CN102279522A - Coloring composition for color filter and color filter - Google Patents

Coloring composition for color filter and color filter Download PDF

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Publication number
CN102279522A
CN102279522A CN2011101596244A CN201110159624A CN102279522A CN 102279522 A CN102279522 A CN 102279522A CN 2011101596244 A CN2011101596244 A CN 2011101596244A CN 201110159624 A CN201110159624 A CN 201110159624A CN 102279522 A CN102279522 A CN 102279522A
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Prior art keywords
pigment
black
composition
color filter
parts
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CN2011101596244A
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CN102279522B (en
Inventor
近藤庆一
门胁智之
早坂努
山本裕一
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Toyocolor Co Ltd
Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
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Priority claimed from JP2011078191A external-priority patent/JP5741141B2/en
Priority claimed from JP2011078192A external-priority patent/JP5673302B2/en
Priority claimed from JP2011078189A external-priority patent/JP2012212054A/en
Application filed by Toyo Ink SC Holdings Co Ltd, Toyochem Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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

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  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)

Abstract

The invention provides a coloring composition for a color filter and the color filter. One embodiment of the invention relates to a coloring composition for the color filter. The coloring composition is characterized by comprising a coloring agent, a resin type dispersant and a solvent. The coloring agent comprises pigment having an average particle size ranging from 20 nm to 50 nm and a particle aspect ratio ranging from 1:1 to 1: 3.5. The resin type dispersant comprises an acrylic acid system segmented copolymer. The acrylic acid system segmented copolymer is an A-B segmented copolymer or B-A-B segmented copolymer composed of an A segment having solvent responsiveness and a B segment having functional groups comprising nitrogen atoms. The amine value of the acrylic acid system segmented copolymer, by effective solid constituents, ranges from 10 mg KOH/g to 99mg KOH/g.

Description

Color composition for color filter and color filter
Technical field
The present invention relates to possess color composition for color filter, the driving substrate of the color filter of filter section and/or black matrix, black-colored resin composition, black matrix and thin film transistor (TFT) (TFT) mode color liquid crystal display arrangement.
Background technology
Liquid crystal indicator is to controlling by the polarisation of light degree of the 1st polaroid and to controlling the display device that shows by the light quantity of the 2nd polaroid, using the type of twisted nematic (TN) type liquid crystal to become main flow by the liquid crystal layer that clips in 2 polaroids.As other the mode of representative liquid crystal indicator, have on the substrate of a side, be provided with pair of electrodes and the direction that is parallel to substrate apply electric field plane conversion (IPS) mode, make vertical orientated homeotropic alignment (VA) mode of nematic crystal with negative dielectric anisotropy and make the optical axis mutually orthogonal of uniaxiality phase retardation film carry out optical compensation curved arrangement (OCB) mode of optical compensation etc., and equal practicability.
Liquid crystal indicator can carry out the colour demonstration by color filter is set between 2 polaroids, in recent years, owing to be used for TV and PC monitor etc. gradually, therefore the high-contrastization of color filter, the requirement of high brightnessization have been improved.
Color filter be parallel on the surface of transparency carriers such as glass or dispose across different tones more than 2 kinds fine band (bar) shape filter section or form by the fine filter section of the certain alignment arrangements of length and width.Filter section is fine to several microns～hundreds of micron, and every kind of tone marshalling configuration in accordance with regulations.
Usually, in the color liquid crystal display arrangement, the transparency electrode that is used on color filter driving liquid crystal forms by evaporation or sputter, and then is formed for alignment films that liquid crystal is orientated by certain orientation thereon.In order fully to obtain the performance of these transparency electrodes and alignment films, it forms usually need be more than 200 ℃, preferably carry out under the high temperature more than 230 ℃.Therefore, at present,, the pigment of photostability, excellent heat resistance is become main flow as the method that is called the pigment dispersing method of colorant as manufacturing method of color filter.
But the color filter that is dispersed with pigment usually exists because the light scattering that pigment causes etc., and chaotic problem takes place the polarization degree of liquid crystal control.That is, must interdict the light time (OFF state), light leaks, and perhaps, must see through the light time (ON state), sees through light and is decaying, and the ratio (contrast) of the brightness on the display device when therefore having ON state and OFF state hangs down such problem.
For high brightnessization, the high-contrastization that realizes color filter, mostly pigment contained in the filter section is carried out miniaturization and handle and use.But, simply by various miniaturization disposal routes to pigment (the so-called rough thing that will be 10～100 μ m by the particle diameter of chemical reaction manufacturing is handled until the potpourri that obtains the offspring that primary particle and gathering thereof form by pigmentation) when carrying out miniaturization, carry out the pigment of the miniaturization of primary particle or offspring and also assembled easily usually, when excessively carrying out miniaturization, also can form huge block pigment solids material.Further, be scattered in the pigment carrier that contains resin etc., make its stabilization, also be difficult to obtain stable coloured composition thereby make the offspring of pigment approach primary particle as far as possible again even carried out the pigment of miniaturization.
Known in addition, will implement pigment dispersing that miniaturization handles in the pigment carrier that contains resin etc. and the color composition for color filter that forms is difficult to stable and high concentration ground dispersed color, thereby can cause variety of issue manufacturing process and goods itself.
For example, the color compositions that contains the pigment that is made of minuteness particle often shows high viscosity, not only becomes difficult from dispersion machine taking-up and conveying goods, and bad situation also is included in generation gelation in the preservation and causes use to become difficult.Further, about the surface of the color development thing of color compositions, it is bad to produce states such as gloss descends, levelability is bad.In addition, when the different types of pigment of mixing uses, because the remarkable decline of color spot, colorability appears in phenomenons such as the color spot that gathering causes, sedimentation sometimes on the color development thing.
Therefore, keep good, utilize the resin type spreading agent usually in order to make disperse state.The resin type spreading agent have concurrently the position that is adsorbed in pigment and with structure as the high position of the solvent compatibility of dispersion medium, performance is decided by the balance at the position of these 2 functions.The resin type spreading agent can be according to using various materials as the surface state of the pigment that is disperseed thing.
With regard to the resin type spreading agent, the resin type spreading agent of known structure control with block type structure (patent documentation 1) and comb shaped structure (patent documentation 2) is as the resin type spreading agent of pigment-dispersing excellence.With regard to arbitrary situation,, therefore,, and has the tendency of a large amount of interpolations in order to ensure dispersion stabilization owing to the development of pigment miniaturization in recent years, the increase of surface area.There is following situation thus: because the increase of spreading agent, cause the decreased solubility of developer solution or spreading agent self dissolubility variation, thereby in official hour, can't develop to developer solution; Perhaps promptly enable to develop the also not dissolved matter of easy residual colored resin composition in non-image after the development.And then, if the not dissolved matter of residual colored resin composition in non-image on substrate, then can cause the transmitance of gained color filter and decrease of contrast etc., in addition, under the situation that residues in pattern edge portion, can cause sealing deterioration in the peeling off of ITO film, the liquid crystal cells chemical industry preface etc., thereby become the situation that the back operation is impacted.
Under the situation of comb shaped structure; oriented polyamino compound grafting with primary amino radical or secondary amino group has the part of the formation broach of functional groups such as carboxyl or acryloyl group; make residual primary amine or secondary amine become the method for the functional group that is adsorbed in surface of pigments; but primary amine or secondary amine have reactive high reactive hydrogen, and therefore this method is not preferred.
About color filter, not only require high-contrastization as previously mentioned, also require high brightnessization.In order to obtain high brightness, in pigment carrier, can make it approach primary particle during dispersed color usually, thereby improve the transparency of dispersion, owing to make the spectrophotometric spectra of dispersion have high permeability, therefore obtain high brightness.
In order to address the above problem, the structure, acid number etc. of improvement acrylic acid series segmented copolymer have been done, with the trial (with reference to patent documentation 3,4,5) of a spot of interpolation improvement pigment-dispersing.
In addition, at the gap portion of the red, green, blue filter section of color filter, be purpose to improve contrast, form and have black matrix of being called of light-proofness the cancellate black pattern of (below, BM made in brief note sometimes) usually.
With regard to black matrix,, require its light-proofness excellence in order to optimize the image quality of liquid crystal display.
In addition, in recent years, in order to tackle high more meticulous, high brightnessization, form the method for black matrix from such in the past at filter substrate, carried out the research that driving at thin film transistor (TFT) (TFT) mode color liquid crystal display arrangement forms BOA (the Black Matrix on Array) mode of black matrix on substrate.In this BOA method, do not need to be used for such in the past stickup operation with the element contraposition, and owing to can significantly increase pixel relative aperture (aperture opening ratio), shorten manufacturing process, also owing to can improve display quality, cutting down cost, therefore to compare advantage many with the BM that forms on filter substrate.
Because these BM also require high light-proofness, therefore require the decentralized stabilization under the high pigment levels, also be necessary also to give simultaneously high definition.With colored resist similarly, with in the coloured composition, also exist following problem at black matrix:, so, can not in official hour, develop because for obtaining the addition that dispersion stabilization tends to increase spreading agent to the dissolubility variation of developer solution; Even perhaps can develop, also not dissolved matter of easy residual colored resin composition etc. in the non-pixel portions after development.
In addition, be when array base palte one side form BM, owing to BM self directly is exposed in the driving electric field of liquid crystal, so the specific inductive capacity Gao Shihui of BM self causes that the demonstration of liquid crystal display is bad.In addition, therefore the mask alignment that BM carries out when forming also needs the light transmission rate of the near infrared region of certain level owing to use infrared camera to carry out.Therefore, for mainly being used as the carbon black of BM material in the past, not only show high-k, lack insulativity, and the light transmission rate of near infrared region being also low, therefore be difficult to calibrate, be difficult to use in the liquid crystal panel of BOA mode.
As the method that solves such problem, disclose the method (with reference to patent documentation 6) of carbon black and at least a organic pigment combination thereby, do not use carbon black and only use the combination of organic pigment possess light-proofness method (with reference to patent documentation 7,8), use carbon black and be the method (with reference to patent documentation 9～11) etc. of black pigment as black organic system pigment De perylene, but can not all satisfy from light-proofness, the electrical specification of black matrix component and the sufficient light transmission rate that is used for the near infrared region of mask alignment operation.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-31713 communique
Patent documentation 2: Japanese kokai publication hei 11-1515 communique
Patent documentation 3: TOHKEMY 2006-265528 communique
Patent documentation 4: TOHKEMY 2006-321979 communique
Patent documentation 5: TOHKEMY 2009-25813 communique
Patent documentation 6: TOHKEMY 2005-215150 communique
Patent documentation 7: TOHKEMY 2009-069822 communique
Patent documentation 8: TOHKEMY 2009-282251 communique
Patent documentation 9: Japanese kokai publication hei 6-289602 communique
Patent documentation 10: Japanese kokai publication hei 4-190362 communique
Patent documentation 11: Japanese kokai publication hei 10-219167 communique
Summary of the invention
In the 1st embodiment, purpose is to provide a kind of excellent dispersion, good fluidity, stable and color composition for color filter that development is also excellent and has used filter section this color composition for color filter, that have high-contrast or the high-quality color filter of the black matrix that optical density is high.
The inventor etc. have carried out active research repeatedly in order to solve aforementioned all problems, found that: containing average primary particle diameter by use is that the aspect ratio of 20～50nm and pigment particles is the colorant of 1: 1～1: 3.5 pigment, and use the acrylic acid series segmented copolymer as the resin type spreading agent, thereby solve above-mentioned problem, described acrylic acid series segmented copolymer is A-B segmented copolymer or the B-A-B segmented copolymer that is made of A block with solvophilic and the B block with functional group of nitrogen atom, and the amine value is scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent.
Promptly, the 1st embodiment relates to a kind of color composition for color filter, it is for containing colorant, the color composition for color filter of resin type spreading agent and solvent, it is characterized by, it is that the aspect ratio of 20～50nm and pigment particles is 1: 1～1: 3.5 a pigment that this colorant contains average primary particle diameter, this resin type spreading agent contains the acrylic acid series segmented copolymer, and described acrylic acid series segmented copolymer is A-B segmented copolymer or the B-A-B segmented copolymer that is made of A block with solvophilic and the B block with functional group of nitrogen atom, and the amine value is scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent.
With regard to aforementioned acrylic acid series segmented copolymer, in having the A block of solvophilic, can contain the represented repetitive of following general formula (I) of 5～40 moles of %, in the B of functional group block, can contain the represented repetitive of following general formula (II) with nitrogen atom.
Figure BSA00000517935500051
[in the general formula (I), n represents 1～5 integer, R 1Expression hydrogen atom or methyl.]
Figure BSA00000517935500052
[in the general formula (II), R 4And R 5Respectively independently expression can have substituent ring-type or chain alkyl, can have substituent aryl and maybe can have substituent aralkyl, R 3The expression carbon number is the alkylidene more than 1, R 2Expression hydrogen atom or methyl.]
In addition, with regard to aforementioned acrylic acid series segmented copolymer, in having the A block of solvophilic, can further contain the formation unit of the formation unit that general formula (I) is represented (methyl) acrylic ester monomer in addition of 50～90 moles of % as presoma.
In addition, to Wei perylene be black pigment to aforementioned colorant Ke Yi.
In addition, foregoing can further contain the pigment derivative as acid derivant or its slaine of organic pigment.
In addition, foregoing can further contain photopolymerization monomer and Photoepolymerizationinitiater initiater.
In addition, the 1st embodiment relates to a kind of color filter, it is characterized by, and possesses the filter section and/or the black matrix that are formed by aforementioned color composition for color filter on the substrate.
The related color composition for color filter of the 1st embodiment is the stable color composition for color filter of mobile and development excellence, by using this color composition for color filter, can form the black matrix pattern of the shades of colour filter section and the high light intensity of high-contrast.Therefore, by using this color composition for color filter, can access high-quality color filter.
In the 2nd embodiment, purpose is to provide a kind of be used to the make flowability of black matrix, the black-colored resin composition of excellent in stability, and all excellent black matrix of light transmission rate that uses its light-proofness, electrical specification and near infrared region, especially for the driving of thin film transistor (TFT) (TFT) mode color liquid crystal display arrangement black matrix with substrate.
The 2nd embodiment relates to a kind of black-colored resin composition, it is the black-colored resin composition that contains light-proofness black pigment, resin and solvent, it is characterized by, this light-proofness black pigment be below the 50nm by average primary particle diameter and the aspect ratio of primary particle be 1: 1～1: 2 De perylene be black pigment and carbon black to constitute Gai perylene of be that the content of black pigment is 78～95 weight % when being benchmark with the total weight of light-proofness black pigment (A), and solid component concentration is that 5 weight % are above and less than 40 weight %.
Qian Shu perylene is that the average primary particle diameter of black pigment can be 20～45nm.
Foregoing can further contain pigment dispersing agent.
Aforementioned pigment dispersing agent can comprise the precursor skeleton with organic pigment and the pigment derivative of alkali subtituent.
Aforementioned pigment dispersing agent can further contain acidic resins type spreading agent.
Foregoing can further contain ethene unsaturated compound and Photoepolymerizationinitiater initiater.
In addition, the 2nd embodiment relates to a kind of black matrix that is formed by aforementioned black-colored resin composition.
The relative dielectric constant of aforementioned black matrix when dry film thickness is 1.0 μ m can be below 8.0.
The light transmission rate of the wavelength 780nm of aforementioned black matrix when dry film thickness is 1.0 μ m can be more than 15% and less than 99%.
The optical density of aforementioned black matrix when dry film thickness is 1.0 μ m can be more than 2.50.
The 2nd embodiment relates to a kind of driving substrate that is characterized as the thin film transistor (TFT) mode color liquid crystal display arrangement that possesses aforementioned black matrix.
The black matrix that the 2nd embodiment is related is because the light-proofness excellence, so demonstration contrast excellence of color liquid crystal display arrangement, and because low-k characteristic, the undesirable condition that the electrical specification of the black matrix that the interelectrode conducting that therefore is difficult to produce the orientation confusion of liquid crystal or forms on the TFT substrate is such causes, and because the light transmission rate excellence of near infrared region, therefore can also carry out the mask alignment operation, thereby also be suitable for the driving substrate of thin film transistor (TFT) (TFT) mode color liquid crystal display arrangement.
In the 3rd embodiment, purpose is to provide all excellent black matrix of transmitance of a kind of light-proofness, electrical specification and near infrared region, especially for the driving of thin film transistor (TFT) (TFT) the mode color liquid crystal display arrangement black matrix of substrate, and be used to make the flowability of this black matrix, the black-colored resin composition of excellent in stability.
The 3rd embodiment relates to a kind of black-colored resin composition, it is the black-colored resin composition that contains light-proofness black pigment, pigment dispersing agent, resin and solvent, it is characterized by, this light-proofness black pigment is that average primary particle diameter is that 50nm aspect ratio following and pigment particles is that 1: 1～1: 2 De perylene is a black pigment.
Qian Shu perylene is that the average primary particle diameter of black pigment can be 20～45nm.
Aforementioned pigment dispersing agent can be the precursor skeleton with organic pigment and the pigment derivative of alkali subtituent.
The precursor skeleton of aforementioned organic pigment can be any in dioxazine series pigments or the diketopyrrolopyrrolecocrystals series pigments.
Aforementioned pigment dispersing agent can further contain the resin type spreading agent.
Foregoing can further contain ethene unsaturated compound and Photoepolymerizationinitiater initiater.
In addition, the 3rd embodiment relates to a kind of black matrix that is formed by aforementioned black-colored resin composition.
The relative dielectric constant of aforementioned black matrix when dry film thickness is 1.0 μ m can be below 4.5.
The transmitance of the wavelength 1000nm of aforementioned black matrix when dry film thickness is 1.0 μ m can be more than 60% and less than 99%.
The optical density of aforementioned black matrix when dry film thickness is 1.0 μ m can be more than 1.30.
In addition, the 3rd embodiment relates to a kind of driving substrate that possesses aforementioned black matrix film transistor (TFT) mode color liquid crystal display arrangement that is characterized as.
According to the 3rd embodiment, black matrix is because the light-proofness excellence, so demonstration contrast excellence of color liquid crystal display arrangement, and because low-k characteristic, the undesirable condition that the electrical specification of the black matrix that the interelectrode conducting that therefore is difficult to produce the orientation confusion of liquid crystal or forms on the TFT substrate is such causes, and because the light transmission rate excellence of near infrared region, therefore can also carry out the mask alignment operation, thereby also be suitable for the driving substrate of thin film transistor (TFT) (TFT) mode color liquid crystal display arrangement.
Embodiment
At first, the various constituents with regard to color composition for color filter of the present invention describe.
＜colorant 〉
With regard to colorant, filter section is arranged with colorant and black matrix colorant.
[filter section colorant]
, be not particularly limited with contained pigment in the colorant as filter section, when considering pigment particles dispersed, preferred average primary particle diameter is more than the 20nm.In addition, when considering contrast and brightness, preferred average primary particle diameter is below the 50nm.That is, along with average primary particle diameter increases, when light scattering backlight, polaroid intersection light leak taking place, therefore causes contrast to reduce.In addition, because transmitance descends, also influence causes brightness to descend.
In addition, when the aspect ratio of pigment particles is 1: 1～1: 3.5 a scope, fully preventing light scattering backlight, the decline of transmitance, is preferred therefore.
As the shape of pigment particles, not needle-like, but preferred spherical or ellipticity.When spherical, because therefore distance homogenising more between each pigment primary particle is difficult to take place scattering of light, contrast, brightness are very high.
As colorant, under the situation that for example forms the shades of colour filter section, can use versicolor pigment such as red pigment, blue pigment, viridine green, yellow uitramarine, violet pigment, orange pigment, brown.In addition, as its chemical constitution, for example can enumerate azo system, phthalocyanine system, quinoline a word used for translation ketone system, benzimidazolone system, isoindolinone is organic pigments such as the, dioxazine is, indanthrene Xi, perylene system.Also can utilize various inorganic pigments etc. in addition.
The object lesson of the spendable pigment of illustration." C.I. " expression Colour Index of below enumerating.
As red pigment, for example can enumerate: C.I. paratonere 1,2,3,4,5,6,7,8,9,12,14,15,16,17,21,22,23,31,32,37,38,41,47,48,48:1,48:2,48:3,48:4,49,49:1,49:2,50:1,52:1,52:2,53,53:1,53:2,53:3,57,57:1,57:2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276 etc.Wherein, from obtaining the viewpoint of high-contrast, high brightness, preferred C.I. pigment red 4 8:1,122,168,177,202,206,207,209,224,242 or 254 is more preferably C.I. paratonere 177,209,224,242 or 254.
