CN1982925A - Colored composition and color filter using the same - Google Patents
Colored composition and color filter using the same Download PDFInfo
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- CN1982925A CN1982925A CN 200610166938 CN200610166938A CN1982925A CN 1982925 A CN1982925 A CN 1982925A CN 200610166938 CN200610166938 CN 200610166938 CN 200610166938 A CN200610166938 A CN 200610166938A CN 1982925 A CN1982925 A CN 1982925A
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Abstract
The present invention provides a colored composition which is a liquid colored composition having colored material carrier composed of transparent resin and its former or their compound, colored material, organ solvent, surface regulator. For the liquid colored composition, dipping a glass plate with the surface is a 22 mm x 22 mm square and thickness is 0.145mm into the liquid colored composition according to Wilhelmy plate method, making one edge of the glass plate dip 2.5 mm in vertical direction perpendicular to the liquid surface of the liquid composition, here, the force A measured under the static status of glass plate and under 25 DEG C is larger than 1.16 mN, and the force A' obtained by minus the buoyancy of the glass plate in the colorized composition from the force A satisfies the following relation with force B measured at the instant that the glass plate separating from the liquid colorized composition when lifting the dipped glass plate in vertical direction with a speed of 2.5 mm/s under 25 DEG C: 0.08 <= B-A' <= 0.18. The present invention provides a color filter which is equipped with filter segment and/or black substrate formed by the colorized composition.
Description
Technical field
The present invention relates to be used for employed coloured composition in the manufacturing of color filter of color liquid crystal display arrangement, colour pick-up tube element etc. and used the color filter of this coloured composition.
Background technology
Constitute color filter that LCD (LCD), colour pick-up tube element (CCD) wait and be by being coated with coating fluid (coloured composition) and dry on transparency carrier, formation thickness is about that filming of 1～3 μ m make.As the mode that coating fluid is applied on the substrate, method of spin coating and mold pressing rubbing method etc. are arranged, can suitably use according to its feature.
Method of spin coating is a kind of film forming method on the substrate of reduced size that is widely used in, this coating process is as described below: make the transparency carrier rotation with certain rotating speed, drip coating fluid at the transparency carrier core simultaneously, utilize the centrifugal force coating fluid that extends thinly, rotating speed by controlling the transparency carrier that is fit to this coating fluid and rotational time etc. form filming of desirable thickness on the surface of transparency carrier.But but there is following shortcoming in this method: because this principle that the centrifugal force that utilizes rotation to produce extends thinly and films, therefore cause the rotation center part of transparency carrier to be compared with the intermediate portion with the coating thickness of peripheral part and become blocked up.
The mold pressing rubbing method is a kind of film forming method on large-sized substrate that is applicable to, this coating process is as described below: from slit, spray coating fluid, on one side travelling slit on the surface of transparency carrier, form on one side and have filming of desirable thickness.But, there is following shortcoming in the mold pressing rubbing method: at the inequality that is easy to generate strip in this mechanism on the direction vertical with respect to the direct of travel of slit (bar inequality (ス ジ system ラ)), and the outer peripheral portion projection of filming, it is thicker than substrate center part that thickness becomes.
In addition, no matter be which kind of coating method, all can cause the surface tension of coating fluid and viscosity is improper and the problem that produces pore (blank spot).
For the problem of the unevenness of filming that solves such method of spin coating and mold pressing rubbing method, various trials have been carried out.
For example, in Japanese kokai publication hei 6-3521 communique, disclose comprise above boiling point of 50 weight % and the solvent of vapour pressure in specific scope composition as the good method of spin coating composition of surface smoothing of filming.
In addition, open the 2004-70352 communique TOHKEMY 2004-66232 communique, spy, the spy opens in the 2004-233993 communique, disclose in the mold pressing rubbing method, the surface tension of coating fluid is adjusted in certain scope, thus uneven and unequal coating fluid and the coating process thereof of thickness of the bar of reduction coated face.
And then in any coating method of rotary coating mode and mold pressing coating method, in order to form uniform thickness on substrate, the viscosity of preferred coloured composition is low as much as possible.Use the high more coloured composition of viscosity, then be difficult to form film more.In addition, in pigment dispersing in organic solvent and in the higher coloured composition of viscosity, the viscosity under the dynamical state and the difference of the viscosity under the static state have the tendency that becomes big (thixotropy height), when using such coloured composition to form film, can form the film of the lack of homogeneity of thickness.
Therefore, be necessary to make the alap coloured composition of viscosity,, the method that comprises low viscous solvent arranged as one of its method.But, owing to the specific inductive capacity and the conductivity of the low viscosity solvent that can be used for color composition for color filter are low, be the high coloured composition of charging property mostly therefore, be easy to generate because the charged crawling that causes.
To this, in Japanese kokai publication hei 10-287816 communique, disclose and in coloured composition, added electrically conductive microparticle, the conductivity of coloured composition is adjusted to more than certain value, thereby reduced the method for thickness inequality.
Summary of the invention
At the coating method of method of spin coating and mold pressing rubbing method and since wherein the various defectives in filming that cause of the proterties of employed coating fluid observe, these defectives are put in order, its result is as described below.
Blank spot: the defective of pore shape.
Irregular colour: be divided in the end irregular colour observed architrave shape, that the border is more clearly (" end irregular colour ") and 2 kinds of feint irregular colours in observed border (" integral color inequality ") on whole base plate.
The thickness inequality: the lack of uniformity of expression thickness, the homogeneity of thickness be divided into the film thickness uniformity of end (" film thickness uniformity (end) ") and from the substrate center to the end before 2 kinds of homogeneitys (" film thickness uniformity (beyond the end) ").
The bar inequality: in the mold pressing coating method, the inequality of the strip that on the direction vertical, is produced with respect to the direct of travel of slit.
How reducing such defective is a problem, but only depend on the selection specific solvent that above-mentioned patent documentation puts down in writing method, use surface tension and viscosity is adjusted to the method for compositions of certain limit, add electrically conductive microparticle the conductivity of coloured composition is adjusted to the method more than certain value in coloured composition, all be not enough to address the above problem.
The object of the present invention is to provide a kind ofly when being coated with, can reduce the coloured composition of observed above-mentioned defective on filming by method of spin coating and mold pressing rubbing method.In addition, the present invention also aims to provide the color filter that almost can not observe above-mentioned paint film defect with filter section and/or black matrix.
According to a first aspect of the invention, a kind of coloured composition is provided, it is a kind of comprising by transparent resin, its precursor or their the coloured material carrier that potpourri constituted, coloured material, organic solvent, and the aqueous coloured composition of surface conditioner, it is characterized in that: according to the Wilhelmy flat band method, with the plane is the square of 22mm * 22mm, thickness is that the glass plate of 0.145mm is immersed in this aqueous coloured composition, make a limit of above-mentioned glass plate on the vertical direction vertical, flood 2.5mm with respect to the liquid level of this liquid composition, at this moment, the power A that measures under the stationary state of above-mentioned glass plate (measuring down at 25 ℃) is for more than the 1.16mN, and the power A ' that after above-mentioned power A deducts the buoyancy of the above-mentioned glass plate the above-mentioned coloured composition, obtains, the power B (measuring down at 25 ℃) that is measured from the moment that aqueous coloured composition breaks away from the above-mentioned glass plate when the speed with 2.5mm/ second vertically promotes the glass plate of above-mentioned dipping satisfies following relation:
0.08≤B-A’≤0.18。
In addition,, provide a kind of color filter, it is characterized in that it possesses by formed filter section of coloured composition of the present invention and/or black matrix according to the 2nd aspect of the present invention.
Coloured composition of the present invention is a kind of value composition of measuring by the Wilhelmy flat band method within the specific limits, by using this coloured composition, can form the uniform coating that the defective of filming has reduced.
Therefore, the coloured composition of the application of the invention forms filter section and/or black matrix, and high-quality color filter can be provided.
The present invention is high especially to the effect of the red colored composition of easy generation crawling.
Description of drawings
Fig. 1 is an example by the curve map of the power of Wilhelmy method mensuration.
Fig. 2 is by the skeleton diagram of Wilhelmy method with the state of glass-impregnated in coloured composition.
Embodiment
At first, about coloured composition of the present invention, suitably use Fig. 1 and Fig. 2 to carry out specific description.
