1 Propylene glycol monomethyl ether Diethylene glycol diethyl ether 89.8％ 10.2％ 0.2
III-6 III-2 Ethylene glycol monomethyl ether acetate The 3-ethoxyl ethyl propionate 89.8％ 10.2％ 0.2
III-7 III-5 Propylene glycol monomethyl ether Cyclohexyl acetate 89.8％ 10.2％ 0.3
III-8 III-5 Propylene glycol monomethyl ether The 3-ethoxyl ethyl propionate 89.8％ 10.2％ 0.3
III-9 III-1 Propylene glycol monomethyl ether Propylene-glycol diacetate 89.8％ 10.2％ 0.2
III-10 III-3 Propylene glycol monomethyl ether Cyclohexyl acetate 89.8％ 10.2％ 0.2
III-11 III-4 Propylene glycol list ethylether acetic acid esters Cyclohexyl acetate 89.8％ 10.2％ 0.2
[comparative example]
Use material shown in table 16, modulate green anticorrosive additive material equally with the modulation of green anticorrosive additive material III-1.And,, add a kind of solvent of 23.2 parts for green anticorrosive additive material III-12 and III-19.The particle diameter of in table 16, also having represented each anticorrosive additive material in addition by SEM mensuration.
[table 16]
Anticorrosive additive material № Pigment dispersion Organic solvent II I-1 Organic solvent II I-2 Particle diameter (μ m) by SEM mensuration
III-12 III-1 Propylene glycol monomethyl ether Do not have 0.2
III-13 III-6 Cyclohexanone The 3-ethoxyl ethyl propionate 0.4
III-14 III-1 Propylene glycol monomethyl ether Isoamyl acetate 0.2
III-15 III-1 Cyclohexanone The 3-ethoxyl ethyl propionate 0.3
III-16 III-1 Cyclohexanone Cyclohexyl acetate 0.3
III-17 III-7 Propylene glycol monomethyl ether The 3-ethoxyl ethyl propionate 0.2
III-18 III-8 Propylene glycol monomethyl ether The 3-ethoxyl ethyl propionate 0.2
III-19 III-6 Cyclohexanone Do not have 0.4
III-20 III-1 Butyl acetate The 3-ethoxyl ethyl propionate 0.2
III-21 III-1 Propylene glycol monomethyl ether The tripropylene glycol methyl ether 0.2
In addition, the characteristic value of the organic solvent that uses in EXAMPLE III series and Comparative Example I II series is shown in table 17.
[table 17]
Organic solvent Boiling point The SP value
Propylene glycol monomethyl ether 146 8.7
The ethylene glycol monomethyl ether acetate 145 9.0
Propylene glycol list ethylether acetic acid esters 156 8.9
Propylene glycol list ethylether acetic acid esters 158 8.7
Cyclohexyl acetate 173 9.2
The 3-ethoxyl ethyl propionate 165 8.9
Propylene-glycol diacetate 190 9.6
Diethylene glycol diethyl ether 188 8.7
Cyclohexanone 156 10.4
Isoamyl acetate 142 7.8
Butyl acetate 126 8.7
The tripropylene glycol methyl ether 242 10.2
(evaluation result)
Estimate viscosity, thixotropic index, the lightness of filming, the contrast ratio of the above-mentioned resist that obtains equally with the 1st embodiment, its result is shown in table 18 and table 19 with the evaluation result of disperseing 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 estimate.At first, describe for the red anticorrosive additive material that in the making of color filter, uses.
After the potpourri of 8.0 parts of C.I. paratoneres 177,40 parts of acrylic resin solns, 48.0 parts of propylene glycol monomethyl ether (PGMAC), 1.0 parts of resin type spreading agents (EFKA4300) mixed equably, use the zirconia bead of diameter as 0.5mm, dispersion is after 5 hours in Chinese mugwort lattice grinding machines (ア イ ガ-ジ ヤ パ Application society system " ミ ニ モ デ Le M-250 MKII "), filters with the filtrator of 5.0 μ m to prepare red pigment dispersion.
(modulation of red anticorrosive additive material)
Mix, so that the potpourri of 23.2 parts of 4.2 parts of 60.0 parts of red pigment dispersion, 11.0 parts of acrylic resin solns, trimethylolpropane triacrylate (Xin Zhong village chemistry society's system " NK エ ス テ Le ATMPT "), 1.2 parts of Photoepolymerizationinitiater initiaters (チ バ ジ ヤ パ Application society system " イ Le ガ キ ュ ア-907 "), 0.4 part of sensitizer (protecting native ケ paddy chemistry society's system " EAB-F ") and PGMAC is formed uniformly, filtrator with 1.0 μ m filters then, obtains the red anticorrosive additive material of alkali developable.