As blue pigment, for example can enumerate: C.I. pigment blue 1,1:2,9,14,15,15:1,15:2,15:3,15:4,15:6,16,17,19,25,27,28,29,33,35,36,56,56:1,60,61,61:1,62,63,66,67,68,71,72,73,74,75,76,78,79 etc.Wherein, from obtaining the viewpoint of high-contrast, high brightness, preferred C.I. pigment blue 15,15:1,15:2,15:3,15:4 or 15:6 are more preferably the C.I. pigment blue 15: 6.
As viridine green, for example can enumerate C.I. naphthol green 1,2,4,7,8,10,13,14,15,17,18,19,26,36,45,48,50,51,54,55 or 58.Wherein, from obtaining the viewpoint of high-contrast, high brightness, preferred C.I. pigment Green 7,36 or 58.
As yellow uitramarine, for example can enumerate: C.I. pigment yellow 1,1:1,2,3,4,5,6,9,10,12,13,14,16,17,24,31,32,34,35,35:1,36,36:1,37,37:1,40,41,42,43,48,53,55,61,62,62:1,63,65,73,74,75,81,83,87,93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139,142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169,170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196,197,198,199,200,202,203,204,205,206,207,208 etc.Wherein, from obtaining the viewpoint of high-contrast, high brightness, preferred C.I. pigment yellow 83,117,129,138,139,150,154,155,180 or 185 is more preferably C.I. pigment yellow 83,138,139,150 or 180.
As violet pigment, for example can enumerate: C.I. pigment violet 1,1:1,2,2:2,3,3:1,3:3,5,5:1,14,15,16,19,23,25,27,29,31,32,37,39,42,44,47,49,50 etc.Wherein, from obtaining the viewpoint of high-contrast, high brightness, preferred C.I. pigment violet 19 or 23 is more preferably the C.I. pigment Violet 23.
As orange pigment, for example can enumerate: C.I. pigment orange 1,2,5,13,16,17,19,20,21,22,23,24,34,36,38,39,43,46,48,49,61,62,64,65,67,68,69,70,71,72,73,74,75,77,78,79 etc.Wherein, from obtaining the viewpoint of high-contrast, high brightness, preferred C.I. pigment orange 38 or 71.
Above-mentioned various pigment also can be also with multiple.For example,,, can and use viridine green and yellow uitramarine, perhaps also with blue pigment and violet pigment as pigment in order to adjust colourity.
[black matrix colorant]
In this instructions, sometimes will contain black matrix and make " black colorant composition " or " black-colored resin composition " with the color composition for color filter note of colorant.
Form when deceiving matrix,, can use the hybrid pigment of black pigment or above-mentioned redness, purple, yellow, green, blue pigment as colorant.
With regard to the average primary particle diameter of pigment, consider light-proofness, when considering pigment-dispersing, be preferably below the 50nm about the upper limit about lower limit, be more preferably 5～50nm, more preferably 20～50nm is preferably 20～45nm especially.That is, along with average primary particle diameter increases, the filling of particle becomes dredges, and produce the gap, thereby sheltering descends.Relative therewith, by average primary particle diameter is suppressed at below the 50nm, close, light-proofness raising that the filling of particle becomes.
The aspect ratio of pigment particles is preferably 1: 1～and 1: 3.5, be more preferably 1: 1～1: 2.0, more preferably 1: 1～1: 1.5.In the time of in above-mentioned scope, because the filling of particle change is close, the gap is few, so sheltering improves.
The shape of pigment particles is not needle-like but preferred spherical or ellipticity.Especially, when spherical, because therefore distance homogenising more between each pigment primary particle is difficult to produce the gap, sheltering is very high.
As spendable black pigment, can be the light-proofness black pigment, for example can enumerate the: perylene and be black pigment, carbon black, acetylene black, dim, bone black, graphite, iron oxide black, titanium is black, and the pigment color mixture system of above-mentioned redness, purple, yellow, green, blue pigment etc.Wherein, You Xuan perylene is a black pigment, carbon black, the pigment color mixture system of redness, purple, yellow, green, blue pigment etc.From the viewpoint of sheltering and electrical specification, being more preferably the only Shi Yong of Dan perylene is that black pigment or Bing Yong perylene are black pigment and carbon black.
When the only Shi Yong of Dan perylene was black pigment, relative dielectric constant, dispersiveness, development were excellent especially.
When Bing Yong perylene was black pigment and carbon black, the De perylene was that the content of black pigment is preferably 78～95 weight % Zhong black pigment 100 weight %, is more preferably 80～95 weight %.The ratio that consideration obtains sufficient light-proofness Shi ， perylene about 1.0 μ m be black pigment is preferably below the 95 weight %.Consider to prevent relative dielectric constant raise, improve wavelength 1000nm place transmitance so that the infrared ray sensor of calibration when fully discerning, preventing when BM forms to make the liquid crystal molecular orientation confusion, be preferably more than the 78 weight % because of driving voltage.
With regard to the content of black pigment, about the upper limit consider sufficient dispersion stabilization, when considering sufficient light-proofness about lower limit, in all solids composition 100 weight % of color composition for color filter, be preferably 20～70 weight %, be more preferably 30～70 weight %, more preferably 30～60 weight % are preferably 40～60 weight % especially.
In addition, make and use that to state perylene be black pigment, the black matrix that the black colorant composition that color mixture system constitutes forms is because the light-proofness excellence, so demonstration contrast excellence of color liquid crystal display arrangement, and because low-k characteristic, the undesirable condition that the electrical specification of the black matrix that the interelectrode conducting that therefore is difficult to produce the orientation confusion of liquid crystal or forms on the TFT substrate is such causes, and because the transmitance excellence of near infrared region, therefore can also carry out the mask alignment operation, thereby also be suitable for the driving substrate of thin film transistor (TFT) (TFT) mode color liquid crystal display arrangement.
With regard to black matrix, as commercially available product, for example can enumerate: the #260 that Mitsubishi Chemical's (strain) makes, #25, #30, #32, #33, #40, #44, #45, #45L, #47, #50, #52, MA7, MA8, MA11, MA100, MA100R, MA100S, MA230, the PrIntex L that DEGUSSA company makes, PrIntex P, PrIntex 30, PrIntex 35, PrIntex 40, PrIntex 45, PrIntex 55, PrIntex60, PrIntex 300, PrIntex 350, SpecIal Black 4, SpecIal Black 350, SpecIal Black550 etc.Wherein, from obtaining the viewpoint of high light intensity (following note is sometimes made OD), preferred #45.Black matrix can use a kind separately, also can mix 2 kinds with on use.
When containing average primary particle diameter in the colorant of the present invention and be 20～50nm and its aspect ratio and be 1: 1～1: 3.5 pigment, its content is preferably 30～100 weight % in all coloring agent 100 weight %, be more preferably 50～100 weight %.
When containing average primary particle diameter in the coloured composition of the present invention and be 20～50nm and its aspect ratio and be 1: 1～1: 3.5 pigment, its content is preferably in all solids composition more than the 1 weight % usually, be more preferably more than the 5 weight %, in addition, be generally below the 95 quality %, be preferably especially below the 85 weight %.Be 5 weight % when above, can not become excessive with respect to the thickness of colour saturation, the clearance control when not worrying liquid crystal cells etc. causes harmful effect.On the other hand, be 95 weight % when following, can access sufficient dispersion stabilization.
[miniaturization of pigment]
Employed pigment can be handled to wait and carry out miniaturization by the salt mill among the present invention.By the pigment that miniaturization has been carried out in use, can form the higher filter section of contrast and can form the high black matrix of light-proofness.
Salt mill handle be meant that mixing rolls such as using kneader, two roller mills, three-roll grinder, bowl mill, attitor, sand mill heat the potpourri of pigment, water-soluble inorganic salt and water-miscible organic solvent and mechanically milling after, the processing of removing water-soluble inorganic salt and water-miscible organic solvent by washing.Water-soluble inorganic salt works as grinding aid, utilizes the high rigidity of inorganic salts that pigment is pulverized during the salt mill.By making pigment carry out the constrained optimization when handling of salt mill, the pigment that can access the very fine and narrow distribution range of primary particle size, has precipitous size-grade distribution.
As water-soluble inorganic salt, can use sodium chloride, barium chloride, potassium chloride, sodium sulphate etc., from considering in price, preferably use sodium chloride (salt).Consider that from treatment effeciency and production efficiency two aspects water-soluble inorganic salt preferably uses 50～2000 weight portions with respect to pigment 100 weight portions, most preferably uses 300～1000 weight portions.
Water-miscible organic solvent has the effect of wetting pigment and water-soluble inorganic salt, so long as dissolving (mixing) then is not particularly limited in water and the material that do not dissolve employed inorganic salts in fact.But therefore the state that temperature rises, solvent is in easy evaporation during owing to the salt mill considers from the security aspect that preferably 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, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, the aqueous single ether of polyglycol, 1-methoxyl-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, aqueous polypropylene glycol etc.Water-miscible organic solvent preferably uses 5～1000 weight portions with respect to pigment 100 weight portions, most preferably uses 50～500 weight portions.
When pigment is carried out the processing of salt mill, can add resin as required.Spendable resin kind is not particularly limited, and can use natural resin, modified natural resin, synthetic resin, use the synthetic resin of natural resin modification etc.Spendable resin preferably at room temperature is solid, water-insoluble, and further preferred part dissolves in the above-mentioned organic solvent.The use amount of resin is preferably the scope of 5～200 weight portions with respect to pigment 100 weight portions.
＜spreading agent 〉
Color composition for color filter of the present invention can contain spreading agent.As spreading agent, can enumerate resin type spreading agent, pigment derivative, surfactant etc.Spreading agent is to the dispersing of pigments excellence, and the pigment after preventing to disperse reassociates.
[resin type spreading agent]
As the resin type spreading agent, can contain the acrylic acid series segmented copolymer, described acrylic acid series segmented copolymer is by the A block with solvophilic and has A-B segmented copolymer that the B block of the functional group of nitrogen atom constitutes or B-A-B segmented copolymer and amine value are scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent.
The resin type spreading agent comprises having the colorant compatibility position that is adsorbed in colorant character and with the colorant carrier position of compatibility is arranged, and has the effect that colorant makes the stably dispersing of colorant in the toner carrier that is adsorbed in, but, therefore pass through crosslinked easily and tackify because the spreading agent of random randomly disposes the pigment adsorption base.On the other hand, because pigment adsorption base high density is arranged in the segmented copolymer, therefore crosslinked by force and not to the absorption of pigment.Therefore segmented copolymer can be guaranteed higher dispersion stabilization.In addition, as long as the amine value is below the above 99mgKOH/g of 10mgKOH/g, the favorable solubility in developer solution then can development at the appointed time in developing procedure, in addition, and the not dissolved matter of residual colored resin composition not in non-image on substrate.
As the monomer of the presoma of A block with solvophilic, so long as do not have nitrogen atoms such as amino functional group and can with the material of the monomer copolymerization that constitutes the B block, then be not particularly limited.
As the A block, for example can enumerate the polymer architecture that following comonomer copolymerization is formed: styrenic monomers such as styrene, α-Jia Jibenyixi; (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) glycidyl acrylate, (methyl) acrylic acid benzyl ester, (methyl) hydroxy-ethyl acrylate, the ethyl propylene acid glycidyl ester, polyglycol (methyl) acrylate, (methyl) acrylic ester monomers such as polypropylene glycol (methyl) acrylate; (methyl) acrylates such as (methyl) acryloyl chloride are monomer; Vinyl acetate is a monomer; Glycidol ethers such as allyl glycidyl ether, crotonic acid glycidol ether are monomer etc.
Wherein, as the A block, preferably contain poly alkylene glycol (methyl) acrylate such as polyglycol (methyl) acrylate, polypropylene glycol (methyl) acrylate (promptly as copolymer composition, contain part-structure from poly alkylene glycol (methyl) acrylate) material, especially preferably have the represented part-structure of following general formula (I).
Figure BSA00000517935500141
[in the general formula (I), n represents 1～5 integer, R 1Expression hydrogen atom or methyl.]
The represented part-structure of general formula (I) especially preferably contains 5～40 moles of % in the A block.
In addition, from improving the viewpoint of dispersion stabilization, preferably further containing in the A block beyond the represented part-structure of the general formula (I) of 50～90 moles of % is the formation unit of presoma with (methyl) acrylic ester monomer, is more preferably 60～80 moles of %.Wherein, because by using (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) 2-ethyl hexyl acrylate to be used as (methyl) acrylic ester monomer, the dispersiveness of coloured composition, excellent in stability, therefore preferred above-mentioned substance.
In the A block, by containing the represented part-structure of general formula (I), thus the water wettability of giving and the dissolubility in the developer solution improved.On the other hand, beyond the represented part-structure of general formula (I) be the formation unit of presoma by further containing with (methyl) acrylic ester monomer, improve with the compatibility of adhesive resin and dispersion stabilization rises.
As the B block of functional group, preferably has primary～uncle amino as functional group with nitrogen atom.Primary～uncle amino contain 10 moles of functional group that ratio is preferably whole nitrogen atoms more than the %, be more preferably 40 moles more than the %.
Amino preferred usefulness-NR 4R 5(wherein, R 4And R 5Respectively independently the expression can have substituent ring-type or chain alkyl, can have substituent aryl or can have substituent aralkyl) expression, as the part-structure that contains it, the structure of preference as representing with following formula.
[in the general formula (II), R 4And R 5Respectively independently expression can have substituent ring-type or chain alkyl, can have substituent aryl and maybe can have substituent aralkyl, R 3The expression carbon number is the alkylidene more than 1, R 2Expression hydrogen atom or methyl.]
Wherein, R 4And R 5Be preferably methyl, R 3Be preferably methylene or ethylidene, R 2Be preferably methyl.As such part-structure, the structure of preference as representing with following formula.
Figure BSA00000517935500152
The aforesaid part-structure that contains amino can contain more than 2 kinds in 1 B block.In this case, contain more than 2 kinds amino part-structure can random copolymerization in this B block or arbitrary mode of block copolymerization contain.In addition, in the scope of not damaging effect of the present invention, can in the B block, part contain the part-structure that does not contain amino,, can enumerate part-structure from (methyl) acrylic ester monomer as the example of such part-structure.The related amino content of part-structure in the B block that do not contain is preferably 0～60 mole of %, is more preferably 0～20 mole of %, most preferably is not contain the related part-structure that does not contain amino in the B block.
In addition,, when using quaternary ammonium salt group, interact with other resins, do not carry out absorption, thereby might produce tackify or gelation colorant because its polarity is strong as the B block of functional group with nitrogen atom.Therefore, as the functional group of nitrogen atom, preferred primary, second month in a season or tertiary amine.Wherein, therefore tertiary amine is preferred owing to the absorption affinity and stable two aspects that have both colorant.
Promptly, from improving the viewpoint of dispersed and developing solution dissolution, the acrylic acid series segmented copolymer preferably contains the represented repetitive of the general formula (I) of 5～40 moles of % in having the A block of solvophilic, have in the B block of functional group of nitrogen atom and contain the represented repetitive of general formula (II).
In addition, when the acrylic acid series segmented copolymer contains acid groups such as carboxylic acid, phosphoric acid, owing to soda acid takes place interact with amine position etc. in the B block, thereby dispersion stabilization is descended, so the low material of preferred acid number, be more preferably 0mgKOH/g.
The content of acrylic acid series segmented copolymer is preferably 1～70 weight portion with respect to colorant 100 weight portions, more preferably 10～60 weight portions.The use level of acrylic acid series segmented copolymer is preferably more than 1 weight portion from the viewpoint of pigment-dispersing.In addition, use this coloured composition, when making the pattern of pixels of color filter,, be preferably below 70 weight portions from obtaining the viewpoint of high alkalinity development by photoetching process.
In addition, color composition for color filter of the present invention can use separately or with above-mentioned resin type spreading agent and usefulness, also can contain other resin type spreading agent.
Resin type spreading agent as other 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, contain the polycarboxylate of hydroxyl and the modifier of these materials, poly-(rudimentary alkyleneimines) and have the pet reaction of free carboxy and oiliness spreading agents such as the acid amides that forms and salt thereof, (methyl) acrylic acid-styrol copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol (PVA), water soluble resin and water-soluble high-molecular compounds such as polyvinylpyrrolidone, polyester system, modified polyacrylate system, the ethylene oxide/propylene oxide additive compound, phosphate system etc.
As spendable commercially available resin type spreading agent among the present invention, can enumerate the DIsperbyk-101 that Bi Ke chemistry corporate system is made, 103,107,108,110,111,116,130,140,154,161,162,163,164,165,166,167,170,171,174,180,181,182,183,184,185,190,9076,9077, or BYK-LPN 6919,21324,21407, or AntI-Terra-U, 203,204, or BYK-P104, P104S, 220S, or LactImon, LactImon-WS or Bykumen etc., the SOLSPERSE-3000 that Japan Lubrizol Corp. makes, 9000,13240,13650,13940,17000,18000,20000,21000,24000,26000,27000,28000,31845,32000,32500,32600,34750,36600,38500,41000,41090,53095,76500 etc., the EFKA-46 that EFKA chemical company makes, 47,48,452, LP4008,4009, LP4010, LP4050, LP4055,400,401,402,403,450,451,453,4540,4550, LP4560,120,150,1501,1502,1503,4300,4330 etc., the AJISPERPA111 that aginomoto fine chemistry company makes, PB711, PB821, PB822, PB824 etc.
The pigment dispersing agent of using as black pigment when using pigment derivative, the preferred pigment derivative of using precursor skeleton with organic pigment and alkali subtituent, because electrical specification becomes better, so is preferred.By further containing the resin type spreading agent,, be preferred therefore owing to further improving electrical specification, taking into account flowability and stability.
The resin type spreading agent comprises having the pigment compatibility position that is adsorbed in light-proofness black pigment character and with the black pigment carrier position of compatibility is arranged, and has by being adsorbed in the light-proofness black pigment and make effect to the stably dispersing of black pigment carrier.With aforementioned pigment derivative similarly, the resin type spreading agent is given with the compatibility of black pigment and pigment derivative, is made the molecules align in the black-colored resin composition more even, further reducing the skew of electric charge, therefore also help electrical specification to improve, is preferred thus.
Especially, when the pigment derivative of use black pigment, precursor skeleton and alkali subtituent and acidic resins type spreading agent,, be preferred therefore because performance takes into account the effect mobile and excellence that electrical specification is such with organic pigment.This is because by acidic resins type spreading agent with have interaction between the soda acid substituting group that pigment derivative had of alkali subtituent, can in and electric charge, as a result of, owing to can suppress the partial charge skew, so electrical specification improves.
In these materials, in order to improve the interaction with alkaline derivant, the resin type spreading agent of preferred acidic, in addition, from the viewpoint of dispersion stabilization, the acid number of resin type spreading agent is preferably below the 129mgKOH/g, most preferably is 13～53mgKOH/g.
[pigment derivative]
Color composition for color filter of the present invention preferably further contains the pigment derivative as acid derivant or its slaine of organic pigment.The acid derivant of organic pigment or its slaine are owing to can further promote the pigment adsorption of pigment and resin type spreading agent and improve dispersing of pigments, and the effect that the pigment after therefore preventing to disperse reassociates is big.Therefore, use with the acid derivant of organic pigment or its slaine pigment dispersing in pigment carrier and during the coloured composition of formation, can be obtained the color filter of excellent in stability.Further, by using simultaneously as by A block with have the A-B segmented copolymer that the B block of the functional group of nitrogen atom constitutes or the resin type spreading agent of B-A-B segmented copolymer, thereby improve dispersed more with solvophilic.Can think that thereby this is to promote the pigment adsorption of spreading agent because the soda acid of the alkali subtituent of acid substituting group by being disposed near the derivant the pigment and spreading agent interacts.
As acid derivant or its slaine of organic pigment, can enumerate the compound of following general formula (1) expression.
P-Lx general formula (1)
(wherein, P: organic pigment residue, L: acid substituting group, x: hydrogen atom or metallic ion)
As the organic pigment of the organic pigment residue that constitutes P, for example can enumerate: the diketopyrrolopyrrolecocrystals series pigments; Azo pigments such as azo, bisdiazo, polyazo; Phthualocyanine pigments such as copper phthalocyanine, copper halide phthalocyanine, zinc phthalocyanine, zinc halide phthalocyanine, metal-free phthalocyanine; Amino anthraquinones, diamido DIANTHRAQUINONE, anthracene pyrimidine, flavanthrone, anthracene are formed anthraquione pigmentss such as anthrone, indanthrene, pyranthrone, violanthrone; Quinoline a word used for translation ketone series pigments; The dioxazine series pigments; Purple cyclic ketones series pigments; Perylene pigment; The accurate indigo series pigments of sulphur; The isoindoline series pigments; Isoindolinone pigment; Intellectual circle's series pigments; The quinophthalone series pigments; The dioxazine series pigments; Metal complex series pigments etc.