Coloured composition of the present invention comprises by transparent resin, its precursor or their coloured material carrier, coloured material, organic solvent and surface conditioner that potpourri constituted.For coloured composition of the present invention, according to the Wilhelmy flat band method, with the plane is the square of 22mm * 22mm, thickness is that the glass plate of 0.145mm is immersed in this aqueous coloured composition, make a limit of above-mentioned glass plate on the vertical direction vertical, flood 2.5mm with respect to the liquid level of this liquid composition, at this moment, the power A that measures under the stationary state of above-mentioned glass plate is more than the 1.16mN, and the power A ' that after above-mentioned power A deducts the buoyancy of the above-mentioned glass plate the above-mentioned coloured composition, obtains, the power B that is measured from the moment that aqueous coloured composition breaks away from the above-mentioned glass plate when the speed with 2.5mm/ second vertically promotes the glass plate of above-mentioned dipping satisfies following relation:
0.08≤B-A’≤0.18。
The Wilhelmy method is a kind of solid or powder etc. to be immersed in the determination object liquid (sample solution), and the dipping glass plate is measured its buoyancy and time dependent method of infiltration power static and when promoting by electronic balance.
In the present invention, the dynamic wellability exerciser WET-600 type that uses Resca company to make is measured machine, and uses the plane to be the square of 22mm * 22mm, the thickness glass plate (MATSUNAMI company manufacturing, thickness is measured value) as 0.145mm.The diameter of accommodating the container of sample solution (liquid composition) is about 45mm and the degree of depth is about 40mm, adds sample solution until reaching apart from the height more than the bottom 15mm of container.A limit of glass plate vertically is immersed in the liquid composition with respect to the liquid level of liquid composition, and the degree of depth reaches 2.5mm.The impregnating depth of this glass plate is to be benchmark with liquid level (putting into sample solution but the fluid level of sample solution when not flooding glass plate in container).Mensuration is that the temperature at liquid composition is to carry out under 25 ℃ the temperature.
[power of stationary state: A]
In the sample solution (coloured composition) 2 (Fig. 2) that glass plate 1 (Fig. 2) is immersed in the container 3, reach under the stable status (scope of the T1 of Fig. 1), as shown in Figure 2, the power A that detects with electronic balance (unit: mN) be by sample solution surface tension was produced to the power A ' of downside effect and with the power that the buoyancy f of the proportional glass plate of volume of the glass plate of dipping part is synthesized, can represent by following formula (1).
A＝A’-f (1)
Wherein,
A’＝γ×cosθ×L
γ: the surface tension of sample solution (mN/m)
θ: the contact angle of sample solution and glass plate
L: glass plate and sample solution soak girth ((width+thickness) * 2 of glass plate) (m)
f＝V×ρ×g
V: the volume (m of the glass plate of dipping part
3)
ρ: the density (g/m of sample solution
3)
G: acceleration of gravity (m/s
2)
Therefore, the power A ' to the downside effect can represent by following formula (2).
A’＝A+f (2)
[detected power in the lifting process: A2]
In the process (scope of the T2 of Fig. 1) that glass plate is raised to power that glass plate acted on except above-mentioned power A, attempt to be returned to the power (f1: the power that hinders the liquid distortion) also effect downwards of previous status attached to the liquid on the glass plate.Therefore, power A2 can represent by following formula (3).
A2＝A+f1＝A’-f+f1 (3)
But, reducing to flood in the process of volume in lifting, buoyancy (f) is also reducing gradually.
[liquid breaks away from the power of moment: B from glass plate]
In the T3 position of Fig. 1, glass plate breaks away from sample solution.In this moment detected power, do not comprise the factor of buoyancy (f), therefore, power B can represent by following formula (4).
B＝A’+f1 (4)
In the state variation from T1 to T3, " hindering the power f1 of distortion " put in order with the relation of " deducting the power A ' of effect downwards that obtains behind the buoyancy of glass under the stationary state " from " liquid is from the power B of the moment that glass plate breaks away from ", then f1 can represent by following formula (5).
f1＝B-A’ (5)
Because the feature of coating fluids such as A presentation surface tension force, contact angle, proportion, so A and the correlation of attributes of filming, in addition, because " B-A ' " be " power that hinders the liquid distortion ", therefore, in the so-called method that liquid is out of shape make film, become important factor.
Discoveries such as the inventor: the characteristic to coloured composition (coating fluid) is controlled, so that the value of A to be 1.16mN above and the relation of the value of the value of B and A ' satisfies 0.08≤B-A '≤0.18[mN], this for the crawling that obtains film coated surface, be that the unequal good film quality that is coated with that all obtains reducing of blank spot, thickness inequality and bar is necessary.
As [B-A '] during less than 0.08mN, its evaluation result is: even A satisfies more than the 1.16mN, " blank spot " is also many, " integral color inequality " is also serious, " film thickness uniformity (end) " and " film thickness uniformity (outside the end) " is also poor, and also can observe " bar inequality " in the mold pressing rubbing method.
As satisfied 0.08≤B-A '≤0.18[mN], but A is during less than 1.16mN, and " end irregular colour length " is elongated.
When [B-A '] surpasses 0.18mN and A satisfies 1.16mN when above, its evaluation result is: " blank spot " is poor slightly, and " length of end irregular colour " is elongated, and " film thickness uniformity (end) " and " film thickness uniformity (outside the end) " is poor.
In addition, more preferably the characteristic of coating fluid is controlled, the value that makes A is 1.20[mN] relation of the value of above and B and the value of A ' satisfies 0.09≤B-A '≤0.14[mN].
For the value that makes A reaches more than certain value and [B-A '] adjusted in the above-mentioned scope, use surface conditioner.
Surface conditioner is so-called surfactant a kind of who has hydrophobic grouping and hydrophilic radical in the molecule, the following surface conditioner of preferred use: though have hydrophilic radical, but the dissolubility to water is little, in the time of in adding coloured composition to, has the characteristic that its surface tension reduction can be lower, though and surface tension reduce can be lower, good to the wellability of glass plate.
As surface conditioner, the preferred dimethyl polysiloxane that uses with polyoxyalkylene.As polyoxyalkylene, polyoxyethylene, PPOX are arranged, dimethyl polysiloxane can have polyoxyethylene and PPOX simultaneously.
In addition, polyoxyalkylene and the combining form of dimethyl polysiloxane can be polyoxyalkylene be combined in side chain type in the repetitive of dimethyl polysiloxane, be combined in the end of dimethyl polysiloxane terminal-modified type, alternately repeat any of segmented copolymer type of the straight chain shape that combines with dimethyl polysiloxane.
Dimethyl polysiloxane with polyoxyalkylene can list for example FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, the FZ-2207 that Toray Dowcorning company sells, but is not limited to these.
With respect to the coloured material of 100 weight portions in the coloured composition, surface conditioner preferably uses 0.01～5.00 weight portion, the more preferably amount of 0.10～3.00 weight portion.
If the addition of surface conditioner surpasses 5.00 weight portions, then the value of A became low, and " length of end irregular colour " is elongated.
In addition, when addition was less than 0.01 weight portion, the value of A became too high, and [B-A '] became low, cause " blank spot ", " integral color inequality ", " film thickness uniformity (end) " and " film thickness uniformity (beyond the end) " variation take place.
The surfactant that also can add anionic property, cationic, nonionic or both sexes with surface conditioner complementaryly.Surfactant also can mix use more than 2 kinds.
As the anionic surfactant, can list monoethanolamine, polyoxyethylene alkyl ether phosphate of basic salt, sodium alkyl naphthalene sulfonate, alkyl diphenyl base ether sodium disulfonate, lauryl sulfate monoethanolamine, triethanolamine lauryl sulfate, Texapon Special, stearic acid monoethanolamine, odium stearate, NaLS, the styrene-propene acid copolymer of polyoxyethylene alkyl ether sulfate salt, neopelex, styrene-propene acid copolymer etc.
As cationic surfactant, can list alkyl quaternary ammonium salts or their ethylene oxide adduct.
As nonionic surfactant, can list polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylplenyl ether, polyoxyethylene alkyl ether phosphate, Tween-60, polyethylene glycol monolaurate etc.; Amphoteric surfactant and fluorine-containing or silicone-based surfactants such as alkyl betaine, alkyl imidazoline such as alkyl dimethyl aminoacetic acid betaine.
When using surfactant, the amount of surfactant is preferably the amount of 1～50 weight % that is equivalent to surface conditioner weight.