(making of color filter)
On the glass substrate of 10cm * 10cm, be coated with the thick above-mentioned red anticorrosive additive material of about 2 μ m, it was left standstill in 70 ℃ baking oven 15 minutes, remaining solvent is removed drying with spinner.Then, use exposure device to carry out the striated pattern exposure.Exposure is 100mJ/cm 2And then, utilize the developer solution that comprises 2% aqueous sodium carbonate to carry out spray developing, remove unexposed portion, use the ion-exchange water washing then, this substrate was heated 30 minutes down at 230 ℃, form the red color filter joint that live width is about 50 μ m.Then,, use the green anticorrosive additive material of EXAMPLE III-1 to form the color filter joint, thereby make the color filter of color filter joint with 2 looks in the adjacent place of red color filter joint by same operation.
[table 18]
Figure A200810182161D00701
[table 19]
Figure A200810182161D00711
When the green anticorrosive additive material III-1～III-11 shown in EXAMPLE III series such, use solvent (c1) to make and used in the resist of zinc halide phthalocyanine color dispersion, use when comprising the mixed organic solvents of solvent (c1) and solvent (c2) at least, can obtain the coloured composition of flowability, coating excellence, form and to realize filming of high lightness, high-transmission rate, high contrast ratio simultaneously.With respect to this,, can not obtain to satisfy simultaneously filming of lightness, contrast ratio, transmissivity, coating for the green anticorrosive additive material III-12～III-21 shown in the Comparative Example I II series.

Claims (15)

1. color filter green coloring composition, it contains:
(A) contain at least the zinc halide phthalocyanine color pigment composition and
(B) comprise the pigment carrier of resin, its precursor or their potpourri, and
Contain and be selected from:
(a) amine value be 35～100mg KOH/g basic resin type spreading agent,
(b) have alkali subtituent pigment derivative and
(c) at least 1 of mixed organic solvents kind, it is 8.0～10.0 (cal/cm that described mixed organic solvents contains solubility parameters (SP value) 3) 1/2, the boiling point under the 760mmHg is 140～159 ℃ organic solvent (c1); And solubility parameters (SP value) is 8.0～10.0 (cal/cm 3) 1/2, the boiling point under the 760mmHg is 160～200 ℃ organic solvent (c2).
2. color filter green coloring composition as claimed in claim 1, wherein, when acid value note is made X (mg KOH/g), when the weight-average molecular weight note is made Y, the resin that constitutes above-mentioned pigment carrier (B) is the resin that all satisfies following formula (F), (G) and condition (H) simultaneously:
(F)Y>-750X+51000
(G)Y>940X-79000
(H)Y>8000。
3. color filter green coloring composition as claimed in claim 1 is characterized in that, when being benchmark with the general assembly (TW) of above-mentioned pigment composition (A), the content of above-mentioned basic resin type spreading agent (a) is 0.001～50 weight %.
4. color filter green coloring composition as claimed in claim 1, wherein, above-mentioned basic resin type spreading agent (a) is the block copolymer resin that comprises alkaline copolymer block (a1) and pigment carrier compatibility copolymer block (a2).
5. color filter green coloring composition as claimed in claim 4, wherein, above-mentioned block copolymer resin is the block copolymer resin that utilizes active free radical polymerization to obtain.
6. color filter green coloring composition as claimed in claim 1 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 weight %.
7. color filter green coloring composition as claimed in claim 1, wherein, above-mentioned organic solvent (c1) is the solvent more than at least a kind that is selected from propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, ethylene glycol monomethyl ether acetate 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 more than at least a kind that is 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 weight %～95 weight %, and above-mentioned organic solvent (c2) is 5 weight %～50 weight %.
10. color filter green coloring composition as claimed in claim 1 is characterized in that, and then contains Photoepolymerizationinitiater initiater.
11. color filter green coloring composition as claimed in claim 1 wherein, contains above-mentioned basic resin type spreading agent (a) and above-mentioned pigment derivative (b).
12. color filter green coloring composition as claimed in claim 1 wherein, contains above-mentioned basic resin type spreading agent (a) and above-mentioned mixed organic solvents (c).
13. color filter green coloring composition as claimed in claim 1 wherein, contains above-mentioned pigment derivative (b) and above-mentioned mixed organic solvents (c).
14. color filter green coloring composition as claimed in claim 13 wherein, and then contains above-mentioned basic resin type spreading agent (a).
15. color filter is characterized in that, has the green color filter joint that is formed with green coloring composition by each described above-mentioned color filter in the claim 1～14.
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