Wherein, quinophthalone series pigments, particularly quinophthalone are yellow uitramarine C.I. pigment yellow 13 8, because therefore excellences such as the throughput rate of coloured composition, dispersion stabilization, thermotolerance, photostability, solvent resistance are preferred.
As the acid substituent substituting group that constitutes L, for example can enumerate sulfonic acid, carboxylic acid, phosphoric acid etc.
As the metallic ion of x, can enumerate alkali metal ions such as sodium, potassium, alkaline-earth metal ions such as magnesium, calcium, barium, amphoteric metal ions such as aluminium, zinc, transition metal ions such as iron, nickel etc.
Wherein, transition metal ions such as amphoteric metal ion, iron, nickel such as alkaline-earth metal ion, aluminium, zinc such as preferred calcium, barium etc.Wherein aluminium ion has high-fire resistance and dispersiveness, thereby preferred especially.
As acid derivant or its slaine of organic pigment, sulfonic acid or its aluminium salt of preferred especially quinophthalone.The dispersion of the sulfonic acid of quinophthalone or its aluminium salt pair colorant excellent and prevent to disperse after the effect that reassociates of colorant big.Therefore, use the sulfonic acid of quinophthalone or its aluminium salt to make colorant be scattered in that resin, organic solvent are waited in the toner carrier and the excellent in stability of the coloured composition that forms.
For example, be that the sulfonic acid of the quinophthalone that constitutes of yellow uitramarine C.I. pigment yellow 13 8 is the represented compound of following formula (2) by quinophthalone, its aluminium salt is the represented compound of following formula (3).
Figure BSA00000517935500181
Figure BSA00000517935500191
The aluminium salt of the sulfonic acid of quinophthalone can be synthetic by common method, but following method industrial be favourable.That is, in the concentrated sulphuric acid or oleum, add pigment, heat and carry out sulfonation.Then, this reaction solution is injected a large amount of frozen water, use pressure filter etc. filters, washes the sulfonic acid of separating out.The water slurry of the sulfonic acid of gained is scattered in a large amount of water again, use sodium hydrate aqueous solution that pH is adjusted to alkalescent after, slowly add aluminum sulfate aqueous solution and make the sulfonic acid salify, thereby form the method for aluminium salt.Afterwards, through filtration, washing, dry, pulverizing process, can obtain the aluminium salt of the sulfonic acid of pulverous quinophthalone.
Can mix the material that the pigment derivative that uses for example can be enumerated records such as Japanese kokai publication sho 63-305173 communique, Japanese Patent Publication 57-15620 communique, Japanese Patent Publication 59-40172 communique, Japanese Patent Publication 63-17102 communique, the special fair 5-9469 communique of Japan with acid derivant or its slaine of this organic pigment.
In addition, the compound that color composition for color filter of the present invention can be represented with following general formula (1 ') is as pigment derivative.Be preferably used as the pigment derivative that the black colorant composition is used especially.
P '-L ' n general formula (1 ')
[wherein, P ': organic pigment residue, anthraquinone residue, acridone residue or three zin residues, L ': alkali subtituent, acid substituting group maybe can have substituent phthalimide methyl, the integer of n:1～4.]
As the organic pigment residue that constitutes P ', for example can enumerate the diketopyrrolopyrrolecocrystals series pigments; Azo pigments such as azo, bisdiazo, polyazo; Phthualocyanine pigments such as copper phthalocyanine, copper halide phthalocyanine, metal-free phthalocyanine; Amino anthraquinones, diamido DIANTHRAQUINONE, anthracene pyrimidine, flavanthrone, anthracene are formed anthraquione pigmentss such as anthrone, indanthrene, pyranthrone, violanthrone; Quinoline a word used for translation ketone series pigments; The dioxazine series pigments; Purple cyclic ketones series pigments; Perylene pigment; The accurate indigo series pigments of sulphur; The isoindoline series pigments; Isoindolinone pigment; The quinophthalone series pigments; Intellectual circle's series pigments; Metal complex series pigments etc.
Wherein, preferred precursor skeleton is the pigment derivative of organic pigment, from the low viewpoint of dielectric loss tangent, can be more preferably and use dioxazine series pigments and diketopyrrolopyrrolecocrystals series pigments.
Can use preferably that L ' is the alkaline derivant of alkali subtituent in the general formula (1 ').Wherein, has the pigment derivative of the precursor skeleton of organic pigment and alkali subtituent owing to give compatibility that the Yu perylene is a black pigment, make molecules align homogenising in the black-colored resin composition, reduce the skew of electric charge, and help to improve electrical specification, be preferred therefore.
In addition, the substituting group of preferred L ' for from the represented group of general formula (2 '), (3 ') and (4 '), selecting.
Figure BSA00000517935500201
[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 1For-NH-,-NR 58-Z-NR 59Or Direct Bonding; R 58And R 59Respectively independently for hydrogen bond, can to have substituent carbon number be 1～36 alkyl, can have substituent carbon number is that 2～36 thiazolinyl maybe can have substituent phenyl; Z maybe can have substituent arylene for having substituent alkylidene; R 50And R 51Respectively independently for hydrogen atom, can to have substituent carbon number be 1～30 alkyl, can have substituent carbon number is 2～30 thiazolinyl or is R 50And R 51Integratedly and further nitrogenous, oxygen or sulphur atom have a substituent heterocycle; R 52, R 53, R 54And R 55Respectively independently for hydrogen atom, can to have substituent carbon number be 1～20 alkyl, can have substituent carbon number is that maybe can to have substituent carbon number be 6～20 arylene for 2～20 thiazolinyl; R 56For hydrogen atom, can to have substituent carbon number be 1～20 alkyl, can have substituent carbon number is 2～20 thiazolinyl; R 57Be above-mentioned general formula (2 ') represented substituting group or the represented substituting group of above-mentioned general formula (3 '); Q is hydroxyl, alkoxy, represented substituting group or the represented substituting group of above-mentioned general formula (3 ') of above-mentioned general formula (2 ').]
As being used to form represented substituent amine component of general formula (2 ')～(4 '), for example can enumerate: dimethylamine, diethylamine, Methylethyl 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 oleyl amines, Di-Stearyl amine, N, N-dimethylamino methylamine, N, N-dimethylamino ethamine, N, N-dimethylamino amylamine, N, N-dimethylamino butylamine, N, the N-diethylamino-ethylamine, N, the N-diethylaminopropylamine, N, N-lignocaine hexylamine, N, N-lignocaine butylamine, N, N-lignocaine amylamine, N, the amino butylamine of N-dipropyl, N, the N-dibutylaminopropylamine, N, N-dibutylamino ethamine, N, N-dibutylamino butylamine, N, the amino amylamine of N-two isobutyls, N, the amino propylamine of N-methyl-bay, N, N-ethyl-own aminoethyl, N, N-distearyl aminoethyl, N, N-two oily aminoethyl, N, the amino butylamine of N-distearyl, piperidines, the 2-pipecoline, the 3-pipecoline, the 4-pipecoline, 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, the N-aminoethyl piperidine, N-aminoethyl-4-pipecoline, the N-aminoethyl morpholine, N-aminopropyl piperidines, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, the N-aminopropyl morpholine, N methyl piperazine, N-butyl piperazine, the high piperazine of N-methyl, the 1-cyclopentyl-based piperazine, 1-amino-4-methyl piperazine, 1-cyclopentyl-based piperazine etc.
Pigment derivative, anthraquinone derivative and acridone derivatives with alkali subtituent can synthesize by various synthesis paths.For example, in organic pigment, anthraquinone or acridone behind the represented substituting group of introducing-type (5 ')～(8 '), form for example N of represented substituent above-mentioned amine component of formula (2 ')～(4 ') by making with above-mentioned substitution reaction, N-dimethylaminopropylamine, N methyl piperazine, diethylamine or 4-[4-hydroxyl-6-[3-(dibutylamino) third amino]-1,3,5-triazine-2-base is amino] aniline etc. reacts and obtains.
Formula (5 ') :-SO 2Cl
Formula (6 ') :-COC1
Formula (7 ') :-CH 2NHCOCH 2Cl
Formula (8 ') :-CH 2Cl
During the reaction of the substituting group of formula (5 ')～(8 ') and above-mentioned amine component, can be mixed with make formula (5 ')～(8 ') thus substituting group hydrolysis partly takes place and chlorine is substituted by the material that hydroxyl forms.In this case, formula (5 ') and formula (6 ') become sulfonic group and carboxylic acid group respectively, and they all can form free acid, also can be metal or the formed salt of above-mentioned monoamine with 1～3 valency.
In addition, organic pigment is an azo when being pigment, and substituting group that also can be in advance that general formula (2 ')～(4 ') is represented imports bisdiazo composition or coupling agent composition, makes the azo pigment derivant by carrying out coupling reaction afterwards.
When considering to prevent decrease of contrast and obtain excellent electric characteristics, the total amount of pigment derivative is preferably more than 0.5 weight portion with respect to weight 100 weight portions of colorant, more preferably more than 1 weight portion, most preferably is more than 3 weight portions.In addition, when considering sufficient photostability and the excellent electric characteristics in black matrix etc., be preferably below 40 weight portions, be more preferably below 35 weight portions, most preferably be below 20 weight portions.
Pigment derivative can be used separately, also can mix use more than 2 kinds.
[surfactant]
As surfactant, can enumerate the anionic surfactant such as monoethanolamine, polyoxyethylene alkyl ether phosphate of alkali metal salt, odium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl base ether sodium disulfonate, dodecyl sulphate monoethanolamine, dodecyltriethanolamine sulfate, ammonium lauryl sulfate, stearic acid monoethanolamine, the styrene-propene acid copolymer of lauryl sodium sulfate, polyoxyethylene alkyl ether sulfate salt, neopelex, styrene-propene acid copolymer; Nonionic surfactants such as polyoxyl 10 oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylplenyl ether, polyoxyethylene alkyl ether phosphate, Tween-60, polyethylene glycol monolaurate: alkyl quaternary ammonium salts, their cationic surfactants such as ethylene oxide adduct; Amphoteric surfactantes such as alkyl betaine, alkyl imidazoline such as alkyl-dimethyl aminoacetic acid betaine, these surfactants can use separately or mix more than 2 kinds and use, but might not be defined in these surfactants.
Consider well when dispersed, the addition of resin type spreading agent, surfactant is preferably 0.1～55 weight portion with respect to colorant 100 weight portions, more preferably 0.1～45 weight portion.
＜resin 〉
Can contain resin in the color composition for color filter of the present invention.The resin that contains in the color composition for color filter of the present invention is the material of toner of being scattered here and there, and can use thermoplastic resin, thermoset resin etc.Spectrophotometric transmittance in the long zone of the all-wave of 400～700nm that aforementioned resin is preferably in the visible region is more than 80%, be more preferably the transparent resin more than 95%.In addition, when using with the form of alkali-developable photosensitive color composition, the preferred alkali solubility vinyl resin that contains the ethylene unsaturated monomer copolymerization of acidic-group and form that uses.In addition, in order further to improve light sensitivity, also can use active energy ray-curable resin with ethene unsaturated double-bond.
Especially,, can improve the stability of erosion resistant by using the active energy ray-curable resin that on side chain, has the ethene unsaturated double-bond, therefore preferred.
As thermoplastic resin, for example can enumerate: acryl resin, butyral resin, styrene-maleic acid copolymer, haloflex, chlorinated polypropylene, Polyvinylchloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate (PVA), polyurethane series resin, vibrin, vinyl resin, alkyd resin, polystyrene resin, polyamide, rubber are that resin, thermoprene are resin, cellulose family, tygon (HDPE, LDPE), polybutadiene and polyimide resin etc.
As thermoset resin, for example can enumerate epoxy resin, benzoguanamine resin, Abietyl modified maleic acid resin, Abietyl modified fumaric resin, melamine resin, urea resin and phenolics etc.
The ethene base system alkali soluble resins that forms as making the ethylene unsaturated monomer copolymerization that contains acidic-group for example can be enumerated the resin of acidic-groups such as having carboxyl, sulfo group.As alkali soluble resins, particularly, can enumerate acryl resin, alpha-olefin/maleic acid (acid anhydride) multipolymer, styrene/styrene sulfonic acid multipolymer, ethene/(methyl) acrylic copolymer or isobutylene/maleic acid (acid anhydride) multipolymer etc. with acidic-group.Wherein, because that at least a resin of selecting from acryl resin with acidic-group and styrene/styrene sulfonic acid multipolymer particularly has thermotolerance, the transparency of the acryl resin of acidic-group is high, therefore preferred the use.
As active energy ray-curable resin, for example can enumerate by method shown below (i) or method (ii) and import the resin that the ethene unsaturated double-bond forms with ethene unsaturated double-bond.
[method (i)]
As method (i), following method is for example arranged: make the side chain epoxy radicals of the multipolymer that ethylene unsaturated monomer by will having epoxy radicals and another above monomer copolymerization obtain carry out addition reaction with unsaturated monacid carboxyl with ethene unsaturated double-bond, make the hydroxyl and the multi-anhydride reaction of generation again, thereby import ethene unsaturated double-bond and carboxyl.
As ethylene unsaturated monomer with epoxy radicals, for example can enumerate (methyl) glycidyl acrylate, (methyl) acrylic acid methyl ethylene oxidic ester, (methyl) acrylic acid-2-glycidoxy ethyl ester, (methyl) acrylic acid-3,4-epoxy butyl ester and (methyl) acrylic acid-3,4-epoxy cyclohexyl, these materials can use separately, also can more than 2 kinds and use.From consider preferred (methyl) glycidyl acrylate with unsaturated monacid reactive viewpoint of subsequent processing.
As unsaturated monoacid, can enumerate: (methyl) acrylic acid, crotonic acid, adjacent,, to vinyl benzoic acid, monocarboxylic acids such as (methyl) acrylic acid α position alkylhalide group, alkoxy, halogen, nitro, cyano group substituent etc.These materials can use separately, also can more than 2 kinds and use.
As multi-anhydride, can enumerate tetrabydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride etc.These materials can use separately, also can more than 2 kinds and use.According to the needs such as number that increase carboxyl, also can use tricarboxylic acid anhydride such as trimellitic anhydride or use tetracarboxylic dianhydride such as pyromellitic acid anhydride to make residual anhydride group hydrolysis etc.In addition, as multi-anhydride, when using tetrabydrophthalic anhydride with ethene unsaturated double-bond or maleic anhydride, can further increase the ethene unsaturated double-bond.
Similar approach as method (i), following method is for example arranged: make the part of the side chain carboxyl group of the multipolymer that ethylene unsaturated monomer by will having carboxyl and another above monomer copolymerization obtain carry out addition reaction, thereby import ethene unsaturated double-bond and carboxyl with ethylene unsaturated monomer with epoxy radicals.
[method (ii)]
As method (ii), following method is arranged: have the ethylene unsaturated monomer of hydroxyl and other by use and have the unsaturated monacid monomers of carboxyl or other monomers and carry out copolymerization and obtain multipolymer, the pendant hydroxyl group of this multipolymer and the isocyanate group with ethylene unsaturated monomer of isocyanate group are reacted.
As ethylene unsaturated monomer with hydroxyl, can enumerate (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) acrylic acid-2 or 3-hydroxypropyl acrylate, (methyl) acrylic acid-2 or 3 or (methyl) acrylic acid hydroxy alkyl ester classes such as 4-hydroxy butyl ester, (methyl) acrylic acid glyceride or cyclohexanedimethanol list (methyl) acrylate, these materials can use separately, also can more than 2 kinds and use.In addition, also can use polyethers list (methyl) acrylate that above-mentioned (methyl) hydroxyalkyl acrylate and oxirane, epoxypropane and/or epoxy butane etc. is carried out addition polymerization and form or carry out addition with (gathering) gamma-valerolactone, (gathering) 6-caprolactone and/or (gathering) 12-hydroxy stearic acid etc. and form (gathering) ester list (methyl) acrylate.From the viewpoint of the foreign matter that suppresses to film, preferred (methyl) acrylic acid-2-hydroxyl ethyl ester or (methyl) acrylic acid glyceride.
As ethylene unsaturated monomer with isocyanate group, can enumerate 2-(methyl) acryloxy ethyl isocyanate or 1, two [(methyl) acryloxy] ethyl isocyanates of 1-etc., but be not limited to these materials, can also more than 2 kinds and use.
For the toner that is scattered here and there well, the weight-average molecular weight of resin (Mw) is preferably 10000～100000 scope, is more preferably 10000～80000 scope.In addition, number-average molecular weight (Mn) is preferably 5000～50000 scope, and the value of Mw/Mn is preferably below 10.
With regard to the acid number of resin, dispersiveness, stability, development and stable on heating viewpoint from colorant, consider as colorant absorption base and carboxyl that the alkali soluble groups when developing works, during with the balance of aliphatic group that works as affinity groups and aromatic group facing to toner carrier and solvent, acid number is preferably 20～300mgKOH/g.Consideration is during to the formation of the dissolubility of developer solution, fine pattern, and acid number is preferably more than the 20mgKOH/g.In addition, when considering the residual degree of fine pattern, be preferably below the 300mgKOH/g.
Consider from film forming and the good angle of various patience, resin preferably uses with the amount more than 30 weight portions with respect to total weight 100 weight portions of colorant, can show good color characteristics because colorant concentration raises, therefore preferably use with the amount below 500 weight portions.
＜solvent 〉
Color composition for color filter of the present invention can contain solvent.For colorant is well-dispersed in the resin, and dye compositions of the present invention is preferably 0.1～10 μ m, forms filter section on the transparency carrier such as the mode that is more preferably 0.2～20 μ m is coated glass substrate according to dry film thickness, and use solvent.
As solvent, can enumerate: 1,2, the 3-trichloropropane, 1, the 3-butylene glycol, 1,3-butylene glycol diacetate, 1, the 4-diox, the 2-heptanone, the 2-methyl isophthalic acid, ammediol, 3,5,5-trimethyl-2-cyclohexene-1-ketone, 3,3, the 5-trimethylcyclohexanone, the 3-ethoxyl ethyl propionate, the 3-methyl isophthalic acid, the 3-butylene glycol, 3-methoxyl-3-methyl isophthalic acid-butanols, 3-methoxyl-3-methyl butyl acetate, 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-butyl benzene, the n-pro-pyl acetate, N-Methyl pyrrolidone, o-xylene, ortho-chlorotolu'ene, adjacent diethylbenzene, o-dichlorobenzene, parachlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl benzene, gamma-butyrolacton, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, butyl cellosolve, the glycol monomethyl isopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, glycol monomethyl uncle butyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol ether, ethylene glycol ether, glycol monoethyl ether, the glycol monoethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol list isopropyl ether, diethylene glycol ether acetate alone, diethylene glycol monobutyl ether, the diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetic ester, cyclohexanone, the dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, the single ether of dipropylene glycol, the dipropylene glycol monobutyl ether, the single propyl ether of dipropylene glycol, dipropylene glycol monomethyl ether, diacetone alcohol, triacetyl glycerine, the tripropylene glycol monobutyl ether, the tripropylene glycol monomethyl ether, PGDA, the propylene glycol phenylate, dihydroxypropane single-ether, the dihydroxypropane single-ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, the propylene glycol monomethyl ether propyl ester, benzylalcohol, methyl isobutyl ketone, methyl cyclohexanol, n-Amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid ester etc.
These solvents can use a kind separately, or as required with arbitrary proportion mix 2 kinds with on use.
Wherein, consider from the angle of the favorable dispersibility of colorant of the present invention, preferably use ketones such as aromatic series alcohols such as glycol acetates, benzylalcohols such as propylene glycol monomethyl ether acetate, dihydroxypropane single-ether acetate, glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate or cyclohexanone.
From coloured composition being adjusted to suitable viscosity, forming the filter section as the homogeneous film thickness of target, solvent preferably uses with the amount of 800～4000 weight portions with respect to colorant 100 weight portions.
Color filter of the present invention can further add photopolymerization monomer with dye compositions and/or Photoepolymerizationinitiater initiater is used as color filter photosensitive coloring composition (erosion resistant) use.
＜photopolymerization monomer 〉
Color composition for color filter of the present invention can contain photopolymerization monomer.Comprise in the photopolymerization monomer by ultraviolet ray or heat etc. and solidify monomer or the oligomer that generates resin, these materials can use separately or mix more than 2 kinds and use.The use level of photopolymerization monomer is preferably 5～400 weight portions with respect to colorant 100 weight portions, from the viewpoint of photo-curable and development, is more preferably 10～300 weight portions, more preferably 10～200 weight portions.As photopolymerization monomer, be preferably compound with 1 or 2 above ethene unsaturated double-bond.