Charged in order to prevent, preferred coloured composition is more than 8.0 and the conductivity under 25 ℃ is more than the 100nS/cm at the specific inductive capacity under 25 ℃, and the upper limit separately has no particular limits.But, because coloured composition is not water system but dicyandiamide solution, therefore, from its fundamental property, specific inductive capacity and conductivity can not become value high as ion component is dissolved in the water, and the specific inductive capacity under 25 ℃ is about below 200, and the conductivity under 25 ℃ is about 1 * 10
6Below the nS/cm.
In preferred form, coloured composition is more than 8.0 and the conductivity under 25 ℃ is more than the 150nS/cm at the specific inductive capacity under 25 ℃, and more preferably coloured composition is more than 8.0 and the conductivity under 25 ℃ is more than the 180nS/cm at the specific inductive capacity under 25 ℃.
In addition, in order to reduce " blank spot ", " irregular colour ", " the thickness inequality " and " bar inequality " of filming, preferred coloured composition the viscosity 25 ℃ under (using the viscosity of measuring under the rotating speed of E type viscosity meter at 20rpm) as 20mPas below, its lower limit does not have especially and limits.But the viscosity of the organic solvent that the viscosity of coloured composition is not less than in the coloured composition to be comprised is approximately more than the 0.5mPas.If the viscosity under 25 ℃ surpasses 20mPas, then in method of spin coating or mold pressing rubbing method, be difficult to carry out stable coating, be difficult to guarantee the homogeneity of filming.Preferred viscosity is below the 10mPas, more preferably below the 6mPas.
For the viscosity with coloured composition is controlled in the above-mentioned scope, total amount with organic solvent is benchmark (100 weight %), at the specific inductive capacity under 25 ℃ is below 10.0, is below the 1nS/cm and in the viscosity under 25 ℃ to be that organic solvent S below the 1.5mPas preferably comprises more than the 5 weight % in the conductivity under 25 ℃.The specific inductive capacity of organic solvent S and the lower limit of conductivity also have no particular limits, and still, specific inductive capacity is about more than 1.8, conductivity is about 1 * 10
-3More than the nS/cm.In addition, the viscosity of organic solvent S does not have lower limit yet, but is about more than the 0.5mPas.
When the total amount with organic solvent is the content of the organic solvent S in benchmark, the organic solvent during less than 5 weight %, can not produce low viscosity as the characteristics of organic solvent S.
As organic solvent S, all very low from specific inductive capacity, conductivity and viscosity, and boiling point, velocity of evaporation, consider the preferred especially at least a organic solvent that is selected from isoamyl acetate, 3-ethoxyl ethyl propionate, the propylene glycol methyl ether acetate that uses with the aspect of the compatibility of pigment or resin.
As other preferred organic S, can list acetone, o-xylene, m-xylene, P-xylene, 3-methoxypropionic acid methyl esters, butyl acetate, isobutyl acetate, propyl acetate etc.But be not limited to these organic solvents, as long as satisfy the condition of organic solvent S of the present invention.
In coloured composition of the present invention, can to comprise total amount with organic solvent be benchmark, the organic solvent except that organic solvent S less than 95%.
As the organic solvent except that organic solvent S, can list cyclohexanone, propylene-glycol diacetate, propylene glycol monomethyl ether, diethylene glycol diethyl ether, methyl isobutyl ketone, normal butyl alcohol, dipropylene glycol monomethyl ether, the tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, the single propyl ether of dipropylene glycol, propylene glycol monobutyl ether, the dipropylene glycol monobutyl ether, the tripropylene glycol monobutyl ether, propylene glycol phenyl ether, the dipropylene glycol monomethyl ether acetic acid esters, 1,3-butylene glycol diacetate esters, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether, butyl carbitol acetate, the 3-methoxybutanol, 1, the 3-butylene glycol, glyceryl triacetate, 3,3,5-trimethyl-2-cyclohexene-1-ketone, ethylene glycol monoethyl ether, gamma-butyrolacton etc.These organic solvents can use separately, perhaps mix more than 2 kinds and use.
With respect to the coloured material of 100 weight portions in the coloured composition, organic solvent (organic solvent S and the organic solvent except that organic solvent S) can use the amount that adds up to 800～4000 weight portions, preferred 1000～2500 weight portions.
Consider that from the viewpoint that viscosity is low organic solvent S has the ability that keeps reducing crawling, but because insulativity is high thereby charged easily, in the time of in being included in coloured composition, the drawback that exists charging property to rise is because this charged effect causes liquid to accumulate in the end of filming easily.In addition, if coloured material has the electricity with the organic solvent opposite polarity, then organic solvent S also can encourage crawling sometimes.
Therefore, the charging property that reduces the coloured composition that comprises the organic solvent S with low viscous advantage is important factor for formation is filmed uniformly, have the surface conditioner of charging preventive property by interpolation, with coloured composition be adjusted into more than 8.0 at the specific inductive capacity under 25 ℃, conductivity under with 25 ℃ is adjusted into more than the 100nS/cm.
The coloured material carrier that is comprised in the coloured composition of the present invention is to be made of transparent resin, its precursor or their potpourri.Transparent resin is for the transmissivity in the long scope of all-wave of 400～700nm of visible-range is preferably more than 80%, the resin more than 95% more preferably.As transparent resin, can list thermoplastic resin, thermoset resin and photoresist,, can list by radiation exposure and solidify monomer or the oligomer that generates transparent resin as its precursor, these materials can use separately, perhaps mix more than 2 kinds and use.
With respect to the coloured material of 100 weight portions, the coloured material carrier can use the amount of 30～700 weight portions, preferred 60～450 weight portions.In addition, when the potpourri with transparent resin and precursor thereof was used as the coloured material carrier, with respect to the coloured material of 100 weight portions, transparent resin can use the amount of 20～400 weight portions, preferred 50～250 weight portions.In addition, with respect to the coloured material of 100 weight portions, the precursor of transparent resin can use the amount of 10～300 weight portions, preferred 10～200 weight portions.
As thermoplastic resin, for example can listing, butyral resin, styrene-maleic acid copolymer, haloflex, chlorinated polypropylene, Polyvinylchloride, vinyl chloride vinyl acetate copolymer, polyvinyl acetate, polyurethane series resin, vibrin, acrylic resin, alkyd resin, polystyrene, polyamide, rubber are that resin, thermoprene are resin, cellulose family, tygon, polybutadiene, polyimide resin etc.In addition, as thermoset resin, can list for example epoxy resin, benzoguanamine resin, Abietyl modified maleic acid resin, Abietyl modified fumaric resin, melamine resin, urea resin, phenolics etc.
As photoresist; use make have hydroxyl, carboxyl, the substituent wire macromolecule of amino isoreactivity with have isocyanate group, aldehyde radical, substituent (methyl) acyclic compound of epoxy radicals isoreactivity or cinnamic acid and react, thereby in this wire macromolecule, import the resin of photocrosslinking reaction groups such as (methyl) acryloyl group, styryl.In addition, also can use (methyl) acyclic compound of having a hydroxyl by (methyl) acrylic acid hydroxyalkyl acrylate etc. that styrene-maleic anhydride copolymer or alpha-olefin-copolymer-maleic anhydride etc. is comprised the photoresist that the full esterification of wire macromolecule of acid anhydrides obtains.
Monomer and oligomer as the precursor of transparent resin; can list (methyl) methyl acrylate; (methyl) ethyl acrylate; (methyl) acrylic acid 2-hydroxy methacrylate; (methyl) acrylic acid 2-hydroxy propyl ester; (methyl) cyclohexyl acrylate; (methyl) propenoic acid beta-carboxyl ethyl ester; polyglycol two (methyl) acrylate; 1; 6-hexanediol two (methyl) acrylate; triethylene glycol two (methyl) acrylate; tripropylene glycol two (methyl) acrylate; trimethylolpropane tris (methyl) acrylate; pentaerythrite three (methyl) acrylate; 1,6-hexanediol diepoxy propyl ether two (methyl) acrylate; bisphenol-A diepoxy propyl ether two (methyl) acrylate; neopentyl glycol diepoxy propyl ether two (methyl) acrylate; dipentaerythritol six (methyl) acrylate; three ring capryl (methyl) acrylate; the esterification of acrylic ester; (methyl) acrylate of methylolation melamine; (methyl) acrylic acid epoxy ester; various acrylate such as urethane acrylate and methacrylate; (methyl) acrylic acid; styrene; vinyl acetate; the hydroxyethyl vinethene; the ethylene glycol bisthioglycolate vinethene; pentaerythrite triethylene ether; (methyl) acrylamide; N-methylol (methyl) acrylamide; the N-vinyl formamide; vinyl cyanide etc.