As photopolymerization monomer, for example can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) cyclohexyl acrylate, (methyl) propenoic acid beta-carboxylic 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, pentaerythrite four (methyl) acrylate, 1,6-hexanediol diglycidyl ether two (methyl) acrylate, bisphenol A diglycidyl ether two (methyl) acrylate, neopentylglycol diglycidyl ether two (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three ring decyl alcohol (methyl) acrylate, the ester acrylate, (methyl) acrylate of methylolation melamine, epoxy (methyl) acrylate, 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., but might not be defined in these.
＜Photoepolymerizationinitiater initiater 〉
Color composition for color filter of the present invention can contain Photoepolymerizationinitiater initiater.When making said composition curing and utilizing photoetching process to form filter section or black matrix by the ultraviolet ray irradiation, adding Photoepolymerizationinitiater initiater etc. can be modulated with the form of solvent develop type or alkali-developable photosensitive color composition.
As Photoepolymerizationinitiater initiater, can use: 4-phenoxy group dichloroacetophenone, the 4-tert-butyl group-dichloroacetophenone, diethoxy acetophenone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxy-cyclohexyl benzophenone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone or 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-acetophenone based compounds such as 1-ketone; Benzoin based compounds such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether or dibenzoyl dimethyl acetal; Benzophenone, benzophenone formic acid, benzophenone methyl formate, 4-phenyl benzophenone, dihydroxy benaophenonel, acrylated benzophenone, 4-benzoyl group-4 '-methyldiphenyl base sulfide or 3,3 ', benzophenone based compounds such as 4,4 '-four (tert-butyl peroxy carbonyl) benzophenone; Thioxanthones, 2-clopenthixal ketone, 2-methyl thioxanthones, isopropyl thioxanthone, 2,4-diisopropyl thioxanthones or 2, thioxanthones based compounds such as 4-diethyl thioxanthone; 2,4, the 6-trichloro-triazine, 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-(naphtho--1-yl)-4,6-two (trichloromethyl) s-triazine, 2-(4-methoxyl-naphtho--1-yl)-4,6-two (trichloromethyl) s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine or 2,4-trichloromethyl-triazine based compounds such as (4 '-methoxyl-styrene)-6-triazine; 1,2-ethohexadiol, 1-[4-(thiophenyl)-2-(O-benzoyl oxime)] or O-(acetyl group)-N-(1-phenyl-2-oxo-2-(4 '-methoxyl-naphthyl) ethylidene) hydramine, ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-oxime ester based compounds such as (O-acetyl oximes); Two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide or 2,4, phosphine based compounds such as 6-trimethylbenzoyl diphenyl phosphine oxide; 9, quinone based compounds such as 10-phenanthrenequione, camphorquinone, EAQ; The borate based compound; The carbazole based compound; Imidazole compound; Or luxuriant titanium sub-group compound etc.
These Photoepolymerizationinitiater initiaters can use a kind separately, or are mixed with two or more with arbitrary proportion as required.
The content of Photoepolymerizationinitiater initiater is preferably 5～200 weight portions with respect to colorant 100 weight portions, from the viewpoint of photo-curable and development, is more preferably 10～150 weight portions.
＜sensitizer 〉
Also can contain sensitizer in the color composition for color filter of the present invention.
As sensitizer, can enumerate: with chalcone derivative, dibenzalacetone derivatives etc. is the unsaturated ketone of representative; With dibenzoyl, camphorquinone etc. is 1 of representative, polymethine pigments such as 2-derovatives, benzoin derivatives, fluorene derivative, naphthoquinone derivatives, anthraquinone derivative, xanthene derivant, thioxanthene derivative, xanthone derivant, thioxanthone derivates, coumarin derivative, coumarin ketone derivates, anthocyanin derivant, Merocyanine derivatives, oxonols derivant; Acridine derivatives; azine derivatives; thiazine derivative oxazine derivant; the indoline derivative thing; azulene derivatives; Azulene (azulenium) derivant; the side acid derivative; derivatives of porphyrin; the tetraphenylporphyrin derivant; triarylmethane derivatives; four benzoporphyrin derivatives; four pyrazine porphyrin (Tetrapyrazinoporphyrazine) derivants; phthalocyanine derivates; tetraazatetradecane porphyrin (tetraazaporphyrazine) derivant; four quinoline promises and porphyrin (tetra (quinoxalino) porphyrazine) derivant; naphthalocyanine derivative; inferior phthalocyanine derivates; pyran derivate; the sulfo-pyran derivate; cyanogen glucoside (Tetraphyllin) derivant; the wheel ene derivative; spiropyran derivatives spiro oxazone derivative; sulfo-spiro-pyrans (Thio Spiropyran) derivant; the metal arene complex compound; the organic ruthenium complex compound; perhaps michler's ketone derivant; the alpha-acyloxy ester; two acyl group hydroxide phosphines; methyl benzoylformate; dibenzoyl; 9; the 10-phenanthrenequione; camphorquinone; EAQ; 4; xylylene phenyl ketone between 4 '-diethyl; 3; 3 '-or 4; 4 '-four (tert-butyl peroxy carbonyl) benzophenone; 4,4 '-lignocaine benzophenone etc.
These sensitizers can use a kind separately, or are mixed with two or more with arbitrary proportion as required.
More specifically, sensitizer of record in " specific function material (special different Machine can material) " (, CMC in 1986) that " functional pigmented chemistry (Machine can property pigment chemistry) " (, CMC in 1981) that can enumerate that " pigment handbook (pigment Ha Application De Block Star Network) " (, talk society in 1986) that the former letter in great river etc. writes, the former letter in great river etc. write and gloomy loyal three youths in pond etc. write, but be not limited to these.In addition, the light to from the ultraviolet to the near infrared region that also can contain other shows the sensitizer of absorption.
The content of sensitizer is 0.1～60 weight portion with respect to Photoepolymerizationinitiater initiater 100 weight portions that comprise in the coloured composition, is preferably 3～60 weight portions, from the viewpoint of photo-curable, development, is more preferably 5～50 weight portions.
＜levelling agent 〉
For the levelability that makes the composition on transparency carrier is good, the preferred levelling agent that adds in color composition for color filter of the present invention.As levelling agent, the dimethyl siloxane that has polyether structure or polyester construction on the preferred main chain.As the object lesson of the dimethyl siloxane that has polyether structure on the main chain, can enumerate BYK-333 that FZ-2122, Bi Ke chemistry corporate system that Dong Li Dow Corning Corporation makes makes etc.As the object lesson of the dimethyl siloxane that has polyester construction on the main chain, can enumerate BYK-310, BYK-370 etc. that Bi Ke chemistry corporate system is made.Having the dimethyl siloxane that has polyester construction on the dimethyl siloxane of polyether structure and the main chain on the main chain also can and use.With regard to the content of levelling agent, in the total weight 100 weight % of coloured composition, preferably use 0.003～0.5 weight % usually.
As the particularly preferred material of levelling agent, can preferably use material as described below: it is a kind of as the so-called surfactant that has hydrophobic group and hydrophilic group in the molecule, though have hydrophilic group, but the dissolubility to water is little, and when making an addition in the coloured composition, it reduces the low feature of capillary ability, in addition, although it is low but be useful to all good characteristic of the wetting state of glass plate to reduce capillary ability, and fully inhibition zone is electrical when adding with the addition of the caused defective of filming that do not occur spuming.As levelling agent, can preferably use dimethyl polysiloxane with polyalkylene oxides unit with such preferred characteristics.As the polyalkylene oxides unit, can be polyethylene oxide unit, polypropyleneoxide unit, dimethyl polysiloxane can have polyethylene oxide unit and polypropyleneoxide unit simultaneously.
In addition, the combining form of polyalkylene oxides unit and dimethyl polysiloxane can for following any: the polyalkylene oxides unit be incorporated into the repetitive of dimethyl polysiloxane hanging type, be incorporated into the end of dimethyl polysiloxane terminal-modified type, alternately repeat the block polymer type of the straight chain shape that combines with dimethyl polysiloxane.Dimethyl polysiloxane with polyalkylene oxides unit can be enumerated for example FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, the FZ-2207 that is sold by Dong Li Dow Corning Corporation, but is not limited to these.
In the levelling agent, can also replenish the surfactant that adds anionic property, cationic, nonionic or both sexes.Surfactant can mix use more than 2 kinds.
As the anionic surfactant who in levelling agent, replenish to add, can enumerate the monoethanolamine, polyoxyethylene alkyl ether phosphate of alkali metal salt, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulphonic acid sodium, dodecyl sulphate monoethanolamine, dodecyltriethanolamine sulfate, ammonium lauryl sulfate, stearic acid monoethanolamine, odium stearate, lauryl sodium sulfate, the styrene-propene acid copolymer of polyoxyethylene alkyl ether sulfate salt, neopelex, styrene-propene acid copolymer etc.
As in levelling agent, replenishing the cationic surfactant that adds, can enumerate alkyl quaternary ammonium salts and ethylene oxide adduct thereof.As in levelling agent, replenishing the nonionic surfactant that adds, can enumerate polyoxyl 10 oleyl ether, polyoxyethylene laurel ether, polyoxyethylene nonylbenzene ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate etc.; The surfactant of amphoteric surfactant such as alkyl betaine, alkyl imidazolines such as alkyl-dimethyl aminoacetic acid betaine and fluorine system and silicon-type.
＜amine compound 〉
The amine compound that can contain in addition, the effect of oxygen in the color composition for color filter of the present invention with reduction of dissolved.As such amine compound, can enumerate triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid-2-dimethylaminoethyl, 4-dimethylaminobenzoic acid 2-Octyl Nitrite and N, N-dimethyl-p-toluidine etc.
＜hardening agent, curing accelerator 〉
In addition, for the curing of auxiliary heat thermosetting resin, in the color composition for color filter of the present invention, can contain hardening agent, curing accelerator etc. as required.As hardening agent, phenol resin, amine compound, acid anhydrides, active ester, carboxylic acid based compound, sulfonic acid based compound etc. are effectively, but are not particularly limited in these, as long as can react with thermoset resin, then can use any hardening agent.In addition, in these hardening agent, preferably enumerating the compound, the amine that have 2 above phenolic hydroxyl groups in 1 molecule is hardening agent.As aforementioned curing accelerator, for example can use amines (for example, dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-N, the N-dimethyl benzyl amine, 4-methoxyl-N, the N-dimethyl benzyl amine, 4-methyl-N, N-dimethyl benzyl amine etc.), quarternary ammonium salt compound (for example triethyl benzyl ammonia chloride etc.), block isocyanate compound (for example dimethylamine etc.), imdazole derivatives bicyclic amidine compound and salt thereof are (for example, imidazoles, glyoxal ethyline, the 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, the 2-phenylimidazole, the 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole etc.), phosphorus compound (for example, triphenylphosphine etc.), the guanamines compound (for example, melamine, guanamines, acetylguanamine, benzoguanamine etc.), Striazine derivative (for example, 2,4-diamido-6-methacryloxyethyl s-triazine, 2-vinyl-2,4-diamido s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid addition product, 2,4-diamido-6-methacryloxyethyl s-triazine isocyanuric acid addition product etc.) etc.These materials can be used alone or two or more kinds may be used.As the content of aforementioned curing accelerator, be that benchmark (100 weight portion) is preferably 0.01～15 weight portion with the total weight of thermoset resin.
＜other additive components 〉
For make composition through the time viscosity stabilization, can contain the storage-stable agent in the color composition for color filter of the present invention.In addition, in order to improve the adaptation with transparency carrier, can also contain driving fit improving agents such as silane coupling agent.
As the storage-stable agent, for example can enumerate organic phosphine, phosphites etc. such as organic acids such as aliquat, lactic acid, oxalic acid such as benzyl trimethyl chloride, diethyl hydramine and methyl ether thereof, tert-butyl catechol, tetraethyl phosphine, tetraphenyl phosphine.The storage-stable agent can 0.1～10 weight portion with respect to total weight 100 weight portions of colorant amount use.
As the driving fit improving agent, can enumerate: vinyl silanes classes such as vinyl three (beta-methoxy-ethoxy) silane, vinyl Ethoxysilane, vinyltrimethoxy silane; γ-methacryloxypropyl trimethoxy silane etc. (methyl) acryloyl group 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; Amino silane classes such as 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, gamma-amino propyl trimethoxy silicane, N-phenyl-gamma-amino propyl trimethoxy silicane, N-phenyl-γ-An Jibingjisanyiyangjiguiwan; Silane coupling agents such as Thiosilicane class such as γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane etc.The driving fit improving agent can 0.01～10 weight portion with respect to total weight 100 weight portions of colorant, the amount of preferred 0.05～5 weight portion is used.
The manufacture method of＜coloured composition 〉
Color composition for color filter of the present invention can use various diverting devices such as three-roll grinder, two roller mills, sand mill, kneader or attitor that each composition is carried out fine dispersion together and make (pigment dispersion).
In addition, when using photosensitive coloring composition (erosion resistant) as color filter, adjustable solvent develop type or the alkali-developable coloured composition of being made for.Solvent develop type or alkali-developable coloured composition can also can have solvent, other pigment dispersing agent and adjuvant to wait and modulate as required by mixing aforementioned pigment dispersion, photopolymerization monomer and/or Photoepolymerizationinitiater initiater.Photoepolymerizationinitiater initiater can add in the stage of modulation coloured composition, also can add after having modulated coloured composition.
When considering viscosity, thickness, flowability and coating, it is above and less than 40 weight % that the solid component concentration of color composition for color filter is preferably 5 weight %.
Color composition for color filter preferably utilize methods such as centrifuging, sintered filter, film filter with the corase particles more than the 5 μ m, be preferably corase particles more than the 1 μ m, more preferably the corase particles more than the 0.5 μ m and the dust of sneaking into are removed.The color composition for color filter that as above obtains does not preferably contain corase particles.Be more preferably below the 0.3 μ m.
In addition, when making the color composition for color filter in the 1st embodiment, can mix following material: as colorant, for average primary particle diameter is that the aspect ratio of 20～50nm and pigment particles is 1: 1～1: 3.5 a pigment; As the resin type spreading agent, be by A block and have A-B segmented copolymer that the B block of the functional group of nitrogen atom constitutes or B-A-B segmented copolymer and amine value are scaled acrylic acid series segmented copolymer below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent with solvophilic; Solvent; And other compositions as required.
In addition, especially, when color composition for color filter of the present invention is formed black-colored resin composition as the black colorant composition (the 2nd embodiment), can mix following material: as the light-proofness black pigment, for average primary particle diameter is below the 50nm and the aspect ratio of primary particle is that 1: 1～1: 2 De perylene is black pigment and carbon black; Resin; Solvent; And other compositions as required, and Gai perylene of Shi is that the content of black pigment is that 78～95 weight % and black-colored resin composition solid component concentration are that 5 weight % are above and less than 40 weight % when being benchmark with the total weight of light-proofness black pigment (A).
In addition, when forming black-colored resin composition as the coloured composition of black (the 3rd embodiment) with color composition for color filter of the present invention, can mix following composition: as the light-proofness black pigment, for average primary particle diameter is below the 50nm and the aspect ratio of primary particle is that 1: 1～1: 2 De perylene is a black pigment; Pigment dispersing agent; Resin, solvent; And other compositions as required.
＜color filter 〉
Next, describe with regard to color filter of the present invention.
Color filter of the present invention possesses filter section and/or the black matrix that is formed by color composition for color filter of the present invention on substrate, for example can possess black matrix and red, green, blue filter section.
Utilize photoetching process formation filter section and/or black matrix to carry out as follows.That is, with coating processes such as spraying, spin coating, slot coated, roller coat, coating is as the colored resin composition of solvent develop type or alkali-developable colored resin composition (erosion resistant) modulation on transparency carrier.To the film after the dried if necessary, carry out the active energy beam exposure by the mask that has predetermined pattern that contacts with this film or contactless state is provided with down.Afterwards, be impregnated in solvent or the alkaline-based developer or pass through to spray etc. sprayed developer solution, removes uncured portion, thereby can form filter section and/or the black matrix with required pattern.Further, in order to promote the polymerization of photosensitive black-colored resin composition, also can heat as required.Utilize photoetching process can form filter section and/or the black matrix higher than print process precision.
As the substrate of color filter, can use resin plates such as glass plate such as the high soda-lime glass of visible light transmissivity, low alkali borosilicate glass, alkali-free alumina borosilicate glass or polycarbonate, polymethylmethacrylate, polyethylene terephthalates.In addition, in order to drive the liquid crystal after the panelization, can on the surface of glass plate or resin plate, form the transparency electrode that constitutes by indium oxide, tin oxide etc.
During development, aqueous solution such as sodium carbonate, NaOH can be used as alkaline-based developer, also organic bases such as dimethyl benzyl amine, triethanolamine can be used.Also can in developer solution, add defoamer, surfactant in addition.
As developing method, can use spray development method, spray development method, impregnation (dipping) development method, stirring (Sheng liquid) development method etc.
In addition, in order to improve the ultraviolet exposure sensitivity, also can be after above-mentioned color composition for color filter coating drying, be coated with water-soluble or alkali soluble resins, for example polyvinyl alcohol (PVA) or water soluble acrylic resin etc. and carry out drying, formation prevents to carry out the active energy beam exposure owing to after oxygen hinders poly-film.
As active energy beam, can use the visible light of electron ray, ultraviolet ray, 400～500nm.With regard to regard to the radiographic source of the electron ray of composition coated face one side irradiation, can use thermionic emission rifle, electric field transmitted rifle etc.In addition, with regard to the radiographic source (light source) of ultraviolet ray and the visible light of 400～500nm, can use for example high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, gallium lamp, xenon lamp, carbon arc lamp etc.Particularly, use extra-high-pressure mercury vapour lamp, xenon mercury vapor lamp, this is because it is pointolite and brightness stability more.Can be set in the scope of 5～1000mJ, the scope of 20 manageable～300mJ on the preferable process from the active energy beam energy of composition coated face one side irradiation in good time.
Be pre-formed when deceiving matrix before on transparency carrier or reflection substrate, forming filter section, can further improve the contrast of display panels.As black matrix, can use the inoranic membrane such as multilayer film, titanium nitride of chromium or chromium/chromium oxide or be dispersed with the resin molding of opacifier, but be not limited to these.In addition, also can on aforementioned transparency carrier or reflection substrate, be pre-formed thin film transistor (TFT) (TFT), form filter section afterwards.By on the TFT substrate, forming filter section and/or black matrix, can improve the aperture opening ratio of display panels and improve brightness.
Herein, the method that forms dyed layer on the TFT substrate is described.At first, on the surface of TFT substrate or formed on the surface of this driving substrate on the substrate surface of passivating films such as silicon nitride film, form light shield layer as required to divide the part that forms pixel, again after coating on this substrate is dispersed with the coloured composition of pigment, carry out prebake and make solvent evaporation, film thereby form.Then, on this is filmed, after photomask exposes, use alkaline-based developer to develop, the unexposed portion dissolving of filming removed, afterwards by after cure pattern of pixels has been disposed in formation with predetermined arrangement pel array.Except the pattern that is used to form pixel, also can be provided for forming the pattern of the pit of through hole or コ font this moment on employed photomask.
As the TFT substrate that when forming dyed layer, uses, can use the substrate same, also can be on these substrates implement to utilize the suitable pre-treatments such as chemical reagent processing, plasma treatment, ion plating, sputter, gas-phase reaction method, vacuum evaporation of silane coupling agent etc. in advance with the substrate of aforementioned color filter.Coating is during coloured composition on substrate, can use the method with the substrate same way as of aforesaid color filter.
With regard to the coating film thickness of filter section, as dried thickness, be preferably 0.1～10 μ m, be more preferably 0.5～6.0 μ m.
With regard to the coating film thickness of black matrix, as dried thickness, be preferably the scope of 0.2～10.0 μ m, be more preferably the scope of 0.2～5.0 μ m.Further, be more preferably the scope of 0.5～2.5 μ m that coating and light-proofness average out easily.
In addition, consider that from the viewpoint of insulativity the relative dielectric constant of the black per 1.0 μ m dry film thickness of matrix is preferably below 8.0, is more preferably below 4.5.
Further, in order to have used ultrared aligning, be the black matrix of 1.0 μ m for dry film thickness, the light transmission rate of wavelength 780nm is preferably more than 15% and less than 99%.The transmitance of wavelength 1000nm is preferably more than 60% and less than 99%.
In addition, considering from the viewpoint of high light-proofness, is the black matrix of 1.0 μ m for dry film thickness, and optical density is preferably more than 1.30, is more preferably more than 2.50.Optical density is high more good more, but is under the situation of ultraviolet ray, visible light at active energy beam, owing to be difficult to obtain cured coating film, therefore is preferably general below 4.5.
During drying coating film, can use drying under reduced pressure machine, convection oven, IR baking oven, hot plate etc.
On color filter, can form cuticula or cylindrical gasket, nesa coating, liquid crystal orientation film etc. as required.
By using sealant that color filter and counter substrate are fitted, inject liquid crystal from the inlet that is arranged at hermetic unit after, seal inlet, and as required light polarizing film or phase retardation film be fitted in the outside of substrate, can make display panels.
Related display panels can be used in and uses twisted nematic (TN), STN Super TN (STN), plane conversion (IPS), homeotropic alignment (VA), optical compensation curved color filters such as (OCB) to carry out the liquid crystal display pattern of colorize.
The driving substrate of＜thin film transistor (TFT) (TFT) mode color liquid crystal display arrangement 〉
The driving of thin film transistor (TFT) (TFT) mode color liquid crystal display arrangement can form black matrix and make by after utilizing coating processes such as spin coating, slot coated, roller coat to form for example red, blue, green chromatic filter joint on the substrate of thin film transistor (TFT) (TFT) with substrate again.
In addition, also can on the substrate of aforementioned thin film transistor (TFT) (TFT), form black matrix, form the chromatic filter joint more thereon.
Embodiment
Below based on embodiment the present invention is described, but the present invention and can't help these embodiment and limit.In addition, among the embodiment, " part " and " % " represents " weight portion " and " weight % " respectively.In addition, the assay method of the average primary particle diameter of the specific surface area of the amine value of the acid number of the weight-average molecular weight of resin (Mw), resin or resin type spreading agent, resin type spreading agent, pigment, pigment and aspect ratio, the contrast of filming, the thickness of filming is as described below.
The weight-average molecular weight of＜resin (Mw) 〉
The weight-average molecular weight of acryl resin (Mw) is used the weight-average molecular weight (Mw) of the polystyrene conversion that THF measures for using TSKgel chromatographic column (eastern Cao company make), utilize the GPC that has been equipped with the RI detecting device (eastern Cao company makes, HLC-8120GPC), eluent.
The acid number of＜resin or resin type spreading agent 〉
Acid number use 0.1N the NaOH ethanolic solution, obtain by potential difference titration.Acid number is represented the acid number of solid constituent.
The amine value of＜resin type spreading agent 〉
The amine value uses the aqueous hydrochloric acid solution of 0.1N, obtain by potential difference titration after, be converted into the equivalent of potassium hydroxide again.The amine value of amine value representation solid constituent.
The specific surface area of＜pigment 〉
The automatic steam adsorbance determinator of the BET method of the mensuration of the specific surface area of pigment by utilizing nitrogen absorption (" BELSORP18 " that Japanese BEL company makes) carries out.
The average primary particle diameter of＜pigment and aspect ratio 〉
The average primary particle diameter of pigment and aspect ratio are measured by the method for directly measuring the primary particle size from electron micrograph.Particularly, measure the minor axis diameter and the major diameter of the primary particle of each pigment, with the particle diameter of average as this pigment particles.Then,, obtain the volume (weight) of each particle according to the approximate cube of obtaining particle diameter to the pigment particles more than 100, with volume average particle size as average primary particle diameter.In addition, as previously mentioned, the ratio of the minor axis diameter during about the minor axis diameter of the primary particle of measuring each pigment and major diameter and the mean value of major diameter is obtained the aspect ratio that the minor axis diameter is made as at 1 o'clock.In addition, electron microscope uses transmission-type (TEM).
＜the contrast of filming 〉
The light that sends from the backlight for liquid crystal display unit is deflected by polaroid, by the dry coating of the coloured composition that is coated with on the glass substrate, arrives polaroid again.The light transmission polaroid if two polaroids are parallel, and the vertical time of plane of polarisation is polarized the sheet blocking.But, during the dry coating of the light that is deflected by polaroid by coloured composition, scattering that pigment particles causes etc. takes place, if produce skew on the part of plane of polarisation, the light quantity that sees through polaroid when then polaroid is parallel reduces, part light printing opacity polaroid when polaroid is vertical.Measure this and see through light, calculate the ratio (contrast) of the brightness of the brightness of polaroid when parallel when vertical as the brightness on the polaroid.
(contrast)=when parallel (brightness)/when vertical (brightness)
In addition, use chroma luminance meter (opening up " BM-5A " of the manufacturing of general Kanggong department), use polaroid (" NPF-G1220DUN " that day eastern electrician company makes) as polaroid as nitometer.During mensuration,, spread the black mask that offers the square hole of 1cm in the mensuration part in order to interdict unwanted light.
＜the thickness of filming 〉
The determining film thickness of filming uses surface-profile measuring instrument (Dektak6M that (strain) Ai Fake company makes) to measure.
At first, about the 1st embodiment, use embodiment and comparative example to illustrate.
The manufacture method of＜resin type spreading agent 〉
(resin type dispersant solution A)
Pack in 4 mouthfuls of detachable flasks that possess thermometer, stirring machine, distillation cascade, refrigeratory 80 parts of methyl ethyl ketones, 86.7 parts of butyl acrylates, 11.8 parts of Block レ Application マ one (Blenmer) PME-200 (methoxy polyethylene glycol methacrylate-styrene polymer), 2.8 parts of sparteine, 1.9 parts of isobutyl ethyl bromides are warming up to 40 ℃ under the nitrogen circulation.Drop into 1.1 parts of stannous chlorides, be warming up to 75 ℃ of beginning polymerizations.The polymeric solution of taking a sample behind the polyase 13 hour confirms that by the solid constituent of polymerization the polymerization yield is 95% or more, weight-average molecular weight (Mw) is 6860, adds 1.4 parts of dimethylaminoethyl methacrylates and 20.0 parts of methyl ethyl ketones, further carries out polymerization.Confirm that by the solid constituent of the polymeric solution after 2 hours the polymerization yield is more than 97%, to be cooled to room temperature, stop polymerization.Dilute for 100 parts with 100 parts of resin solutions of methyl ethyl ketone gained, add Zeo-karb " DIAION PK228LH (Mitsubishi Chemical Ind's manufacturing) " 60 parts, at room temperature stirred 1 hour, further add 6 parts of Kyowaad 500SN (consonance chemical industrial company makes) as neutralizing agent, and carry out stirring in 30 minutes.Thereby remove by filter the residue that Zeo-karb and adsorbent are removed polymerization catalyst by utilization.Further, concentrated resin type dispersant solution and be the glycol monoethyl ether acetate with solvent replacing, thus obtain the resin type dispersant solution A (dispersant A) that the solid constituent ratio is 50 weight % (the amine value is 5mgKOH/g, and acid number is 0mgKOH/g).
(resin type dispersant solution B)
Pack in 4 mouthfuls of detachable flasks that possess thermometer, stirring machine, distillation cascade, refrigeratory 80 parts of methyl ethyl ketones, 85.5 parts of butyl acrylates, 11.7 parts of Blenmer PME-200 (methoxy polyethylene glycol methacrylate-styrene polymer), 2.8 parts of sparteine, 1.9 parts of isobutyl ethyl bromides are warming up to 40 ℃ under the nitrogen circulation.Drop into 1.1 parts of stannous chlorides, be warming up to 75 ℃ of beginning polymerizations.The polymeric solution of taking a sample behind the polyase 13 hour confirms that by the solid constituent of polymerization the polymerization yield is 95% or more, weight-average molecular weight (Mw) is 6860, adds 2.9 parts of dimethylaminoethyl methacrylates and 20.0 parts of methyl ethyl ketones, further carries out polymerization.Confirm that by the solid constituent of the polymeric solution after 2 hours the polymerization yield is more than 97%, to be cooled to room temperature, stop polymerization.Dilute for 100 parts with 100 parts of resin solutions of methyl ethyl ketone gained, add Zeo-karb " DIAION PK228LH (Mitsubishi Chemical Ind's manufacturing) " 60 parts, at room temperature stirred 1 hour, further add 6 parts of Kyowaad 500SN (consonance chemical industrial company makes) as neutralizing agent, and carry out stirring in 30 minutes.Thereby remove by filter the residue that Zeo-karb and adsorbent are removed polymerization catalyst by utilization.Further, concentrated resin type dispersant solution and be the glycol monoethyl ether acetate with solvent replacing, thus obtain the resin type dispersant solution B (dispersant B) that the solid constituent ratio is 50 weight % (the amine value is 10mgKOH/g, and acid number is 0mgKOH/g).
(resin type dispersant solution C)
Pack in 4 mouthfuls of detachable flasks that possess thermometer, stirring machine, distillation cascade, refrigeratory 80 parts of methyl ethyl ketones, 71.0 parts of butyl acrylates, 9.0 parts of Blenmer PME-200 (methoxy polyethylene glycol methacrylate-styrene polymer), 2.8 parts of sparteine, 1.9 parts of isobutyl ethyl bromides are warming up to 40 ℃ under the nitrogen circulation.Drop into 1.1 parts of stannous chlorides, be warming up to 75 ℃ of beginning polymerizations.The polymeric solution of taking a sample behind the polyase 13 hour confirms that by the solid constituent of polymerization the polymerization yield is 95% or more, weight-average molecular weight (Mw) is 6860, adds 20.0 parts of dimethylaminoethyl methacrylates and 20.0 parts of methyl ethyl ketones, further carries out polymerization.Confirm that by the solid constituent of the polymeric solution after 2 hours the polymerization yield is more than 97%, to be cooled to room temperature, stop polymerization.Dilute for 100 parts with 100 parts of resin solutions of methyl ethyl ketone gained, add Zeo-karb " DIAION PK228LH (Mitsubishi Chemical Ind's manufacturing) " 60 parts, at room temperature stirred 1 hour, further add 6 parts of Kyowaad 500SN (consonance chemical industrial company makes) as neutralizing agent, and carry out stirring in 30 minutes.Thereby remove by filter the residue that Zeo-karb and adsorbent are removed polymerization catalyst by utilization.Further, concentrated resin type dispersant solution and be the glycol monoethyl ether acetate with solvent replacing, thus obtain the resin type dispersant solution C (dispersing agent C) that the solid constituent ratio is 50 weight % (the amine value is 70mgKOH/g, and acid number is 0mgKOH/g).
(resin type dispersant solution D)
Pack in 4 mouthfuls of detachable flasks that possess thermometer, stirring machine, distillation cascade, refrigeratory 80 parts of methyl ethyl ketones, 64.1 parts of butyl acrylates, 8.7 parts of Blenmer PME-200 (methoxy polyethylene glycol methacrylate-styrene polymer), 2.8 parts of sparteine, 1.9 parts of isobutyl ethyl bromides are warming up to 40 ℃ under the nitrogen circulation.Drop into 1.1 parts of stannous chlorides, be warming up to 75 ℃ of beginning polymerizations.The polymeric solution of taking a sample behind the polyase 13 hour confirms that by the solid constituent of polymerization the polymerization yield is 95% or more, weight-average molecular weight (Mw) is 6860, adds 27.1 parts of dimethylaminoethyl methacrylates and 20.0 parts of methyl ethyl ketones, further carries out polymerization.Confirm that by the solid constituent of the polymeric solution after 2 hours the polymerization yield is more than 97%, to be cooled to room temperature, stop polymerization.Dilute for 100 parts with 100 parts of resin solutions of methyl ethyl ketone gained, add Zeo-karb " DIAION PK228LH (Mitsubishi Chemical Ind's manufacturing) " 60 parts, at room temperature stirred 1 hour, further add 6 parts of Kyowaad 500SN (consonance chemical industrial company makes) as neutralizing agent, and carry out stirring in 30 minutes.Thereby remove by filter the residue that Zeo-karb and adsorbent are removed polymerization catalyst by utilization.Further, concentrated resin type dispersant solution and be the glycol monoethyl ether acetate with solvent replacing, thus obtain the resin type dispersant solution D (spreading agent D) that the solid constituent ratio is 50 weight % (the amine value is 95mgKOH/g, and acid number is 0mgKOH/g).
(resin type dispersant solution E)
Pack in 4 mouthfuls of detachable flasks that possess thermometer, stirring machine, distillation cascade, refrigeratory 80 parts of methyl ethyl ketones, 57.8 parts of butyl acrylates, 7.9 parts of Blenmer PME-200 (methoxy polyethylene glycol methacrylate-styrene polymer), 2.8 parts of sparteine, 1.9 parts of isobutyl ethyl bromides are warming up to 40 ℃ under stream of nitrogen gas.Drop into 1.1 parts of stannous chlorides, be warming up to 75 ℃ of beginning polymerizations.The polymeric solution of taking a sample behind the polyase 13 hour confirms that by the solid constituent of polymerization the polymerization yield is 95% or more, weight-average molecular weight (Mw) is 6860, adds 34.3 parts of dimethylaminoethyl methacrylic acids and 20.0 parts of methyl ethyl ketones, further carries out polymerization.Confirm that by the solid constituent of the polymeric solution after 2 hours the polymerization yield is more than 97%, to be cooled to room temperature, stop polymerization.Dilute for 100 parts with 100 parts of resin solutions of methyl ethyl ketone gained, add Zeo-karb " DIAION PK228LH (Mitsubishi Chemical Ind's manufacturing) " 60 parts, at room temperature stirred 1 hour, further add 6 parts of Kyowaad 500SN (consonance chemical industrial company makes) as neutralizing agent, and carry out stirring in 30 minutes.Thereby remove by filter the residue that Zeo-karb and adsorbent are removed polymerization catalyst by utilization.Further, concentrated resin type dispersant solution and be the glycol monoethyl ether acetate with solvent replacing, thus obtain the resin type dispersant solution E (spreading agent E) that the solid constituent ratio is 50 weight % (the amine value is 120mgKOH/g, and acid number is 0mgKOH/g).
(resin type dispersant solution F)
Pack in 4 mouthfuls of detachable flasks that possess thermometer, stirring machine, distillation cascade, refrigeratory 80 parts of methyl ethyl ketones, 70.4 parts of butyl acrylates, 9.6 parts of Blenmer PME-200 (methoxy polyethylene glycol methacrylate-styrene polymer), 2.8 parts of sparteine, 1.9 parts of isobutyl ethyl bromides, 20.0 parts of dimethylaminoethyl methacrylates are warming up to 40 ℃ under stream of nitrogen gas.Drop into 1.1 parts of stannous chlorides, be warming up to 75 ℃ of beginning polymerizations.The polymeric solution of taking a sample behind the polyase 13 hour confirms that by the solid constituent of polymeric solution the polymerization yield is more than 97%, to be cooled to room temperature, stops polymerization.Dilute for 100 parts with 100 parts of resin solutions of methyl ethyl ketone gained, add Zeo-karb " DIAION PK228LH (Mitsubishi Chemical Ind's manufacturing) " 60 parts, at room temperature stirred 1 hour, further add 6 parts of Kyowaad 500SN (consonance chemical industrial company makes) as neutralizing agent, and carry out stirring in 30 minutes.Thereby remove by filter the residue that Zeo-karb and adsorbent are removed polymerization catalyst by utilization.Further, concentrated resin type dispersant solution and be the glycol monoethyl ether acetate with solvent replacing, thus obtain the resin type dispersant solution F (spreading agent F) that the solid constituent ratio is 50 weight % (the amine value is 70mgKOH/g, and acid number is 0mgKOH/g).
The amine value of the resin structure of each resin type spreading agent and effectively solid constituent conversion is summarized in table 1.
Table 1
The resin type spreading agent Resin structure Amine value (mgKOH/g)
Dispersant A Block 5
Dispersant B Block 10
Dispersing agent C Block 70
Spreading agent D Block 95
Spreading agent E Block 120
Spreading agent F Random 70
The manufacture method of＜pigment derivative 〉
(pigment derivative 1 (slaine of quinophthalone skeleton sulfonic acid))
With quinophthalone is that 30 parts of yellow uitramarines (C.I. pigment yellow 13 8) are dissolved in 300 parts in 98% sulfuric acid, stirs 8 hours at 70 ℃, carries out sulfonating reaction.The terminal point of reaction does not observe the point of spectrum change when measuring the spectrophotometric spectra of sulfuric acid solution.Then, this reaction solution is injected 3000 parts of frozen water, the sulfonation pigment derivative of separating out is filtered, wash, drying, promptly get quinophthalone skeleton sulfonic acid with the represented structure of formula (4) as the sulfonated derivative of C.I. pigment yellow 13 8.Dried harvest yield is that 334 parts, yield are 99%.
Figure BSA00000517935500411
The slurry of quinophthalone skeleton sulfonic acid is scattered in 10000 parts in the water (pH is 2.5) again.Then, being adjusted to pH with sodium hydrate aqueous solution is 11, dissolves, and forms red solution.In this solution, slowly add 278 parts of aluminum sulfate aqueous solutions (liquid aluminium sulfate).Gradually precipitate occurs from the place that drips, and along with interpolation, pH descends, pH is 3.6 when adding end.Do not observe and fade.Filter out the slurry that contains this precipitate, wash, obtain pigment derivative 1 as the slaine of the quinophthalone skeleton sulfonic acid with the represented structure of formula (5) of the aluminium salt of the sulfonated derivative of C.I. pigment yellow 13 8.Dried harvest yield is that 334 parts, yield are 99%.
Figure BSA00000517935500412
The manufacture method of＜miniaturization pigment 〉
(viridine green PG-1)
Phthalocyanine is 500 parts of viridine green C.I. pigment green 36s (Toyo Ink Manufacturing Co., Ltd. make " Lionol green 6YK "), 1500 parts in sodium chloride and 250 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 8 hours at 80 ℃.Then, this mixing thing dropped in 5 liters the warm water, the limit is heated to 70 ℃ of limits and stirred 1 hour, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 80 ℃ of dry diels, obtain viridine green PG-1.
(viridine green PG-2)
Phthalocyanine is 500 parts of viridine green C.I. pigment green 36s (Toyo Ink Manufacturing Co., Ltd. make " Lionol green 6YK "), 1500 parts in sodium chloride and 250 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 2 hours at 80 ℃.Then, this mixing thing dropped in 5 liters the warm water, the limit is heated to 70 ℃ of limits and stirred 1 hour, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 80 ℃ of dry diels, obtain viridine green PG-2.
(viridine green PG-3)
Phthalocyanine is 500 parts of viridine green C.I. pigment green 36s (Toyo Ink Manufacturing Co., Ltd. make " Lionol green 6YK "), 1500 parts in sodium chloride and 250 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 12 hours at 40 ℃.Then, this mixing thing dropped in 5 liters the warm water, the limit is heated to 70 ℃ of limits and stirred 1 hour, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 80 ℃ of dry diels, obtain viridine green PG-3.
(viridine green PG-4)
Phthalocyanine is 500 parts of viridine green C.I. pigment green 36s (Toyo Ink Manufacturing Co., Ltd. make " Lionol green 6YK "), 1500 parts in sodium chloride and 250 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 2 hours at 80 ℃.Then, this mixing thing dropped in 5 liters the warm water, the limit is heated to 70 ℃ of limits and stirred 1 hour, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 80 ℃ of dry diels, obtain viridine green PG-4.
(viridine green PG-5)
Phthalocyanine is 500 parts of viridine green C.I. pigment green 36s (Toyo Ink Manufacturing Co., Ltd. make " Lionol green 6YK "), 1500 parts in sodium chloride and 250 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 4 hours at 80 ℃.Then, this mixing thing dropped in 5 liters the warm water, the limit is heated to 70 ℃ of limits and stirred 1 hour, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 80 ℃ of dry diels, obtain viridine green PG-5.
(yellow uitramarine PY-1)
Nickel complex is 200 parts of yellow uitramarine C.I. pigment yellows 150 (Lanxess Corporation make " E-4GN "), 1400 parts in sodium chloride and 360 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 8 hours at 80 ℃.Then, this mixing thing dropped in 8000 parts the warm water, the limit is heated to 80 ℃ of limits and stirred 2 hours, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 85 ℃ of dry diels, obtain yellow uitramarine PY-1.
(yellow uitramarine PY-2)
Quinophthalone is 200 parts of yellow uitramarine C.I. pigment yellow 13s 8 (BASF AG make " K0961HD "), 1400 parts in sodium chloride and 360 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 8 hours at 80 ℃.Then, this mixing thing dropped in 8000 parts the warm water, the limit is heated to 80 ℃ of limits and stirred 2 hours, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 85 ℃ of dry diels, obtain yellow uitramarine PY-2.
(yellow uitramarine PY-3)
Isoindoline is 200 parts of yellow uitramarine C.I. pigment yellows 185 (BASF AG make " PalIotolYellow L1155 "), 1400 parts in sodium chloride and 360 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 8 hours at 80 ℃.Then, this mixing thing dropped in 8000 parts the warm water, the limit is heated to 80 ℃ of limits and stirred 2 hours, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 85 ℃ of dry diels, obtain yellow uitramarine PY-3.