As the coloured material that is comprised in the coloured composition of the present invention, organic or inorganic pigment can be used separately, perhaps mix more than 2 kinds and use.In pigment, preferred colour rendering height and the high pigment of thermotolerance, the high pigment of preferred especially heat-resisting decomposability uses organic pigment usually.
Below, use Colour Index (color index) number expression can be preferred for the concrete example of the organic pigment in the coloured composition of the present invention.
In being used to form the red colored composition of red filter joint, for example can use C.I. paratonere 7,9,14,41,48:1,48:2,48:3,48:4,81:1,81:2,81:3,97,122,123,146,149,168,177,178,180,184,185,187,192,200,202,208,210,215,216,217,220,223,224,226,227,228,240,246,254,255,264, red pigments such as 272.In red colored composition, can mix and use yellow uitramarine, orange pigment.
In the yellow coloring composition that is used to form the yellow filter joint, can use for example C.I. pigment yellow 1,2,3,4,5,6,10,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199 yellow uitramarines such as grade.
In being used to form the orange coloured composition of orange filter section, for example can use C.I. pigment orange 36,43,51,55, orange pigments such as 61.
In being used to form the green coloring composition of green filter joint, for example can use C.I. pigment Green 7,10,36, viridine greens such as 37.In green coloring composition, can mix the use yellow uitramarine.
In being used to form the blue colored composition of blue electric-wave filter joint, for example can use C.I. pigment blue 15,15:1,15:2,15:3,15:4,15:6,16,22,60, blue pigments such as 64.In blue colored composition, can mix and use C.I. pigment violet 1, violet pigments such as 19,23,27,29,30,32,37,40,42,50.
In being used to form the cyan coloured composition of cyan filter section, can use for example C.I. pigment blue 15: 1,15:2,15:4,15:3,15:6,16, blue pigments such as 81.
In being used to form the peony coloured composition of peony filter section, can use for example violet pigment and red pigment such as C.I. pigment violet 1,19, C.I. paratonere 144,146,177,169,81.In the peony coloured composition, can mix the use yellow uitramarine.
In being used to form the black colorant composition of black matrix, for example can use that carbon black, nigrosine, anthraquinone are that black pigment, perylene are black pigment, specifically, can use C.I. pigment black 1,6,7,12,20,31 etc.In the black colorant composition, also can use the potpourri of red pigment, blue pigment, viridine green.As black pigment, consider that from the size of price, light-proofness be preferably carbon black, carbon black also can carry out surface treatment with resin etc.In addition, in order to adjust tone, in the black colorant composition, can mix and use blue pigment and violet pigment.
In addition, as inorganic pigment, can list metal oxide powder, metallic sulfide powder, metal powders etc. such as barium sulphate, zinc white, lead sulfate, chrome yellow, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine, general Shandong soil indigo plant, chrome oxide green, cobalt green, amber, black, the synthetic iron oxide black of titanium, titanium dioxide, four iron oxide.In order to keep balance between colorfulness and brightness, to guarantee good coating, sensitivity, development etc. simultaneously, inorganic pigment can be used in combination with organic pigment.
In coloured composition of the present invention,, can in not reducing stable on heating scope, comprise dyestuff in order to mix colours.
In coloured composition of the present invention, when said composition being solidified, can add Photoepolymerizationinitiater initiater by rayed such as ultraviolet rays.
As 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-acetophenones such as 1-ketone are Photoepolymerizationinitiater initiater; benzoin; the benzoin methyl ether; the benzoin ether; the benzoin isopropyl ether; benzoins such as benzyl dimethyl ketal are Photoepolymerizationinitiater initiater; benzophenone; the benzoyl benzoic acid; benzoyl benzoic acid methyl esters; the 4-phenyl benzophenone; dihydroxy benaophenonel; the acrylated benzophenone; 4-benzoyl-4 '-benzophenone series Photoepolymerizationinitiater initiaters such as methyldiphenyl base sulfide; thioxanthones; the 2-clopenthixal ketone; 2-methyl thioxanthones; isopropyl thioxanthone; 2; thioxanthones such as 4-diisopropyl thioxanthones are Photoepolymerizationinitiater initiater; 2; 4; the 6-trichloro-triazine; 2-phenyl-4; two (the trichloromethyl)-s-triazine of 6-; 2-(p-methoxyphenyl)-4; two (the trichloromethyl)-s-triazine of 6-; 2-(p-methylphenyl)-4; two (the trichloromethyl)-s-triazine of 6-; 2-2 acyl group (ピ ペ ニ Le)-4; two (the trichloromethyl)-s-triazine of 6-; 2; two (the trichloromethyl)-6-styryl-s-triazine of 4-; 2-(naphthalene-1-yl)-4; two (the trichloromethyl)-s-triazine of 6-; 2-(4-methoxynaphthalene-1-yl)-4; two (the trichloromethyl)-s-triazine of 6-; 2; 4-trichloromethyl-(piperonyl)-6-triazine; 2,4-trichloromethyl (4 '-methoxyl-styrene)-triazines such as 6-triazine are Photoepolymerizationinitiater initiater; borate-based Photoepolymerizationinitiater initiater; carbazole is a Photoepolymerizationinitiater initiater; imidazoles is a Photoepolymerizationinitiater initiater etc.With respect to the coloured material of 100 weight portions in the coloured composition, Photoepolymerizationinitiater initiater can use the amount of 5～200 weight portions, preferred 10～150 weight portions.
Above-mentioned Photoepolymerizationinitiater initiater can use separately; perhaps mix more than 2 kinds and use; also can mix and use alpha-acyloxy oxime ester, acylphosphine oxide, aminomethyl phenyl glyoxylic ester, benzyl, 9; 10-phenanthrenequione, camphorquinone, EAQ, 4; phenyl-diformyl base benzene, 3,3 ', 4 between 4 '-diethyl; 4 '-four (t-butyl peroxy carbonyl) benzophenone, 4, compounds such as 4 '-diethylamino benzophenone are as sensitizer.With respect to the Photoepolymerizationinitiater initiater of 100 weight portions in the coloured composition, sensitizer can use the amount of 0.1～60 weight portion.
Coloured composition of the present invention can be by using various dispersion means such as triple-roller mill, two roller mill, sand milling, kneader, comminutor with the coloured material more than a kind or 2 kinds, as required with above-mentioned Photoepolymerizationinitiater initiater-fine be dispersed in coloured material carrier and the organic solvent and make.In addition, the coloured composition that comprises coloured material more than 2 kinds also can mix and make then by various coloured materials fine are dispersed in respectively in coloured material carrier and the organic solvent.When coloured material being distributed in coloured material carrier and the organic solvent, can suitably use painted dispersion of materials agent such as resin type pigment dispersing agent, pigment derivative, surfactant.The dispersing of pigments of coloured material spreading agent is good, the effect of the aggegation again of the pigment after preventing to disperse is obvious, therefore, using by using the coloured material spreading agent that pigment dispersing during formed coloured composition, can be obtained the good color filter of the transparency in coloured material carrier and organic solvent.With respect to the coloured material of 100 weight portions in the coloured composition, the coloured material spreading agent can use the amount of 0.1～40 weight portion, preferred 0.1～30 weight portion.
The resin type spreading agent is to comprise pigment compatibility position with the character that is adsorbed onto in the pigment and have the resin at the position of compatibility with the coloring pigment carrier, play a part to be adsorbed onto in the pigment so that pigment to the stably dispersing of painted material support.As the resin type pigment dispersing agent, specifically, can use polyurethane, polycarboxylates such as polyacrylate, 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 hydroxyl polycarboxylate, their modifier, the oiliness spreading agent of the acid amides that the reaction by poly-(low-grade alkylidene acid imide) and the polyester with free carboxy forms or its salt etc., (methyl) acrylic acid-styrol copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol (PVA), water soluble resin or water-soluble high-molecular compounds such as polyvinylpyrrolidone, polyester system, modified polyacrylate system, the ethylene oxide/propylene oxide additive compound, phosphate system etc., these pigment dispersing agents can use separately, perhaps mix more than 2 kinds and use.
Pigment derivative is to import substituent compound in organic pigment.In such organic pigment, also comprise flaxen aromatic series polycyclic compunds such as the naphthalene system that usually is not called as pigment, anthraquinone system.As pigment derivative, can use the pigment derivative of being put down in writing in Japanese kokai publication sho 63-305173 communique, special public clear 57-15620 communique, special public clear 59-40172 communique, special public clear 63-17102 communique, the special fair 5-9469 communique etc., these pigment derivatives can use separately, perhaps can mix more than 2 kinds and use.