(black pigment PBLK-2)
Perylene is 500 parts of black pigment C.I. pigment blacks 32 (BASF AG make " PalIogen Black L0086 "), 2500 parts in sodium chloride and 250 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 12 hours at 80 ℃.Then, this mixing thing dropped in 5 liters the warm water, the limit is heated to 70 ℃ of limits and stirred 1 hour, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 80 ℃ of dry diels, obtain black pigment PBLK-2.
(black pigment PBLK-3)
Perylene is 500 parts of black pigments (BASF AG make " Lumogen Black FK4281 "), 2500 parts in sodium chloride and 250 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 12 hours at 40 ℃.Then, this mixing thing dropped in 5 liters the warm water, the limit is heated to 70 ℃ of limits and stirred 1 hour, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 80 ℃ of dry diels, obtain black pigment PBLK-3.
(black pigment PBLK-4)
Perylene is 500 parts of black pigment C.I. pigment blacks 31 (BASF AG make " PalIogen Black S0084 "), 2500 parts in sodium chloride and 250 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 5 hours at 80 ℃.Then, this mixing thing dropped in 5 liters the warm water, the limit is heated to 70 ℃ of limits and stirred 1 hour, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 80 ℃ of dry diels, obtain black pigment PBLK-4.
(black pigment PBLK-5)
Perylene is 500 parts of black pigments (BASF AG make " Lumogen Black FK4281 "), 2500 parts in sodium chloride and 250 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 5 hours at 80 ℃.Then, this mixing thing dropped in 5 liters the warm water, the limit is heated to 70 ℃ of limits and stirred 1 hour, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 80 ℃ of dry diels, obtain black pigment PBLK-5.
Table 2
Pigment No. Pigment Average primary particle diameter Aspect ratio
PG-1 Phthalocyanine is a viridine green 25nm 1∶2.3
PG-2 Phthalocyanine is a viridine green 48nm 1∶2.3
PG-3 Phthalocyanine is a viridine green 15nm 1∶2.6
PG-4 Phthalocyanine is a viridine green 95nm 1∶2.6
PG-5 Phthalocyanine is a viridine green 45nm 1∶4.5
PY-1 Metal complex system yellow uitramarine 23nm 1∶1.6
PY-2 Quinophthalone is a yellow uitramarine 26nm 1∶1.6
PY-3 Isoindoline is a yellow uitramarine 35nm 1∶1.6
PY-4 Metal complex system yellow uitramarine 150nm 1∶4.3
PY-5 Quinophthalone is a yellow uitramarine 120nm 1∶5.0
PY-6 Isoindoline is a yellow uitramarine 98nm 1∶4.7
PBLK-1 Perylene is a black pigment 30nm 1∶1.5
PBLK-2 Perylene is a black pigment 45nm 1∶1.5
PBLK-3 Perylene is a black pigment 15nm 1∶1.5
PBLK-4 Perylene is a black pigment 100nm 1∶1.5
PBLK-5 Perylene is a black pigment 50nm 1∶4.0
PBLK-6 Carbon is black pigment 24nm 1∶1.5
PBLK-7 Carbon is black pigment 55nm 1∶4.4
PY-4: nickel complex is yellow uitramarine C.I. pigment yellow 150 (" E-4GN " that Lanxess Corporation makes)
PY-5: quinophthalone is yellow uitramarine C.I. pigment yellow 13 8 (" K0961HD " that BASF AG makes)
PY-6: isoindoline is yellow uitramarine C.I. pigment yellow 185 (" PalIotolYellow L1155 " that BASF AG makes)
PBLK-1: perylene is black pigment (" Lumogen Black FK4281 " that BASF AG makes)
PBLK-6: carbon is " #45 " that black pigment Mitsubishi Chemical Ind makes
PBLK-7: carbon is " MA220 " that black pigment Mitsubishi Chemical Ind makes
The manufacture method of＜acrylic resin soln 〉
(modulation of acrylic resin soln 1)
70.0 parts of the cyclohexanone of packing in the reaction vessel of thermometer, cooling tube, nitrogen ingress pipe, stirring apparatus are installed in detachable 4 mouthfuls of flasks, be warming up to 80 ℃, after carrying out nitrogen replacement in the reaction vessel, with buret with dripped 13.3 parts of n-BMAs, methacrylic acid-4.6 parts of 2-hydroxy methacrylates, 4.3 parts of methacrylic acids in 2 hours, to 7.4 parts of cumylphenol oxirane modification acrylates (" ARONIX M110 " that Toagosei Co., Ltd makes), 2, the potpourri that 2 '-azoisobutyronitrile is 0.4 part.After drip finishing, continue reaction 3 hours again, obtain weight-average molecular weight (Mw) and be the solution of 26000 acryl resin.After being cooled to room temperature, the about 2g of sample tree lipoprotein solution, measure nonvolatile component at 180 ℃ of heat dryings after 20 minutes, in synthetic before resin solution, add the dihydroxypropane single-ether acetate, thereby obtain acrylic resin soln 1 according to the mode that makes nonvolatile component become 20 weight %.
(modulation of acrylic resin soln 2)
In possessing detachable 4 mouthfuls of flasks of thermometer, cooling tube, nitrogen ingress pipe, buret and stirring apparatus, pack into 370 parts of cyclohexanone, be warming up to 80 ℃, after carrying out nitrogen replacement in the flask, with buret with dripping in 2 hours to 25 parts of 18 parts of cumylphenol oxirane modification acrylates (" ARONIX M110 " that Toagosei Co., Ltd makes), 10 parts of methacrylic acid benzyl esters, 18.2 parts of glycidyl methacrylate, methyl methacrylate and 2, the potpourri that 2 '-azoisobutyronitrile is 2.0 parts.After dripping end,, add with 1.0 parts of resulting solution of cyclohexanone 50 parts of dissolvings azoisobutyronitrile, after 3 hours 100 ℃ of reactions more further 100 ℃ of continuation reactions 1 hour.Then, air displacement will be replaced with in the container, in said vesse, drop into 0.1 part of 9.3 parts in acrylic acid (glycidyl 100%), 0.5 part of three-dimethyl p-aminophenol and quinhydrones, 120 ℃ of sustained responses 6 hours, when the solid constituent acid number is 0.5, finish reaction, obtain the solution of acryl resin.Further, continue to add 0.5 part of 19.5 parts of tetrabydrophthalic anhydrides (hydroxyl of generation 100%), triethylamine,, obtain weight-average molecular weight (Mw) and be 19000 acrylic resin soln 120 ℃ of reactions 3.5 hours.After being cooled to room temperature, the about 2g of sample tree lipoprotein solution, measure nonvolatile component at 180 ℃ of heat dryings after 20 minutes, in synthetic before resin solution, add cyclohexanone, thereby obtain acrylic resin soln 2 as the active energy ray-curable resin according to the mode that makes nonvolatile component become 20 weight %.
[embodiment 1]
(pigment dispersion (D-1))
After following potpourri mixed, use the zirconium oxide bead of diameter as 0.5mm, after 3 hours,, thereby make pigment dispersion (DP-11) with Eiger mill (" MINI MODEL M-250MKII " that Eiger Japanese firm makes) dispersion with the filtrator filtration of 5.0 μ m.
Viridine green PG-1:10.0 part
Acrylic resin soln 1:35.0 part
Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts
Resin type dispersant solution C (dispersing agent C): 6.0 parts
[embodiment 2～14, comparative example 1～16]
Below, except pigment, pigment derivative being changed to composition shown in table 3, the table 4 and use level, similarly operate conditioned pigment dispersion (D-2～30) with pigment dispersion (D-1).
Table 3
Table 4
Figure BSA00000517935500471
The evaluation of＜pigment dispersion 〉
About viscosity characteristics, contrast (CR) or the optical density (OD) of the pigment dispersion of gained, estimate by following method.The results are shown in table 5,6.
(viscosity characteristics)
The viscosity of pigment dispersion is used the initial viscosity of E type viscosity meter (" ELD type viscosity meter " that eastern machine industry company makes) when being determined at 25 ℃.In addition, with this pigment dispersion 25g with air-tight state in glass container, after leaving standstill 7 days under 40 ℃, by measuring viscosity with above-mentioned same method, with this as through the time viscosity.In addition, be divided into 3 grade evaluations according to following benchmark.
Zero: viscosity is less than 20mPas
△: viscosity is more than the 20mPas and less than 40mPas
*: viscosity is more than the 40mPas
(contrast (CR))
Use spin coater to change the pigment dispersion (D-1～17) of revolution ground coating gained, dry film thickness is reached about 1 μ m, make 3 coated base plates.Coating back uses hot-air oven at 80 ℃ down after dry 30 minutes, measures each thickness and contrast, the contrast (CR) when 3 data are used the linear dependence method to obtain thickness to be 1 μ m.In addition, be divided into 3 grade evaluations according to following benchmark.
Zero: CR is more than 8000
△: CR is more than 6000 and less than 8000
*: CR is less than 6000
(optical density (OD))
Use spin-coating method behind the pigment dispersion of coating gained on the glass substrate of 100mm * 100mm, making dry film thickness is filming of 1.0 μ m, heats 20 minutes down at 230 ℃.Utilize Macbeth densimeter (GRETAG D200-II) to measure the as above optical density (OD) of the pigment dispersion coated substrates of gained, the optical density (OD) when obtaining thickness and being 1.0 μ m.
In addition.OD is divided into 3 grade evaluations according to following benchmark.
Zero: OD is more than 1.5
△: OD is more than 1.3 and less than 1.5
*: OD is less than 1.3
Table 5
Figure BSA00000517935500481
Color composition for color filter of the present invention contains colorant and resin type spreading agent, it is that the aspect ratio of 20～50nm and pigment particles is 1: 1～1: 3.5 a pigment that described colorant contains average primary particle diameter, described resin type spreading agent contains the acrylic acid series segmented copolymer, described acrylic acid series segmented copolymer is A-B segmented copolymer or the B-A-B segmented copolymer that is made of A block with solvophilic and the B block with functional group of nitrogen atom, and its amine value is scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent, and it is low and stable that color composition for color filter of the present invention has all obtained viscosity, the good result that CR is also high (embodiment 1～8).
Wherein, the pigment dispersion (D-3) of embodiment 3 that has further added the slaine of quinophthalone skeleton sulfonic acid for the pigment dispersion (D-1) of embodiment 1 is compared with embodiment 1, and CR and viscosity are better.
Relative therewith, the average primary particle diameter of pigment particles is comparative example 1 tackify significantly of 15nm.The average primary particle diameter of pigment particles is that the aspect ratio of comparative example 2, the pigment particles of 95nm is that CR is variation greatly in 1: 4.5 the comparative example 3.
In addition, the amine value of resin type spreading agent less than the pigment dispersion (D-13) of the comparative example 5 of 10mgKOH/g, be that the pigment dispersion (D-12) of the above comparative example 4 of 99mgKOH/g is high viscosity, especially, CR less than the pigment dispersion (D-13) of the comparative example 5 of 10mgKOH/g is also low, uses the viscosity height of pigment dispersion (D-14) of comparative example 6 of the spreading agent of random.
Table 6
Figure BSA00000517935500491
Color composition for color filter of the present invention contains colorant and resin type spreading agent, it is that the aspect ratio of 20～50nm and pigment particles is 1: 1～1: 3.5 a pigment that described colorant contains average primary particle diameter, described resin type spreading agent contains the acrylic acid series segmented copolymer, described acrylic acid series segmented copolymer is A-B segmented copolymer or the B-A-B segmented copolymer that is made of A block with solvophilic and the B block with functional group of nitrogen atom, and its amine value is scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent, and it is low and stable that color composition for color filter of the present invention has all obtained viscosity, the good result that OD is also high (embodiment 9～14).
Especially, it is better to add pigment dispersion (D-20) viscosity of embodiment 11 of slaine of quinophthalone skeleton sulfonic acid for the pigment dispersion (D-18) of embodiment 9.
Relative therewith, contain average primary particle diameter and be pigment dispersion (D-24) tackify significantly of comparative example 10 of the pigment particles of 15nm.Contain average primary particle diameter and be the OD variation greatly of pigment dispersion (D-25) of comparative example 11 of the pigment particles of 100nm.Further contain aspect ratio and be the OD variation greatly of pigment dispersion (D-26) of comparative example 12 of 1: 4.0 pigment particles.
In addition, the amine value of resin type spreading agent uprises less than the pigment dispersion (D-28) of the comparative example 14 of 10mgKOH/g, for the viscosity of the pigment dispersion (D-127) of the above comparative example 13 of 99mgKOH/g.Especially, also low less than the OD of the pigment dispersion (D-28) of the comparative example 14 of 10mgKOH/g, use the viscosity height of pigment dispersion (D-29) of comparative example 15 of the spreading agent of random.
[embodiment 15]
(photosensitive coloring composition (R-1))
After following potpourri mixed, filter, obtain photosensitive coloring composition (R-1) with the filtrator of 1.0 μ m.
(pigment dispersion) (totally 50 parts)
Pigment dispersion 1: pigment dispersion (D-1): 30.0 parts
Pigment dispersion 2: pigment dispersion (D-6): 20.0 parts
Acrylic resin soln 2:10.6 part
Trimethylolpropane triacrylate: 4.2 parts (" NK ester ATMPT " that Xin Zhong village chemical company makes)
Photoepolymerizationinitiater initiater (" IRGACURE 907 " that Ciba company makes): 1.2 parts
Sensitizer (" EAB-F " that hodogaya chemical company makes): 0.4 part
Silane coupling agent (" KBM-803 " that chemical industrial company of SHIN-ETSU HANTOTAI makes): 0.4 part
Glycol monoethyl ether acetate: 23.2 parts
[embodiment 16～31, comparative example 17～31]
(photosensitive coloring composition (R-2～32))
Except the kind and use level that pigment dispersion are become the pigment dispersion shown in table 7, the table 8, similarly obtain photosensitive coloring composition (R-2～32) with photosensitive coloring composition (R-1).In the photosensitive coloring composition and used pigment dispersion 1,2, but, in whole whole photosensitive coloring compositions, it is 50 parts as the total of pigment dispersion.
Table 7
Embodiment No. Photosensitive coloring composition Pigment dispersion 1 Part Pigment dispersion 2 Part
Embodiment 15 R-1 D-1 30.0 D-6 20.0
Embodiment 16 R-2 D-2 30.0 D-6 20.0
Embodiment 17 R-3 D-3 30.0 D-6 20.0
Embodiment 18 R-4 D-4 30.0 D-6 20.0
Embodiment 19 R-5 D-5 30.0 D-6 20.0
Embodiment 20 R-6 D-1 30.0 D-7 20.0
Embodiment 21 R-7 D-1 30.0 D-8 20.0
Embodiment 22 R-8 D-1 30.0 D-15 20.0
Embodiment 23 R-9 D-1 30.0 D-16 20.0
Embodiment 24 R-10 D-1 30.0 D-17 20.0
Comparative example 17 R-11 D-9 30.0 D-15 20.0
Comparative example 18 R-12 D-10 30.0 D-15 20.0
Comparative example 19 R-13 D-11 30.0 D-15 20.0
Comparative example 20 R-14 D-12 30.0 D-15 20.0
Comparative example 21 R-15 D-13 30.0 D-15 20.0
Comparative example 22 R-16 D-14 30.0 D-15 20.0
Comparative example 23 R-17 D-10 30.0 D-16 20.0
Comparative example 24 R-18 D-10 30.0 D-17 20.0
Table 8
Embodiment No. Photosensitive coloring composition Pigment dispersion 1 Part Pigment dispersion 2 Part
Embodiment 25 R-19 D-18 50.0
Embodiment 26 R-20 D-19 50.0
Embodiment 27 R-21 D-20 50.0
Embodiment 28 R-22 D-21 50.0
Embodiment 29 R-23 D-22 50.0
Embodiment 30 R-24 D-18 40.0 D-23 10.0
Embodiment 31 R-25 D-18 40.0 D-30 10.0
Comparative example 25 R-26 D-24 50.0
Comparative example 26 R-27 D-25 50.0
Comparative example 27 R-28 D-26 50.0
Comparative example 28 R-29 D-27 50.0
Comparative example 29 R-30 D-28 50.0
Comparative example 30 R-31 D-29 50.0
Comparative example 31 R-32 D-25 40.0 D-30 10.0
The evaluation of＜photosensitive coloring composition 〉
About viscosity characteristics, contrast (CR) or the optical density (OD) and the developing powder of the photosensitive coloring composition of gained, estimate by following method.The results are shown in table 9～10.
(viscosity characteristics)
The viscosity of photosensitive coloring composition uses E type viscosity meter (" ELD type viscosity meter " that eastern machine industry company makes) to be determined at 25 ℃ initial viscosity.In addition, with this pigment dispersion 25g with air-tight state in glass container, after leaving standstill 7 days under 40 ℃, by measuring viscosity with above-mentioned same method, as through the time viscosity.
Zero: viscosity is less than 4.0mPas
△: viscosity is more than the 4.0mPas and less than 7.0mPas
*: viscosity is more than the 7.0mPas
(contrast (CR))
Use spin coater to change the photosensitive coloring composition (R-1～18) of revolution ground coating gained, dry film thickness is reached about about 2 μ m, make 3 coated base plates.Coating back uses hot-air oven at 80 ℃ down after dry 30 minutes, measures each thickness and contrast, the contrast (CR) when 3 data are obtained thickness and are 1 μ m by the linear dependence method.In addition, be divided into 3 grade evaluations according to following benchmark.
Zero: CR is more than 8000
△: CR is more than 6000 and less than 8000
*: CR is less than 6000
(optical density (OD))
Use spin-coating method behind the photosensitive coloring composition (R-19～32) of coating gained on the glass substrate of 100mm * 100mm, making dry film thickness is filming of 1.0 μ m, heats 20 minutes down at 230 ℃.Utilize Macbeth densimeter (GRETAG D200-II) to measure the as above optical density (OD) of the pigment dispersion coated substrates of gained, the optical density (OD) when obtaining thickness and being 1.0 μ m.
In addition.OD is divided into 3 grade evaluations according to following benchmark.
Zero: OD is more than 1.5
△: OD is more than 1.3 and less than 1.5
*: OD is less than 1.3
(developing powder)
Use spin-coating method behind coating photosensitive coloring composition on the glass substrate of 10cm * 10cm, in cleaning oven, 70 ℃ of heating 15 minutes and remove and desolvate down, obtain filming of about 2 μ m.Then, utilize high-pressure mercury-vapor lamp across mask pattern with 60mJ/cm 2After this substrate exposed, use 0.04 weight % potassium hydroxide aqueous solution (developer temperatur is 26 ℃) to carry out the spray development of pressure, measure the painted dissolving of filming until time (development dissolution time) that substrate surface exposes as 0.25MPa.Measure the development dissolution time of each photosensitive coloring composition, be divided into 3 grade evaluations according to following benchmark.
Zero: be less than 20 seconds
△: more than 20 seconds and be less than 30 seconds
*: more than 30 seconds
Table 9
Figure BSA00000517935500531
Color composition for color filter of the present invention contains colorant and resin type spreading agent, it is that the aspect ratio of 20～50nm and pigment particles is 1: 1～1: 3.5 a pigment that described colorant contains average primary particle diameter, described resin type spreading agent contains the acrylic acid series segmented copolymer, described acrylic acid series segmented copolymer is A-B segmented copolymer or the B-A-B segmented copolymer that is made of A block with solvophilic and the B block with functional group of nitrogen atom, and its amine value is scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent, and it is low and stable that color composition for color filter of the present invention has all obtained viscosity, the good result that CR is also high and developing powder is also fast (embodiment 15～19 and 23～24).
Wherein, the CR and the viscosity of photosensitive coloring composition (R-3) of embodiment 17 of slaine that has further added quinophthalone skeleton sulfonic acid for the photosensitive coloring composition (R-1) of embodiment 15 is better, therefore the result for being more preferably.
Relative therewith, the average primary particle diameter of pigment particles is the initial viscosity height of photosensitive coloring composition (R-11) of the comparative example 17 of 15nm and 150nm, passes in time and tackify significantly.On the other hand, the average primary particle diameter of pigment particles is the CR variation greatly of photosensitive coloring composition (R-12) of the comparative example 18 of 95nm and 150nm.Further, the aspect ratio of pigment particles is the CR variation greatly of photosensitive coloring composition (R-13) of the comparative example 19 of 1: 4.5 and 1: 4.3.
As mentioned above, comparative example all can not satisfy the whole of CR, viscosity and developing powder.
Table 10
Figure BSA00000517935500541
Color composition for color filter of the present invention contains colorant and resin type spreading agent, it is that the aspect ratio of 20～50nm and pigment particles is 1: 1～1: 3.5 a pigment that described colorant contains average primary particle diameter, described resin type spreading agent contains the acrylic acid series segmented copolymer, described acrylic acid series segmented copolymer is A-B segmented copolymer or the B-A-B segmented copolymer that is made of A block with solvophilic and the B block with functional group of nitrogen atom, and its amine value is scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent, and it is low and stable that color composition for color filter of the present invention has all obtained viscosity, the good result that OD is also high and developing powder is also fast (embodiment 25～31).
Wherein, the viscosity of photosensitive coloring composition (R-21) of embodiment 27 of slaine that has added quinophthalone skeleton sulfonic acid for the photosensitive coloring composition (R-19) of embodiment 25 is better, therefore the result for being more preferably.
Relative therewith, the average primary particle diameter of pigment particles is photosensitive coloring composition (R-26) tackify significantly of the comparative example 25 of 15nm.The average primary particle diameter of pigment particles is the OD variation greatly of photosensitive coloring composition (R-27) of the comparative example 26 of 100nm.Further, the aspect ratio of pigment particles is the OD variation greatly of photosensitive coloring composition (R-28) of 1: 4.0 comparative example 27.
In addition, the amine value of resin type spreading agent less than the photosensitive coloring composition (R-30) of the comparative example 29 of 10mgKOH/g, be the viscosity height of the photosensitive coloring composition (R-29) of the above comparative example 28 of 99mgKOH/g.In addition, the photosensitive coloring composition of comparative example 28 (R-29) is owing to high amine value, so developing powder is slow.In addition, the viscosity height of the photosensitive coloring composition (R-31) of the comparative example 30 of use random spreading agent.
The manufacturing of＜color filter 〉
At first, total to viridine green in the photosensitive coloring composition (R-1) and yellow uitramarine is replaced for 5.0 parts: replacing with carbon in the black photosensitive colouration composition 1 is 5.0 parts of black pigments (PBLK-7), replace with C.I. paratonere 254/C.I. paratonere 177=3.0 part/2.0 parts in the red photosensitive coloring composition 1, replace with C.I. naphthol green 58/C.I. pigment yellow 150=3.0 part/2.0 parts in the green photosensitive coloured composition 1, replace with 5 parts of C.I. pigment blue 15s in the blue photosensitive coloring composition 1: 3, in addition, (R-1) similarly modulates the shades of colour photosensitive coloring composition with photosensitive coloring composition, thereby obtains black photosensitive colouration composition 1, red photosensitive coloring composition 1, green photosensitive coloured composition 1, blue photosensitive coloring composition 1.
[manufacturing of color filter 1]
Use extrusion coater on the glass substrate of 100mm * 100mm, to be coated with the thick black photosensitive colouration composition 1 of about 1.0 μ m, removed in 20 minutes at 70 ℃ baking oven inner dryings and desolvate.Then, use exposure device utilization ultraviolet ray to carry out the candy strip exposure.Exposure is made as 100mJ/cm 2After further utilizing the developer solution that comprises aqueous sodium carbonate to carry out spray development and remove unexposed portion, clean, under 230 ℃, this substrate was heated 20 minutes with ion exchange water, thus the black matrix of the about 10 μ m of formation live width.
Then, on the glass substrate that has formed black matrix, be coated with the thick red photosensitive coloring composition 1 of about 2 μ m, removed in 20 minutes at 70 ℃ baking oven inner dryings and desolvate.Then, use exposure device utilization ultraviolet ray to carry out the candy strip exposure.Exposure is made as 100mJ/cm 2After further utilizing the developer solution that comprises aqueous sodium carbonate to carry out spray development and remove unexposed portion, clean, under 230 ℃, this substrate was heated 30 minutes with ion exchange water, thus the red filter joint of the about 50 μ m of formation live width.Then, by same operation, use photosensitive coloring composition (R-1) to form the green filter joint on the next door of red filter joint, then use blue photosensitive coloring composition 1 to form the blue electric-wave filter joint, thereby obtain possessing on the same glass substrate color filter 1 of 3 color filters joint.
[manufacturing of color filter 2]
Use extrusion coater on the glass substrate of 100mm * 100mm, to be coated with the thick photosensitive coloring composition (R-24) of about 1.0 μ m, removed in 20 minutes at 70 ℃ baking oven inner dryings and desolvate.Then, use exposure device utilization ultraviolet ray to carry out the candy strip exposure.Exposure is made as 100mJ/cm 2After further utilizing the developer solution that comprises aqueous sodium carbonate to carry out spray development and remove unexposed portion, clean, under 230 ℃, this substrate was heated 20 minutes with ion exchange water, thus the black matrix of the about 10 μ m of formation live width.
Then, on the glass substrate that has formed black matrix, be coated with the thick red photosensitive coloring composition 1 of about 2 μ m, removed in 20 minutes at 70 ℃ baking oven inner dryings and desolvate.Then, use exposure device utilization ultraviolet ray to carry out the candy strip exposure.Exposure is made as 100mJ/cm 2After further utilizing the developer solution that comprises aqueous sodium carbonate to carry out spray development and remove unexposed portion, clean, under 230 ℃, this substrate was heated 30 minutes with ion exchange water, thus the red filter joint of the about 50 μ m of formation live width.Then, by same operation, use green photosensitive coloured composition 1 to form the green filter joint on the next door of red filter joint, then use blue photosensitive coloring composition 1 to form the blue electric-wave filter joint, thereby obtain possessing on the same glass substrate color filter 2 of 3 color filters joint.
In the color filter 1,2 owing to all possess at least a of the filter section that forms by color composition for color filter of the present invention and black matrix, therefore can be in developing procedure not residual residue and form pattern at short notice, again because contrast height and color reproduction area field width, therefore use the liquid crystal indicator of this color filter can show to have and strengthen and more weak chromatic colour.
In addition, though color filter of the present invention 2 is to form BM on TFT, electrical specification excellence and askiatic are residual.In addition, owing to can simplify manufacturing process, therefore use the answer speed of liquid crystal indicator of this color filter fast, low-cost and can reproduce chromatic colour.
Next, about the 2nd embodiment, use embodiment and comparative example to describe.
At first, be that the physics value of black pigment, the structural formula of pigment derivative, the manufacturing of black pigment dispersion describe about the modulation, perylene of the acryl resin that is used for embodiment and comparative example.
[modulation of acrylate solution]
70.0 parts of the cyclohexanone of packing in the reaction vessel of thermometer, cooling tube, nitrogen ingress pipe, stirring apparatus are installed in detachable 4 mouthfuls of flasks, be warming up to 80 ℃, after carrying out nitrogen replacement in the reaction vessel, with buret with dripped 13.3 parts of n-BMAs, methacrylic acid-4.6 parts of 2-hydroxy methacrylates, 4.3 parts of methacrylic acids in 2 hours, to 7.4 parts of cumylphenol oxirane modification acrylates (" ARONIX M110 " that Toagosei Co., Ltd makes), 2, the potpourri that 2 '-azoisobutyronitrile is 0.4 part.After drip finishing, continue reaction 3 hours again, obtain weight-average molecular weight and be the solution of 26000 acryl resin.After being cooled to room temperature, the about 2g of sample tree lipoprotein solution, measure nonvolatile component at 180 ℃ of heat dryings after 20 minutes, in synthetic before resin solution, add the methoxy-propyl acetate according to the mode that makes nonvolatile component become 30 weight %, thus the modulation acrylic resin soln.
The [perylene is the physics value of black pigment]
Table 1 '
Perylene is a black pigment Average primary particle diameter Aspect ratio Shape of particle
Perylene is a black pigment 1 ' 30nm 1∶1.5 Spherical
Perylene is a black pigment 2 ' 200nm 1∶4.0 Needle-like
Perylene is a black pigment 3 ' 200nm 1∶7.5 Sharp-pointed needle-like
Perylene is a black pigment 4 ' 100nm 1∶7.5 Sharp-pointed needle-like
Perylene is a black pigment 5 ' 100nm 1∶1.5 Spherical
Perylene is a black pigment 6 ' 45nm 1∶4.0 Needle-like
Perylene is a black pigment 7 ' 15nm 1∶1.5 Spherical
Perylene is a black pigment 8 ' 45nm 1∶1.5 Spherical
Perylene is a black pigment 1 '
Perylene is " the Lumogen Black FK4280 " that black pigment BASF AG makes
Perylene is a black pigment 2 '
Perylene be black pigment C.I. pigment black 31 (BASF AG make " Paliogen Black S0084 "),
Perylene is a black pigment 3 '
Perylene is black pigment C.I. pigment black 32 (" Paliogen Black L0086 " that BASF AG makes)
Perylene is a black pigment 4 '
Perylene is " the Lumogen Black FK4281 " that black pigment BASF AG makes
Perylene is a black pigment 5 '
Perylene is 500 parts of black pigment C.I. pigment blacks 31 (BASF AG make " Paliogen Black S0084 "), 2500 parts in sodium chloride and 250 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 5 hours at 80 ℃.Then, this mixing thing dropped in 5 liters the warm water, the limit is heated to 70 ℃ of limits and stirred 1 hour, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 80 ℃ of dry diels, De is a black pigment 5 ' Dao perylene.
Perylene is a black pigment 6 '
Perylene is 500 parts of black pigments (BASF AG make " Lumogen Black FK4281 "), 2500 parts in sodium chloride and 250 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 5 hours at 80 ℃.Then, this mixing thing dropped in 5 liters the warm water, the limit is heated to 70 ℃ of limits and stirred 1 hour, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 80 ℃ of dry diels, De is a black pigment 6 ' Dao perylene.
Perylene is a black pigment 7 '
Perylene is 500 parts of black pigments (BASF AG make " Lumogen Black FK4281 "), 2500 parts in sodium chloride and 250 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 12 hours at 40 ℃.Then, this mixing thing dropped in 5 liters the warm water, the limit is heated to 70 ℃ of limits and stirred 1 hour, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 80 ℃ of dry diels, De is a black pigment 7 ' Dao perylene.
Perylene is a black pigment 8 '
Perylene is 500 parts of black pigment C.I. pigment blacks 32 (BASF AG make " Paliogen Black L0086 "), 2500 parts in sodium chloride and 250 parts of 1 gallon of kneaders of stainless steel of packing into of diethylene glycol (aboveground making institute company make), mixing 12 hours at 80 ℃.Then, this mixing thing dropped in 5 liters the warm water, the limit is heated to 70 ℃ of limits and stirred 1 hour, thereby forms pulpous state, filters repeatedly, washes, remove sodium chloride and diethylene glycol after, at 80 ℃ of dry diels, obtaining table 1 ’ De perylene is black pigment 8 '.
[structural formula of pigment derivative]
Table 2 '
Figure BSA00000517935500591
[making of black pigment dispersion]
(black pigment dispersion 1 ')
After the potpourri of following composition mixed, use the zirconium oxide bead of diameter as 0.5mm, after 5 hours,, thereby make black pigment dispersion 1 ' with Eiger mill (" MINI MODEL M-250MKII " that Eiger Japanese firm makes) dispersion with the filtrator filtration of 5.0 μ m.
Carbon black: 14.4 parts " #45 " (Mitsubishi Chemical's (strain) manufacturing)
1 ': 0.6 part of pigment derivative
1 ': 1.5 parts of " BYK-110 " (Bi Ke chemistry Japanese firm makes) (acid number are that 53mgKOH/g, nonvolatile component are 52%) of resin type spreading agent
Acrylic resin soln: 14.1 parts
Solvent: cyclohexanone: 69.4 parts
(black pigment dispersion 2 '～25 ')
Except that changing to table 3 ' shown in composition and use level, similarly make black pigment dispersion 2 '～25 ' with black pigment dispersion 1 '.
Table 3 '
Figure BSA00000517935500601
About table 3 ' in abbreviation and compound, be expressed as follows.
Pigment
R/B/Y pigment color mixture 1: the black pigment that mixes with the weight rate of PR177/PB15:6/PY139=50/40/10
R/B/Y pigment color mixture 2: the black pigment that mixes with the weight rate of PR179/PB15:6/PY185=50/40/10
Pigment derivative
Derivant 1 '～4 ': be respectively table 2 ' shown in pigment derivative 1 '～4 '
The resin type spreading agent
Resin type spreading agent 1 ': acidic resins type spreading agent " BYK-110 " (Bi Ke chemistry Japanese firm makes) (acid number is that 53mgKOH/g, nonvolatile component are 52%)
Resin type spreading agent 2 ': acidic resins type spreading agent " BYK-111 " (Bi Ke chemistry Japanese firm makes) (acid number is that 129mgKOH/g, nonvolatile component are 100%)
Resin type spreading agent 3 ': acidic resins type spreading agent " BYK-171 " (Bi Ke chemistry Japanese firm makes) (acid number is that 13mgKOH/g, nonvolatile component are 40%)
Resin type spreading agent 4: basic resin type spreading agent " BYK-6919 " (Bi Ke chemistry Japanese firm makes) (nonvolatile component is 60%)
Solvent: cyclohexanone
[embodiment 1 '～22 ', comparison 1 '～11 ']
(black-colored resin composition 1 '～33 ')
With table 4 ' shown in black pigment dispersion, acrylic resin soln, stirring solvent mix, make black-colored resin composition 1 '～33 '.
Table 4 '
About table 4 ' in abbreviation and compound, be expressed as follows.
Perylene pigment content (%): the total weight with light-proofness black pigment (A) is the content (%) of benchmark De perylene pigment
Solid constituent weight (%): the solid component concentration in the black-colored resin composition
Solvent: cyclohexanone
About the black-colored resin composition of gained, measure viscosity, optical density, thickness and light transmission rate by following method.The results are shown in table 5.
[viscosity]
About second day viscosity of the black-colored resin composition made, use TVE-20L type viscosity meter (eastern machine industry company make) under 25 ℃, to measure, as initial viscosity (η 0:mPas).In addition,, similarly be determined at 40 ℃ of viscosity (η 7:mPas) of preserving after 7 days, calculate rate of change according to following formula as estimation of stability.
Rate of change (%)=at viscosity (the η 7)/initial viscosity (η 0) * 100 of 40 ℃ of preservations after 7 days
In addition, through the time rate of change be divided into 3 grade evaluations according to following benchmark.
Zero: through the time rate of change less than 110%
△: through the time rate of change be more than 110% and less than 140%
*: through the time rate of change be more than 140%
[optical density]
Use spin-coating method behind painting black resin combination on the glass substrate of 100mm * 100mm, making dry film thickness is filming of 1.0 μ m, heats 20 minutes down at 230 ℃.Utilize Macbeth densimeter (GRETAG D200-II) to measure the as above optical density (OD) of the black-colored resin composition coated substrates of gained, the optical density (OD) when obtaining thickness and being 1.0 μ m.
In addition, OD is divided into 3 grade evaluations according to following benchmark.
Zero: OD is more than 2.70
△: OD is more than 2.50 and less than 2.70
*: OD is less than 2.50
[light transmission rate]
Using spin-coating method behind painting black pigment dispersion on the glass substrate of 100mm * 100mm, through 20 minutes firing process, is filming of 1.0 μ m thereby make dry film thickness under 230 ℃.Utilize spectrophotometer (HITACHI U.3900H) to measure the light transmission rate of the black pigment dispersion coated substrates of gained, obtain light transmission rate, be divided into 3 grade evaluations according to following benchmark.
Zero: light transmission rate (wavelength is 1000nm) is more than 30%
△: light transmission rate (wavelength is 1000nm) is more than 15% and less than 30%
*: light transmission rate (wavelength is 1000nm) is less than 15%
Table 5 '
Figure BSA00000517935500641
As the light-proofness black pigment in the 2nd embodiment, the black pigment dispersion that to contain specific Liang De perylene be black pigment and carbon black is the dispersion of flowability, excellent in stability.In addition, by being that the ratio that contains of black pigment is made as below the 95 weight % with light-proofness black pigment Zhong De perylene, thereby show the also high good light-proofness of optical density.In addition, the light transmission rate during about 780nm also all satisfies more than 15% of mask alignment when operation needs level.
By pigment derivative is used as pigment dispersing agent, initial viscosity descends, flowability also can be observed ageing stability when improving and improves (embodiment 1 '～17 ', 19 '～25 ').In addition, by using pigment derivative and resin type spreading agent simultaneously, thereby show good ageing stability (embodiment 1 '～5 ', 10 '～17 ', 20 '～25 '), when particularly using acidic resins type spreading agent, flowability is good more (embodiment 1 '～5 ', 10 ', 11 ', 13 '～17 ', 20 '～25 ') also.
Light-proofness black pigment Zhong De perylene be black pigment ratio after a little while, the light transmission rate of near infrared region is variation (comparative example 1 ', 9 '～11 ') greatly, in addition, most cases is result's (comparative example 2 ') of light-proofness difference.In addition, perylene is a black pigment when not satisfying the arbitrary value of specific mean grain size and aspect ratio, obtains optical density step-down or ageing stability variation or the two simultaneous result (comparative example 3 '～7 ').
In addition, when solid component concentration is 40 weight %, be high viscosity, do not have the flowability (comparative example 8 ') that is suitable for being coated with.
The combination of using organic pigment is during as colorant, and the result is that light transmission rate, the ageing stability of near infrared region is good, but light-proofness poor (comparative example 9 ', 10 ').
[embodiment 23 ']
(erosion resistant 1 ' (photosensitive black-colored resin composition 1 '))
After the potpourri of following composition mixed, filter with the filtrator of 1 μ m, thereby obtain erosion resistant 1 ' (photosensitive black-colored resin composition 1 ').
1 ': 12.00 parts of pigment dispersions
3 ': 48.00 parts of pigment dispersions
Acrylic resin soln: 8.00 parts
1 ': 0.04 part of " IRGACURE OXE-02 " (vapour crust Japanese firm makes) of Photoepolymerizationinitiater initiater
Ethene unsaturated compound: 2.00 parts " ARONIX M-402 " (manufacturing of East Asia Synesis Company)
Surface conditioner: 1.00 parts (with 98 parts of dilutions of propylene glycol monomethyl ether acetate " BYK-330 " (Bi Ke chemistry Japanese firm makes) (nonvolatile component is 50 weight %) 2 parts of solution that form)
Solvent: cyclohexanone: 30.60 parts
[embodiment 24 '～29 ', comparative example 12 '～20 ']
[erosion resistant 2 '～16 ']
Except changing to table 6 ' shown in composition and use level, similarly make erosion resistant 2 '～16 ' (photosensitive black-colored resin composition 2 '～16 ') with erosion resistant 1 ' (photosensitive black-colored resin composition 1 ').
Table 6 '
Figure BSA00000517935500661
About table 6 ' in abbreviation and compound, be expressed as follows.
Photoepolymerizationinitiater initiater
Initiating agent 1 ': " IRGACURE OXE-02 " (vapour crust Japanese firm makes)
Initiating agent 2 ': " IRGACURE 379EG " (vapour crust Japanese firm makes)/" EAB-F " (manufacturing of hodogaya chemical company) cooperated the material that forms with 90/10
Initiating agent 3: " IRGACURE 379EG " (vapour crust Japanese firm makes)/" IRGACURE 907 " (vapour crust Japanese firm makes)/" DETX-S " (Japanese chemical drug corporate system is made) cooperated the material that forms with 45/45/10
Ethene unsaturated compound: " ARONIX M-402 " (manufacturing of East Asia Synesis Company)
Surface conditioner: with 98 parts of dilutions of propylene glycol monomethyl ether acetate " BYK-330 " (Bi Ke chemistry Japanese firm makes) (nonvolatile component is 50 weight %) 2 parts of solution that form
Solvent: cyclohexanone
About the erosion resistant of gained, measure optical density, light transmission rate and relative dielectric constant by following method.The results are shown in table 7 '.
[optical density]
Use spin-coating method behind coating erosion resistant on the glass substrate of 100mm * 100mm, carry out vacuum drying.Afterwards, use extra-high-pressure mercury vapour lamp with 100mJ/cm 2The exposure ultraviolet ray.Then, after the use aqueous sodium carbonate carries out spray development to unexposed portion, thereby, heated 20 minutes down at 230 ℃ with the clean unexposed portion of removing of ion exchange water.Thereby making thickness is the erosion resistant coated substrates of 1.0 μ m.Utilize Macbeth densimeter (GRETAG D200-II) to measure the as above optical density of the substrate of gained (OD), the optical density (OD) when obtaining thickness and being 1.0 μ m.
In addition, OD is divided into 3 grade evaluations according to following benchmark.
Zero: OD is more than 2.70
△: OD is more than 2.50 and less than 2.70
*: OD is less than 2.50
[light transmission rate]
Using spin-coating method behind coating erosion resistant on the glass substrate of 100mm * 100mm, through 20 minutes firing process, is filming of 1.0 μ m thereby make dry film thickness under 230 ℃.Utilize spectrophotometer (HITACHI U3900H) to measure the light transmission rate of the erosion resistant coated substrates of gained, obtain light transmission rate, be divided into 3 grade evaluations according to following benchmark.