As surfactant, can use and to mix the surfactant that uses with aforesaid surface conditioner.
In coloured composition of the present invention,, can comprise the storage-stable agent in order to make the time dependent viscosity stabilization of composition.In addition, in order to improve the adaptation with transparency carrier, also can comprise driving fit reinforcing agents such as silane coupling agent.
As the storage-stable agent, for example can list organic phosphine, phosphites etc. such as organic acid such as hydrochloric acid such as benzyl trimethyl chloride, diethyl hydramine quaternary ammonium salt, lactic acid, oxalic acid and methyl ether thereof, the burnt youngster's phenol of the tert-butyl group, tetraethyl phosphine, tetraphenyl phosphine.With respect to the coloured material of 100 weight portions in the coloured composition, the storage-stable agent can be used the amount of 0.1～10 weight portion.
As silane coupling agent, can list vinyl silanes classes such as vinyl three ('beta '-methoxy ethoxy) silane, vinyl Ethoxysilane, vinyltrimethoxy silane; γ-methacryloxypropyl trimethoxy silane etc. (methyl) acrylic silanes, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, β-(3, the 4-epoxycyclohexyl) methyltrimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, β-(3, the 4-epoxycyclohexyl) methyl triethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-epoxy silane classes such as glycidoxy propyl-triethoxysilicane, N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl) γ-An Jibingjisanyiyangjiguiwan, N-β (amino-ethyl) gamma-amino propyl group methyldiethoxysilane, γ-An Jibingjisanyiyangjiguiwan, the gamma-amino propyl trimethoxy silicane, N-phenyl-gamma-amino propyl trimethoxy silicane, amino silane classes such as N-phenyl-γ-An Jibingjisanyiyangjiguiwan, γ-Qiu Jibingjisanjiayangjiguiwan, Thiosilicane classes such as γ-sulfydryl propyl-triethoxysilicane etc.With respect to the coloured material of 100 weight portions in the coloured composition, silane coupling agent can use the amount of 0.01～10 weight portion, preferred 0.05～5 weight portion.
Coloured composition of the present invention can be prepared into intaglio offset printing-ink, driography printing-ink, silk screenink, solvent develop type or the painted anticorrosive additive material of alkali-developable.The painted anticorrosive additive material of solvent develop type or alkali-developable be by comprise thermoplastic resin, thermoset resin or photoresist as the coloured material carrier, and the composition of monomer, Photoepolymerizationinitiater initiater, surface conditioner, organic solvent in the dispersion staining material form.
Coloured composition of the present invention is preferably by means such as centrifuging, sintered filter, membrane filters, with the oversize grain more than the 5 μ m, be preferably oversize grain more than the 1 μ m, more preferably the oversize grain more than the 0.5 μ m and the dust of sneaking into are removed.
Then, describe at the manufacturing method of color filter of having used coloured composition of the present invention.
Color filter of the present invention has filter section and black matrix on substrate, for example can possess black matrix and red, green, blue filter section.Above-mentioned filter section and/or black matrix can be coated with coloured composition of the present invention by rotary coating mode or mold pressing coating method, thereby are formed on the substrate.
As the substrate of color filter, can use glass plates such as the high soda-lime glass of visible light transmittance, low alkali pyrex, alkali-free aluminium pyrex, resin plates such as polycarbonate, polymethylmethacrylate, polyethylene terephthalate.In addition, for the liquid crystal drive after the panelization, can on the surface of glass plate or resin plate, form the transparency electrode that indium oxide, tin oxide etc. constitute.
When developing, use aqueous solution such as sodium carbonate, NaOH as alkaline-based developer, also can use organic bases such as dimethyl benzyl amine, triethanolamine.In addition, in developer solution, also can add defoamer and surfactant.
As developing method, can use shower development method, spray development method, immersion development method, coating (liquid is contained り) development method (puddle devolopment method) etc.
In addition, in order to improve the sensitivity of ultraviolet exposure, also can be after above-mentioned painted anticorrosive additive material of coating and drying, be coated with water-soluble or alkali soluble resin, for example polyvinyl alcohol (PVA) or water soluble acrylic resin etc. and dry, prevent because the film of the obstruction polymerization that oxygen causes carries out ultraviolet exposure then thereby form.
Embodiment
Below, by embodiment the present invention is carried out more specific description, but in the scope that does not exceed main idea of the present invention, the present invention is not limited to following examples.
In addition, in embodiment and comparative example, " part " and " % " represents " weight portion " and " weight % " respectively.
At first, the preparation at employed acrylic resin soln in embodiment and the comparative example describes.The molecular weight of resin is the weight-average molecular weight by the polystyrene conversion of GPC (gel permeation chromatography) mensuration.
(preparation of acrylic resin soln)
The cyclohexanone that in reaction vessel, adds 370 parts, on one side in container nitrogen injection, heat 80 ℃ on one side, under uniform temp, in 1 hour, drip the potpourri of following monomer and thermal polymerization, carry out polyreaction.
20.0 parts of methacrylic acids
10.0 parts of methyl methacrylates
55.0 parts of butyl methacrylates
15.0 parts of 2-hydroxyethyl methacrylates
4.0 parts of azobis isobutyronitriles
After dropping,, add making 1.0 parts of azobis isobutyronitriles be dissolved in resulting solution in 50 parts the cyclohexanone then, further continue reaction 1 hour down, obtain the solution of acryl resin at 100 ℃ further 100 ℃ of down reactions 3 hours.The weight-average molecular weight of acryl resin is about 40000.
After being cooled to room temperature, get about 2g resin solution as sample, 180 ℃ of following heat dryings 20 minutes, measure nonvolatile component,, add cyclohexanone based on this measured value, nonvolatile component in the previous resin solution that synthesizes reaches 20%, prepares desirable acrylic resin soln.
Embodiment 1
The potpourri of following composition is mixed, use the beaded glass of diameter then, use sand milling to disperse 5 hours, use the filtrator of 5 μ m to filter then, preparation copper phthalocyanine dispersion as 1mm.
Epsilon-copper phthalocyanine (C.I. pigment blue 15: 6) (" ヘ リ オ ゲ Application Block Le one L-6700F " that BASF AG makes) 12.0 parts
2.4 parts of coloured material spreading agents (" ソ Le ス パ one ス 20000 " that Zeneca company makes)
28.1 parts of acrylic resin solns
57.5 parts of cyclohexanone
Then, the potpourri of following composition is mixed, use the filtrator of 1 μ m to filter then, obtain making the coloured composition of blue anticorrosive additive material.The composition of having represented coloured composition at table among the 1A (is 100 weight ratio with the coloured composition total amount; Expression is with respect to the weight of the pigment of 100 weight portions in the bracket).
45.0 parts of copper phthalocyanine dispersions
12.5 parts of acrylic resin solns
4.8 parts of trimethylolpropane triacrylates (" NK EsterATMPT " that Xin Zhong village chemical company makes)
2.5 parts of Photoepolymerizationinitiater initiaters (" the イ Le ガ キ ユ ア one " 907 that Ciba Speciality Chemicals company makes)
0.2 part of sensitizer (protecting " EAB-F " that native ケ paddy chemical company makes)
Surface conditioner A (the dimethyl polysiloxane with polyoxyalkylene: " FZ-2122 " that Toray Dowcorning company makes) 0.01 part
0.99 part of cyclohexanone
34.0 parts of ethylene glycol monoethyl ether acetates
Embodiment 2～13 and comparative example 1～8
Same with embodiment 1, the coloured composition of forming shown in table 1A～table 1E is made versicolor anticorrosive additive material.
Table 1A:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | ||||||
| Color | Blue | Green | Black | Red | Red | |||||
| Composition | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment |
| Pigment | 5.40 | (100) | 5.60 | (100) | 5.50 | (100) | 6.10 | (100) | 6.10 | (100) |
| Pigment dispersing agent | 1.08 | 20 | 1.12 | 20 | 1.10 | 20 | 1.24 | 20 | 1.24 | 20 |
| Acryl resin | 5.03 | 93 | 4.78 | 85 | 4.90 | 89 | 4.66 | 76 | 4.66 | 76 |
| Monomer | 4.80 | 89 | 4.80 | 86 | 4.80 | 87 | 4.60 | 75 | 4.60 | 75 |
| Photoepolymerizationinitiater initiater | 2.50 | 46 | 2.50 | 45 | 2.50 | 45 | 2.20 | 36 | 2.20 | 36 |
| Sensitizer | 0.20 | 3.7 | 0.20 | 3.6 | 0.20 | 3.6 | 0.20 | 3.3 | 0.20 | 3.3 |
| Organic solvent 1 | 46.98 | 870 | 46.99 | 839 | 46.99 | 854 | 46.99 | 770 | 47.00 | 770 |
| Organic solvent 2 | 34.00 | 630 | 34.00 | 607 | 34.00 | 618 | 34.00 | 557 | 34.00 | 557 |
| Organic solvent 3 | - | - | - | - | - | - | - | - | - | - |
| Organic solvent 4 | - | - | - | - | - | - | - | - | - | - |
| Organic solvent 5 | - | - | - | - | - | - | - | - | - | - |
| Surface conditioner A | 0.01 | 0.19 | 0.01 | 0.18 | 0.001 | 0.18 | 0.01 | 0.16 | 0.005 | 0.08 |
| Surface conditioner B | - | - | - | - | - | - | - | - | - | - |
| Surfactant C | - | - | - | - | - | - | - | - | - | - |
| Surfactant D | - | - | - | - | - | - | - | - | - | - |
| Add up to | 100.0 | - | 100.0 | - | 100.0 | - | 100.0 | - | 100.0 | - |
Table 1B
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |||||
| Color | Red | Red | Blue | Green | ||||
| Composition | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment |
| Pigment | 6.10 | (100) | 6.10 | (100) | 5.40 | (100) | 5.60 | (100) |
| Pigment dispersing agent | 1.24 | 20 | 1.24 | 20 | 1.08 | 20 | 1.12 | 20 |
| Acryl resin | 4.66 | 76 | 4.66 | 76 | 5.03 | 93 | 4.78 | 85 |
| Monomer | 4.60 | 75 | 4.60 | 75 | 4.80 | 89 | 4.80 | 86 |
| Photoepolymerizationinitiater initiater | 2.20 | 36 | 2.20 | 36 | 2.50 | 46 | 2.50 | 45 |
| Sensitizer | 0.20 | 3.3 | 0.20 | 3.3 | 0.20 | 3.7 | 0.20 | 3.6 |
| Organic solvent 1 | 47.00 | 770 | 46.99 | 770 | 46.90 | 869 | 46.91 | 838 |
| Organic solvent 2 | 34.00 | 557 | 34.00 | 557 | - | - | - | |
| Organic solvent 3 | - | - | - | - | 34.00 | 630 | 34.00 | 607 |
| Organic solvent 4 | - | - | - | - | - | - | - | |
| Organic solvent 5 | - | - | - | - | - | - | - | |
| Surface conditioner A | 0.03 | 0.49 | - | - | 0.09 | 1.67 | 0.09 | 1.61 |
| Surface conditioner B | - | - | 0.01 | 0.16 | - | - | ||
| Surfactant C | - | - | - | - | - | - | ||
| Surfactant D | - | - | - | - | - | - | ||
| Add up to | 100.0 | - | 100.0 | - | 100.0 | - | 100.0 | - |
Table 1C
| Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | |||||
| Color | Red | Red | Red | Red | ||||
| Composition | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment |
| Pigment | 6.10 | (100) | 6.10 | (100) | 6.10 | (100) | 6.10 | (100) |
| Pigment dispersing agent | 1.24 | 20 | 1.24 | 20 | 1.24 | 20 | 1.24 | 20 |
| Acryl resin | 4.66 | 76 | 4.66 | 76 | 4.66 | 76 | 4.66 | 76 |
| Monomer | 4.60 | 75 | 4.60 | 75 | 4.60 | 75 | 4.60 | 75 |
| Photoepolymerizationinitiater initiater | 2.20 | 36 | 2.20 | 36 | 2.20 | 36 | 2.20 | 36 |
| Sensitizer | 0.20 | 3.3 | 0.20 | 3.3 | 0.20 | 3.3 | 0.20 | 3.3 |
| Organic solvent 1 | 46.91 | 769 | 46.95 | 770 | 46.93 | 769 | 46.91 | 769 |
| Organic solvent 2 | - | - | - | - | - | - | - | |
| Organic solvent 3 | 34.00 | 557 | - | - | 20.00 | 328 | - | - |
| Organic solvent 4 | - | - | 34.00 | 557 | - | - | 34.00 | 557 |
| Organic solvent 5 | - | - | - | - | 14.00 | 230 | - | - |
| Surface conditioner A | 0.09 | 1.48 | 0.05 | 0.82 | 0.07 | 1.15 | - | - |
| Surface conditioner B | - | - | - | - | - | - | 0.09 | 1.48 |
| Surfactant C | - | - | - | - | - | - | - | - |
| Surfactant D | - | - | - | - | - | - | - | - |
| Add up to | 100.0 | 100.0 | - | 100.0 | - | 100.0 | - | |
Table 1D
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |||||
| Color | Red | Red | Red | Red | ||||
| Composition | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment |
| Pigment | 6.10 | (100) | 6.10 | (100) | 6.10 | (100) | 6.10 | (100) |
| Pigment dispersing agent | 1.24 | 20 | 1.24 | 20 | 1.24 | 20 | 1.24 | 20 |
| Acryl resin | 4.66 | 76 | 4.66 | 76 | 4.66 | 76 | 4.66 | 76 |
| Monomer | 4.60 | 75 | 4.60 | 75 | 4.60 | 75 | 4.60 | 75 |
| Photoepolymerizationinitiater initiater | 2.20 | 36 | 2.20 | 36 | 2.20 | 36 | 2.20 | 36 |
| Sensitizer | 0.20 | 3.3 | 0.20 | 3.3 | 0.20 | 3.3 | 0.20 | 3.3 |
| Organic solvent 1 | 47.00 | 770 | 46.68 | 765 | 46.99 | 770 | 46.99 | 770 |
| Organic solvent 2 | 34.00 | 557 | 34.00 | 557 | 34.00 | 557 | 34.00 | 557 |
| Organic solvent 3 | - | - | - | - | - | - | - | - |
| Organic solvent 4 | - | - | - | - | - | - | - | - |
| Organic solvent 5 | - | - | - | - | - | - | - | - |
| Surface conditioner A | - | - | 0.32 | 5.2 | -- | -- | - | - |
| Surface conditioner B | - | - | - | - | - | - | - | |
| Surfactant C | - | - | - | - | 0.01 | 0.16 | - | - |
| Surfactant D | - | - | - | - | - | - | 0.01 | 0.16 |
| Add up to | 100.0 | - | 100.0 | - | 100.0 | - | 100.0 | - |
Table 1E
| Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |||||
| Color | Blue | Red | Red | Red | ||||
| Composition | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment | Part | Part with respect to 100 parts of pigment |
| Pigment | 5.40 | (100) | 6.10 | (100) | 6.10 | (100) | 6.10 | (100) |
| Pigment dispersing agent | 1.08 | 20 | 1.24 | 20 | 1.24 | 20 | 1.24 | 20 |
| Acryl resin | 5.02 | 93 | 4.66 | 76 | 4.66 | 76 | 4.66 | 76 |
| Monomer | 4.80 | 89 | 4.60 | 75 | 4.60 | 75 | 4.60 | 75 |
| Photoepolymerizationinitiater initiater | 2.50 | 46 | 2.20 | 36 | 2.20 | 36 | 2.20 | 36 |
| Sensitizer | 0.20 | 3.7 | 0.20 | 3.3 | 0.20 | 3.3 | 0.20 | 3.3 |
| Organic solvent 1 | 46.99 | 870 | 47.00 | 770 | 46.91 | 769 | 46.91 | 769 |
| Organic solvent 2 | 34.00 | 630 | - | - | - | - | - | - |
| Organic solvent 3 | - | - | 34.00 | 557 | 34.00 | 557 | 34.00 | 557 |
| Organic solvent 4 | - | - | - | - | - | - | - | - |
| Organic solvent 5 | - | - | - | - | - | - | - | - |
| Surface conditioner A | - | - | - | - | - | - | - | - |
| Surface conditioner B | - | - | - | - | - | - | - | - |
| Surfactant C | - | - | - | - | 0.09 | 1.48 | - | - |
| Surfactant D | 0.01 | 0.19 | - | - | - | - | 0.09 | 1.48 |
| Add up to | 100.0 | - | 100.0 | - | 100.0 | - | 100.0 | - |
In table 1A～table 1E:
Organic solvent 1: cyclohexanone
Organic solvent 2: ethylene glycol monoethyl ether acetate
Organic solvent 3: isoamyl acetate
Organic solvent 4:3-ethoxyl ethyl propionate
Organic solvent 5: propylene glycol methyl ether acetate
The red pigment of using:
5.08 parts of diketopyrrolo-pyrrole series pigments (C.I. paratonere 254) (" イ Le ガ Off オ one レ Star De B-CF " that Ciba Speciality Chemicals company makes)
0.82 part of anthraquione pigments (C.I. paratonere 177) (" Network ロ モ Off one Le レ Star De A2B " that Ciba Speciality Chemicals company makes)
0.20 part of anthraquione pigments (C.I. pigment yellow 199) (" Network ロ モ Off one Le エ ロ one GT-AD " that Ciba Speciality Chemicals company makes)
Add up to 6.10 parts
The green pigment of using:
3.60 parts of copper halide phthualocyanine pigments (C.I. pigment green 36) (" リ オ ノ one Le グ リ one Application 6YK " that Toyo Ink manufacturing company makes)
2.00 parts of nickel azo complex compound series pigments (C.I. pigment yellow 150) (" E4GN " that Lanxess company makes)
Add up to 5.60 parts
The blue pigment of using:
Epsilon-copper phthalocyanine (C.I. pigment blue 15: 6) (" ヘ リ オ ゲ Application Block Le one L-6700F " that BASF AG makes) 5.40 parts
Black pigment:
5.50 parts of carbon blacks (" Printex 75 " that テ グ サ company makes)
Surface conditioner A: dimethyl polysiloxane (" FZ-2122 " that Toray Dowcorning company makes) with polyoxyalkylene
Surface conditioner B: dimethyl polysiloxane (" FZ-2110 " that Toray Dowcorning company makes) with polyoxyalkylene
Surfactant C: the aralkyl modified silicone is surfactant (" BYK-323 " that BYK-Chemie company makes)
Surfactant D: fluorochemical surfactant (" BL-20 " that Japanese ink chemical industrial company makes)
Measure the A value and the B value of embodiment 1～7 and comparative example 1～5 resulting anticorrosive additive material of all kinds according to the Wilhelmy flat band method, and use the normal hydrometer mensuration proportion separately of peace rattan gauge system worker manufacturing, calculate the value of A ', derive " B-A ' ".The result is shown in table 3A～3D.
Measure specific inductive capacity, conductivity and the viscosity characteristics of employed organic solvent S in embodiment 8～13 and the comparative example 6～8 by following analyzer.The result is as shown in table 2.
Specific inductive capacity: the 870 liquid dielectric instrument that BROOKHAVEN instrument company makes
Conductivity: 645 types and 627 type electric conductivity meters that Scientifica company makes
Viscosity: E type viscosity meter (the TUE-20L type that TOKI SANGYO company makes), under the rotating speed of 100rpm, measure.
Table 2
| Solvent | Specific inductive capacity | Conductivity | Viscosity |
| nS/cm | mPa·s | ||
| Isoamyl acetate | 4.81 | 0.028 | 0.87 |
| The 3-ethoxyl ethyl propionate | 5.88 | 0.15 | 1.24 |
| Propylene glycol methyl ether acetate | 8.15 | 0.88 | 1.14 |
Measure embodiment 8～13 and specific inductive capacity and the conductivity of comparative example 6～8 resulting versicolor anticorrosive additive materials under 25 ℃ by the said determination device.The result is shown in table 3A～3D.
Then, use E type viscosity meter (the TUE-20L type that TOKI SANGYO company makes), measuring embodiment 1～13 and the viscosity of comparative example 1～8 resulting versicolor anticorrosive additive material under 25 ℃ under the rotating speed of 20rpm.The result is shown in table 3A～3D.
In addition, use the apparatus for coating of mold pressing coating method and rotary coating mode, on the glass substrate of 360mm * 465mm size, be coated with respectively, reach 2.0 μ m until average film thickness, under 70 ℃, resulting coated substrates carried out 20 minutes prebake, obtain dry coating.Method for expressing to assessment item, content and result describes below.
(blank spot)
" blank spot ": at coated substrates, use white transmitted light by visualization substrate integral body, the situation that the situation of no blank spot is designated as zero, have the situation of 1～3 blank spot to be designated as △, observe 4 above blank spots is designated as *.
(irregular colour)
" length of end irregular colour ": make the face of white light transmission coating, by the end that visualization is filmed, uneven boundary length less than the situation of 5mm be designated as zero, more than the 5mm but be designated as △, situation more than the 10mm less than the situation of 10mm and be designated as *.
" integral color inequality ": make the face of white light transmission coating,, estimate uneven degree by the end that visualization is filmed.Do not have uneven situation to be designated as zero, have uneven situation to be designated as △, serious situation slightly to be designated as *.
(film thickness uniformity)
" film thickness uniformity (end) ": the central authorities of minor face one end of filming from coating up to 5cm, measure thickness every 5mm along substrate center's direction.Maximum film thickness is designated as Tmax, and minimum thickness is designated as Tmin, and average film thickness is designated as Tavg, calculates film thickness uniformity (end) by following formula (6).
" film thickness uniformity (beyond the end) ": from the substrate center of coated substrates along diagonal up to 26cm, measure thickness every 2mm.With above-mentioned the same, calculate film thickness uniformity (beyond the end) by following formula (6).
Film thickness uniformity [%]=((Tmax-Tmin)/(Tavg * 2)) * 100 (6)
Film thickness uniformity [%] is preferably below 5%, if be below 2%, can judge that then homogeneity is very high.
(bar inequality)
" bar inequality ": the substrate at the mold pressing coating, use white transmitted light to carry out the evaluation of bar inequality.By visualization, the situation of no bar inequality is designated as zero, and the situation of observing the bar inequality is designated as *.
Each evaluation result is shown in table 3A～3D.
Table 3A
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| The measured value of composition | A(mN) | 1.24 | 1.26 | 1.21 | 1.22 | 1.27 | 1.20 | 1.23 |
| Proportion (g/cm 3) | 0.997 | 1.006 | 0.999 | 1.002 | 1.002 | 1.002 | 1.001 | |
| B-A’(mN) | 0.14 | 0.12 | 0.10 | 0.09 | 0.09 | 0.10 | 0.09 | |
| Specific inductive capacity | - | - | - | - | - | - | - | |
| Conductivity (nS/cm) | - | - | - | - | - | - | - | |
| Coating fluid viscosity (mPas) | 5.2 | 5.3 | 5.5 | 4.3 | 4.2 | 4.1 | 4.2 | |
| Method of spin coating is estimated | Blank spot | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The length of end irregular colour | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| The integral color inequality | ○ | ○ | ○ | ○ | △ | ○ | ○ | |
| Film thickness uniformity 1 (end) | 2.58 | 3.21 | 2.76 | 1.87 | 2.23 | 1.15 | 1.98 | |
| Film thickness uniformity 2 (beyond the end) | 2.54 | 3.12 | 2.95 | 1.64 | 2.66 | 1.33 | 2.06 | |
| The mold pressing rubbing method is estimated | Blank spot | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| The length of end irregular colour | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| The integral color inequality | ○ | ○ | ○ | ○ | △ | ○ | ○ | |
| Film thickness uniformity 1 (end) | 2.97 | 3.17 | 2.20 | 1.69 | 1.95 | 1.39 | 1.60 | |
| Film thickness uniformity 2 (beyond the end) | 1.78 | 2.67 | 2.08 | 1.55 | 1.99 | 1.22 | 1.72 | |
| The bar inequality | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Table 3B
| Project | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | |
| The measured value of composition | A(mN) | - | - | - | - | - | - |
| Proportion (g/cm 3) | - | - | - | - | - | - | |
| B-A’(mN) | - | - | - | - | - | - | |
| Specific inductive capacity | 8.21 | 8.35 | 8.32 | 8.56 | 8.89 | 8.15 | |
| Conductivity (nS/cm) | 1.55 | 2.80 | 220 | 250 | 340 | 185 | |
| Coating fluid viscosity (mPas) | 7.5 | 8.1 | 5.1 | 5.1 | 5.1 | 5.2 | |
| Method of spin coating is estimated | Blank spot | ○ | ○ | ○ | ○ | ○ | ○ |
| The length of end irregular colour | ○ | ○ | ○ | ○ | ○ | ○ | |
| The integral color inequality | ○ | ○ | ○ | ○ | ○ | ○ | |
| Film thickness uniformity 1 (end) | 2.86 | 3.09 | 2.51 | 1.71 | 2.18 | 1.98 | |
| Film thickness uniformity 2 (beyond the end) | 2.10 | 2.78 | 2.15 | 1.82 | 2.08 | 1.92 | |
| The mold pressing rubbing method is estimated | Blank spot | ○ | ○ | ○ | ○ | ○ | ○ |
| The length of end irregular colour | ○ | ○ | ○ | ○ | ○ | ○ | |
| The integral color inequality | ○ | ○ | ○ | ○ | ○ | ○ | |
| Film thickness uniformity 1 (end) | 2.99 | 3.15 | 2.76 | 1.95 | 2.26 | 2.00 | |
| Film thickness uniformity 2 (beyond the end) | 2.02 | 2.72 | 1.96 | 1.65 | 1.89 | 1.89 | |
| The bar inequality | ○ | ○ | ○ | ○ | ○ | ○ |
Table 3C
| Project | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| The measured value of composition | A(mN) | 1.29 | 1.15 | 1.14 | 1.12 |
| Proportion (g/cm 3) | 1.001 | 1.003 | 1.002 | 1.001 | |
| B-A’(mN) | 0.02 | 0.16 | 0.11 | 0.20 | |
| Specific inductive capacity | - | - | - | - | |
| Conductivity (nS/cm) | - | - | - | - | |
| Coating fluid viscosity (mPas) | 4.5 | 5.4 | 4.3 | 4.3 | |
| Method of spin coating is estimated | Blank spot | × | ○ | ○ | △ |
| The length of end irregular colour | ○ | × | × | × | |
| The integral color inequality | × | ○ | ○ | ○ | |
| Film thickness uniformity 1 (end) | 7.89 | 2.19 | 3.28 | 6.57 | |
| Film thickness uniformity 2 (beyond the end) | 8.92 | 1.88 | 3.54 | 5.89 | |
| The mold pressing rubbing method is estimated | Blank spot | × | ○ | ○ | △ |
| The length of end irregular colour | ○ | × | × | × | |
| The integral color inequality | × | ○ | ○ | ○ | |
| Film thickness uniformity 1 (end) | 8.28 | 2.11 | 3.16 | 6.94 | |
| Film thickness uniformity 2 (beyond the end) | 6.59 | 1.61 | 2.88 | 4.76 | |
| The bar inequality | × | ○ | ○ | × |
Table 3D
| Project | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| The measured value of composition | A(mN) | 1.16 | - | - | - |
| Proportion (g/cm 3) | 0.996 | - | - | - | |
| B-A’(mN) | 0.19 | - | - | - | |
| Specific inductive capacity | - | 6.88 | 7.21 | 6.82 | |
| Conductivity (nS/cm) | - | 77 | 75 | 82 | |
| Coating fluid viscosity (mPas) | 5.4 | 5.1 | 5.1 | 5.1 | |
| Method of spin coating is estimated | Blank spot | △ | × | ○ | ○ |
| The length of end irregular colour | × | △ | × | × | |
| The integral color inequality | ○ | × | × | × | |
| Film thickness uniformity 1 (end) | 6.89 | 5.80 | 5.26 | 6.75 | |
| Film thickness uniformity 2 (beyond the end) | 6.01 | 5.57 | 4.17 | 5.14 | |
| The mold pressing rubbing method is estimated | Blank spot | △ | × | ○ | ○ |
| The length of end irregular colour | × | △ | × | × | |
| The integral color inequality | ○ | × | × | × | |
| Film thickness uniformity 1 (end) | 6.59 | 5.88 | 5.35 | 6.97 | |
| Film thickness uniformity 2 (beyond the end) | 4.78 | 5.19 | 4.02 | 4.87 | |
| The bar inequality | ○ | × | ○ | ○ |
That uses that the coloured composition of embodiment 1～4,6 and 7 forms films in method of spin coating evaluation and mold pressing rubbing method are estimated, and whole assessment items has all obtained good evaluation result.Though the discovery slightly " integral color inequality " of filming of using the coloured composition of embodiment 5 to form, other assessment item is the same with other embodiment, has all obtained good evaluation result.
Though it is more than the 1.16mN that comparative example 1 satisfies A, but " B-A ' " less than 0.08, so its evaluation result is: " blank spot " is many, and " integral color inequality " is serious, " film thickness uniformity (outside end, the end) " is poor, and observes " bar inequality " in the mold pressing rubbing method.
In comparative example 2 and 3, though satisfy 0.08≤B-A '≤0.18[mN], A is below the 1.16mN, " length of end irregular colour " is long.
In comparative example 4, " B-A ' " surpasses 0.18mN and A less than 1.16mN, so its evaluation result is: " blank spot " is poor slightly, and " length of end irregular colour " is long, " film thickness uniformity (outside end, the end) " is poor, and observes " bar inequality " in the mold pressing rubbing method.
In comparative example 5, be more than the 1.16mN though satisfy A, " B-A ' " surpass 0.18mN, so its evaluation result is: " blank spot " is poor slightly, and " length of end irregular colour " is long, and " film thickness uniformity (outside end, the end) " is poor.
The specific inductive capacity of the coloured composition that embodiment 8～13 obtains is more than 8.0 and conductivity has fully surpassed 100nS/em, therefore, has all obtained good result in all estimating.
The specific inductive capacity of the coloured composition that comparative example 6～8 obtains less than 8.0 and conductivity less than 100nS/cm, therefore, can not obtain good film.
Claims (5)
1. coloured composition, it is for comprising by transparent resin, its precursor or their the coloured material carrier that potpourri constituted, coloured material, organic solvent, and the aqueous coloured composition of surface conditioner, it is characterized in that: according to the Wilhelmy flat band method, with the plane is the square of 22mm * 22mm, thickness is that the glass plate of 0.145mm is immersed in the described aqueous coloured composition, make a limit of described glass plate on the vertical direction vertical, flood 2.5mm with respect to the liquid level of this liquid composition, at this moment, the power A of mensuration are more than the 1.16mN under the stationary state of described glass plate and under 25 ℃, and the power A ' that obtains after described power A deducts the buoyancy of the described glass plate the described coloured composition, the power B that the described glass plate when vertically promoting the glass plate of described dipping with the speed of 2.5mm/ second under 25 ℃ was measured from the moment that aqueous coloured composition breaks away from satisfies following relation: 0.08≤B-A '≤0.18.
2. coloured composition according to claim 1 is characterized in that: described surface conditioner is the dimethyl polysiloxane with polyoxyalkylene.
3. coloured composition according to claim 1 and 2, it is characterized in that: described organic solvent comprises organic solvent S with the ratio more than the 5 weight %, and this organic solvent S at the specific inductive capacity under 25 ℃ is below 10.0, be below the 1nS/cm and the viscosity under 25 ℃ is below the 1.5mPas in the conductivity under 25 ℃; Described coloured composition at the specific inductive capacity under 25 ℃ is more than 8.0, be more than the 100nS/cm and the viscosity under 25 ℃ is below the 20mPas in the conductivity under 25 ℃.
4. want 3 described coloured compositions according to right, it is characterized in that: described organic solvent S is at least a organic solvent that is selected from isoamyl acetate, 3-ethoxyl ethyl propionate, the propylene glycol methyl ether acetate.
5. color filter, it possesses by formed filter section of the described coloured composition of claim 1 and/or black matrix.
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| JP5176430B2 (en) * | 2007-08-23 | 2013-04-03 | 東洋インキＳｃホールディングス株式会社 | Color filter formed by using coloring composition for spin coating |
| KR101608292B1 (en) * | 2008-02-22 | 2016-04-01 | 후지필름 가부시키가이샤 | Colored curable composition, colored pattern, color filter and method of manufacturing the same, and liquid crystal display device |
| JP5446507B2 (en) * | 2009-06-26 | 2014-03-19 | 大日本印刷株式会社 | Resin composition containing lake pigment |
| JP6914330B2 (en) * | 2017-06-02 | 2021-08-04 | 富士フイルム株式会社 | Method for manufacturing coating composition and laminate |
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| JP4691877B2 (en) * | 2002-08-08 | 2011-06-01 | 住友化学株式会社 | Colored photosensitive resin composition |
| JP3860806B2 (en) * | 2002-12-19 | 2006-12-20 | Ｊｓｒ株式会社 | Method for forming colored layer for color filter |
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