Zero: light transmission rate (wavelength is 1000nm) is more than 30%
△: light transmission rate (wavelength is 1000nm) is more than 15% and less than 30%
*: light transmission rate (wavelength is 1000nm) is less than 15%
[relative dielectric constant]
Use spin coater, 100mm * 100mm, evaporation on the electrode glass substrate thick with the 1.1mm of aluminium with certain revolution coating photosensitive black-colored resin composition, make that thickness is the thickness of 1.0 μ m after following heating process, thereby obtain coated substrates.Then, behind the drying under reduced pressure, use extra-high-pressure mercury vapour lamp to be 100mJ/cm with the accumulation light quantity 2, illumination is 25mW/cm 2Carry out ultraviolet exposure.Under 230 ℃ to coated substrates heating 20 minutes and cooling after, the aluminium that the electrode of evaporation 3.464E-4m2 area is used on the cured coating film of gained is made the sample that forms with aluminium electrode clamping cured coating film.Using electric impedance analyzer (" 1260 type " electric impedance analyzer that Solartron company makes), is the mensuration of relative dielectric constant of carrying out the sample of gained under the 100mV at impressed voltage.Relative dielectric constant divides 3 grade evaluations according to following benchmark.
Zero: relative dielectric constant is below 8.0
△: relative dielectric constant surpasses 8.0 and be below 9.0
*: relative dielectric constant surpasses 9.0
Table 7 '
Figure BSA00000517935500681
As table 7 ' shown in, contain 78～95 weight % be black pigment as light-proofness black pigment De perylene the time, optical density is more than 2.5, in addition, light transmission rate during 780nm also is more than 15%, and relative dielectric constant is also below 9.0, all satisfies the characteristic that requires of BM that the TFT colour display device as the BOA mode possesses.
Perylene in the light-proofness black pigment be black pigment ratio after a little while, the light transmission rate of relative dielectric constant and near infrared region is variation (comparative example 12 ') greatly, in addition, most cases is not for satisfying result's (comparative example 13 ') of light-proofness.
In addition, perylene is a black pigment when not satisfying the arbitrary value of specific mean grain size and aspect ratio, and the result is light-proofness and electrical specification poor (comparative example 14 '～18 ').The combination of using organic pigment is during as colorant (comparative example 19 ', 20 '), and the result is that the light transmission rate and the relative dielectric constant near infrared field is good, but light-proofness is poor.
As previously discussed, comparative example all can not satisfy the whole of light-proofness, light transmission rate and relative dielectric constant.
The making of＜color liquid crystal display arrangement 〉
Color liquid crystal display arrangement can pass through known method in the past, and for example the method shown in the TOHKEMY 2000-162643 is made.
Use possesses the driving of thin film transistor (TFT) (TFT) the mode color liquid crystal display arrangement of the black matrix that is formed by the related black-colored resin composition of the 2nd embodiment and makes of substrate.
At first, on the surface on (the 1st) glass substrate,, form the color filter of RGB more thereon with TFT and transparent ITO electrode layer patternization.On aforementioned color filter, form ITO film as pixel electrode, be etched into the pattern of regulation after, between rgb pixel, form black matrix, thereby make array base palte.
On the other hand, on the surface on other (the 2nd) glass substrate,, form polyimide alignment layers more thereon, thereby make counter substrate ITO electrode layer patterning.
Make array base palte and the counter substrate as above prepared opposed, make electrode layer toward each other, use every interval maintenance necessarily simultaneously the carry out contraposition of pearl with two substrates, the mode of using peristome with residual liquid-crystal composition injection is with around the sealant sealing.Behind peristome injection liquid-crystal composition, sealed open portion.Thereby the liquid crystal indicator of making like this and 3 wavelength CCFL combination of light sources of back light unit are made colour display device.
Its result is: the driving that contains thin film transistor (TFT) (TFT) the mode color liquid crystal display arrangement that possesses the black matrix that uses black-colored resin composition formation of the present invention is used the colour display device of substrate because light-proofness is all excellent, so demonstration contrast excellence of color liquid crystal display arrangement, in addition because the low-k characteristic, therefore very little to the harmful effect of the such electrical specification of the orientation confusion of liquid crystal, and because therefore the light transmission rate excellence of near infrared region also can carry out the mask alignment operation.
Next, about the 3rd embodiment, describe with embodiment and comparative example.
[modulation of acryl resin]
In reaction vessel, pack into 800.0 parts of cyclohexanone, nitrogen is injected container and be heated to 100 ℃, synthermal down with the potpourri of 10.0 parts of 1 hour 60.0 parts of methacrylic acid of dropping, 65.0 parts of butyl methacrylates, 65.0 parts of methyl methacrylates, 60.0 parts of styrene and azoisobutyronitriles, and then 100 ℃ the reaction 3 hours after, add solution with 2.0 parts of gained of cyclohexanone 50.0 parts of dissolvings azoisobutyronitrile, and then 100 ℃ of continuation reactions 1 hour, thereby synthetic resin solution.After being cooled to room temperature, the about 2.0g of sample tree lipoprotein solution, measure nonvolatile component at 180 ℃ of heat dryings after 20 minutes, in synthetic before resin solution, add cyclohexanone according to the mode that makes nonvolatile component become 20 weight %, thus the modulation acrylic resin soln.In addition, the weight-average molecular weight of acrylic resin soln is 40000.
The [perylene is a black pigment]
Prepare and table 1 ' shown in the De perylene be that black pigment 1 '～8 ' Tong Yang De perylene is a black pigment.
[structural formula of pigment derivative]
Prepare and table 2 ' shown in the same pigment derivative of pigment derivative 1 '～4 '.
[embodiment 1 "]
After the potpourri of following composition mixed, use the zirconium oxide bead of diameter as 0.5mm, after disperseing 5 hours with Eiger mill (Eiger Japanese firm make " MINI MODEL M-250MKII "), filtrator with 5.0 μ m filters, thereby the making black-colored resin composition (black pigment dispersion 1 ").
Perylene is 1 ': 6.5 parts of black pigments
1 ': 0.7 part of pigment derivative
1 ': 1.4 parts of " BYK-110 " Bi Ke chemistry of resin type spreading agent Japanese firm makes (acid number is 53mgKOH/g)
Acrylic resin soln: 33.6 parts
Solvent: cyclohexanone: 57.8 parts
[embodiment 2 "～13 ", comparative example 1 ", 2 ", 4 "～9 "]
Except that changing to table 3 " shown in composition and use level, with embodiment 1 " (black pigment dispersion 1 ") similarly make black pigment dispersion 2 "～13 ", 15 "～122 ".
Table 3 "
About table 3 " in abbreviation and compound, with table 3 ' material put down in writing is identical.
[comparative example 3 "]
After following potpourri mixed, use the zirconium oxide bead of diameter as 0.5mm, after 5 hours,, thereby make black pigment dispersion 14 with Eigermill (" MINI MODEL M-250MKII " that Eiger Japanese firm makes) dispersion " with the filtrator filtration of 5.0 μ m.
Carbon black (Mitsubishi Chemical's (strain) makes #45): 6.5 parts
1 ': 0.7 part of pigment derivative
Acrylic resin soln: 33.6 parts
1 ': 1.4 parts of " BYK-110 " Bi Ke chemistry of resin type spreading agent Japanese firm makes (acid number is 53mgKOH/g)
Solvent: cyclohexanone: 57.8 parts
[the viscosity evaluation of black pigment dispersion and through time rate of change]
With regard to the viscosity of black pigment dispersion, under 25 ℃ of pigment dispersion modulation same day, the viscosity (initial viscosity) when using E type viscosity meter (TVE-20L type viscosity meter (eastern machine industry company make)) mensuration revolution as 20rpm.
Then, for counting the same day from the modulation of black pigment dispersion, 40 ℃ of black pigment dispersions of placing 7 days down, will make specimen temperature get back to 25 ℃ after, according to above-mentioned viscosity measurement measure through the time viscosity, by following formula obtain through the time rate of change.
Through the time rate of change (%)=(through the time viscosity)/(initial viscosity) * 100
In addition, through the time rate of change divide 3 grade evaluations according to following benchmark.
The results are shown in table 4 ".
Zero: through the time rate of change less than 110%
△: through the time rate of change be more than 110% and less than 140%
*: through the time rate of change be more than 140%
[optical density]
Use spin-coating method behind painting black pigment dispersion on the glass substrate of 100mm * 100mm, carry out vacuum drying, heated 20 minutes down at 230 ℃.Thereby making thickness is the black pigment dispersion coated substrates of 1.0 μ m.Utilize Macbeth densimeter (GRETAG D200-II) to measure the optical density (OD) of this substrate, the optical density (OD) when obtaining thickness and being 1.0 μ m.
The results are shown in table 4 ".
[transmitance]
Using spin-coating method behind painting black pigment dispersion on the glass substrate of 100mm * 100mm, through 20 minutes firing process, is filming of 1.0 μ m thereby make dry film thickness under 230 ℃.Utilize spectrophotometer (HITACHI U3900H) to measure the transmitance of the black pigment dispersion coated substrates of gained, obtain transmitance, be divided into 3 grade evaluations according to following benchmark.
The results are shown in table 4 ".
Zero: transmitance (wavelength is 1000nm) is more than 80%
△: transmitance (wavelength is 1000nm) is more than 60% and less than 80%
*: transmitance (wavelength is 1000nm) is less than 60%
Table 4 "
Figure BSA00000517935500721
Light-proofness black pigment as feature of the present invention, by average primary particle diameter be below the 50nm and the aspect ratio of pigment particles to have flowability, stability that particular value De perylene is the black pigment dispersion that constitutes of black pigment, pigment dispersing agent, resin and solvent all excellent, and the OD value is high, show good light-proofness, transmitance also excellent (embodiment 1 "～13 ").
In addition, by using pigment derivative and resin type spreading agent simultaneously, thereby show good ageing stability (embodiment 1 "～4 ", 9 "～13 "), especially, good more when using acidic resins type spreading agent (embodiment 1 "～4 ", 9 ", 10 ", 12 ", 13 ").
[embodiment 14 "]
(erosion resistant 1 ")
Then, after the potpourri of following composition mixed, use the filtrator of 1 μ m to filter, thereby obtain photosensitive black-colored resin composition (erosion resistant 1 ").
Black pigment dispersion 1 ": 48.0 parts
Acrylic resin soln: 17.2 parts
Photoepolymerizationinitiater initiater: 0.4 part (" IRGACURE OXE-02 " that vapour crust Japanese firm makes)
Ethene unsaturated compound: 2.9 parts (" ARONIX M-402 " that East Asia Synesis Company makes)
Surface conditioner: 1.0 parts (with 2 parts of solution that form of " BYK-330 " (nonvolatile component is 50 weight %) of 98 parts of dilutions of propylene glycol monomethyl ether acetate Bi Ke chemistry Japanese firm manufacturing)
Solvent: cyclohexanone: 30.5 parts
[embodiment 15 "～26 ", comparative example 10 "～18 "]
[erosion resistant 2 "～22 "]
Except changing to table 5 " shown in the black pigment dispersion, with embodiment 14 " (erosion resistant 1 ") similarly make erosion resistant 2 "～22 ".
[optical density]
Use spin-coating method behind coating erosion resistant on the glass substrate of 100mm * 100mm, carry out vacuum drying, afterwards, use extra-high-pressure mercury vapour lamp exposure 100mJ/cm 2Ultraviolet ray.Then, after the use aqueous sodium carbonate carries out spray development to unexposed portion, thereby with the clean unexposed portion of removing of ion exchange water, heating 20 minutes down at 230 ℃, is the erosion resistant coated substrates of 1.0 μ m thereby make thickness.Utilize Macbeth densimeter (GRETAG D200-II) to measure the optical density (OD) of gained substrate like this, the optical density (OD) when obtaining thickness and being 1.0 μ m.
The results are shown in table 5 ".
[transmitance]
Using spin-coating method behind coating erosion resistant on the glass substrate of 100mm * 100mm, through 20 minutes firing process, is filming of 1.0 μ m thereby make dry film thickness under 230 ℃.Utilize spectrophotometer (HITACHI U3900H) to measure the transmitance of the erosion resistant coated substrates of gained, obtain transmitance, be divided into 3 grade evaluations according to following benchmark.
The results are shown in table 5 ".
Zero: transmitance (wavelength is 1000nm) is more than 80%
△: transmitance (wavelength is 1000nm) is more than 60% and less than 80%
*: transmitance (wavelength is 1000nm) is less than 60%
[relative dielectric constant, tan δ (dielectric loss angle tangent)]
Use spin coater, 100mm * 100mm, evaporation on the electrode glass substrate thick with the 1.1mm of aluminium with certain revolution coating photosensitive black-colored resin composition, make that thickness is the thickness of 1.0 μ m after the following heating process, thereby obtain coated substrates.Then, behind the drying under reduced pressure, use extra-high-pressure mercury vapour lamp to be 100mJ/cm with the accumulation light quantity 2, illumination is 25mW/cm 2Carry out ultraviolet exposure.Under 230 ℃ to coated substrates heating 20 minutes and cooling after, evaporation 3.464E-4m on the cured coating film of gained 2The aluminium that the electrode of area is used is made the sample with aluminium electrode clamping cured coating film.Using electric impedance analyzer (" 1260 type " electric impedance analyzer that Solartron company makes), is to carry out the relative dielectric constant of sample of gained and the mensuration of tan δ under the 100mV at impressed voltage.Relative dielectric constant divides 3 grade evaluations according to following benchmark.
Zero: relative dielectric constant is less than 3.5
△: relative dielectric constant is more than 3.5, below 4.5
*: relative dielectric constant surpasses 4.5
Tan δ divides 3 grade evaluations according to following benchmark.
Zero: tan δ is less than 0.1
△: tan δ is more than 0.1 and less than 0.2
*: tan δ is more than 0.2
The results are shown in table 5 ".
Table 5 "
Figure BSA00000517935500751
As table 5 " shown in; used have average primary particle diameter as below the 50nm, aspect ratio is that to be black pigment, pigment dispersing agent, resin and solvent be for 1: 1～1: 2 crystal particles De perylene as the result of the related erosion resistant of the 3rd embodiment of light-proofness black pigment: optical density height, light-proofness excellence, low-k, and the transmitance of near infrared region also excellent (embodiment 14 "～26 ").Relative therewith, when perylene pigment did not satisfy the arbitrary value of specific mean grain size and aspect ratio, the result is: not only optical density was low, light-proofness is poor, electrical specification also poor (comparative example 13 "～17 ").
Wherein, the pigment derivative that use has the precursor skeleton of organic pigment and an alkali subtituent shows the excellent more result of electrical specification (embodiment 24 ") as the erosion resistant of pigment dispersing agent, that the tan δ of the erosion resistant of the precursor skeleton of organic pigment Wei dioxazine or diketopyrrolopyrrolecocrystals also becomes is better (embodiment 19 ", 21 "～23 ").
In addition, having used pigment derivative and acid number simultaneously is that the tan δ of erosion resistant of the acidic resins type spreading agent of 100～200mgKOH/g becomes better, initial viscosity also can be suppressed to one low-level, stability also good (embodiment 22 ").
In addition, for the comparative example 10 that forms black-colored resin composition by mixing as the organic pigment of light-proofness black pigment ", 11 " (erosion resistant 12 ", 13 "), relative dielectric constant and transmitance are realistic scale, but optical density is low, and has used the comparative example 12 of carbon black " (erosion resistant 14 ") result is: optical density excellence but the non-constant of the transmitance of relative dielectric constant and near infrared region.
In addition, be the comparative example 13 of mineral black arbitrary value of not satisfying specific mean grain size and aspect ratio with regard to perylene "～17 " (erosion resistant 15 "～19 ") with regard to, the result is for not only optical density is low, light-proofness is poor, and electrical specification is also poor.
As mentioned above, comparative example all can not satisfy the whole of relative dielectric constant, transmitance and light-proofness.
The making of＜color liquid crystal display arrangement 〉
Color liquid crystal display arrangement can pass through known method in the past, and for example the method shown in the TOHKEMY 2000-162643 is made.
Use possesses the driving of thin film transistor (TFT) (TFT) the mode color liquid crystal display arrangement of the black matrix that is formed by the related black-colored resin composition of the 3rd embodiment and makes of substrate.
At first, on the surface on (the 1st) glass substrate,, form the color filter of RGB more thereon with TFT and transparent ITO electrode layer patternization.On aforementioned color filter, form ITO film as pixel electrode, be etched into the pattern of regulation after, between rgb pixel, form black matrix, thereby make array base palte.
On the other hand, on the surface on other (the 2nd) glass substrate,, form polyimide alignment layers more thereon, thereby make counter substrate the transparent ITO electrode layer patternization.
Make array base palte and the counter substrate arranged opposite as above prepared, make electrode layer toward each other, use every interval maintenance necessarily simultaneously the carry out contraposition of pearl with two substrates, the mode of using peristome with residual liquid-crystal composition injection is with around the sealant sealing.Behind peristome injection liquid-crystal composition, sealed open portion.Thereby the liquid crystal indicator of making like this and 3 wavelength CCFL combination of light sources of back light unit are made colour display device.
Its result is: the driving that contains thin film transistor (TFT) (TFT) the mode colour display device that possesses the black matrix that uses black-colored resin composition formation of the present invention is used the colour display device of substrate because light-proofness is all excellent, so demonstration contrast excellence of colour display device, in addition because the low-k characteristic, therefore very little to the harmful effect of the electrical specifications such as orientation confusion of liquid crystal, and because therefore the transmitance excellence of near infrared region also can carry out the mask alignment operation.

Claims (29)

1. color composition for color filter, it is characterized in that, it is the color composition for color filter that contains colorant, resin type spreading agent and solvent, and it is that the aspect ratio of 20～50nm and pigment particles is 1: 1～1: 3.5 a pigment that described colorant contains average primary particle diameter
Described resin type spreading agent contains the acrylic acid series segmented copolymer, and described acrylic acid series segmented copolymer is by the A block with solvophilic and has A-B segmented copolymer that the B block of the functional group of nitrogen atom constitutes or B-A-B segmented copolymer and its amine value are scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent.
2. color composition for color filter as claimed in claim 1, it is characterized in that, described acrylic acid series segmented copolymer, the represented repetitive of following general formula (I) that in having the A block of solvophilic, contains 5～40 moles of %, in the B of functional group block, contain the represented repetitive of following general formula (II) with nitrogen atom
Figure FSA00000517935400011
In the general formula (I), n represents 1～5 integer, R 1Expression hydrogen atom or methyl,
Figure FSA00000517935400012
In the general formula (II), R 4And R 5Respectively independently expression can have substituent ring-type or chain alkyl, can have substituent aryl and maybe can have substituent aralkyl, R 3The expression carbon number is the alkylidene more than 1, R 2Expression hydrogen atom or methyl.
3. color composition for color filter as claimed in claim 2, it is characterized in that, described acrylic acid series segmented copolymer, in having the A block of solvophilic, further contain 50～90 moles of % except that the represented formation unit of general formula (I) with the formation unit of (methyl) acrylic ester monomer as presoma.
4. color composition for color filter as claimed in claim 1 is characterized in that described colorant is a black pigment Wei perylene.
5. color composition for color filter as claimed in claim 1 is characterized in that, further contains the pigment derivative as acid derivant or its slaine of organic pigment.
6. color composition for color filter as claimed in claim 1 is characterized in that, further contains photopolymerization monomer and Photoepolymerizationinitiater initiater.
7. a color filter is characterized in that, possesses the filter section and/or the black matrix that are formed by each described color composition for color filter in the claim 1～6 on the substrate.
8. black-colored resin composition, it is characterized in that, it is the black-colored resin composition that contains light-proofness black pigment, resin and solvent, described light-proofness black pigment be below the 50nm by average primary particle diameter and the aspect ratio of pigment primary particle be 1: 1～1: 2 De perylene be black pigment and carbon black to constitute Suo Shu perylene be that the content of black pigment is 78～95 weight % when being benchmark with the total weight of light-proofness black pigment, and solid component concentration is that 5 weight % are above and less than 40 weight %.
9. black-colored resin composition as claimed in claim 8 is characterized in that, Suo Shu perylene is that the average primary particle diameter of black pigment is 20～45nm.
10. black-colored resin composition as claimed in claim 8 is characterized in that, further contains pigment dispersing agent.
11. black-colored resin composition as claimed in claim 10 is characterized in that, described pigment dispersing agent comprises the precursor skeleton with organic pigment and the pigment derivative of alkali subtituent.
12. black-colored resin composition as claimed in claim 10 is characterized in that, described pigment dispersing agent further contains acidic resins type spreading agent.
13. black-colored resin composition as claimed in claim 8 is characterized in that, further contains ethene unsaturated compound and Photoepolymerizationinitiater initiater.
14. a black matrix is formed by the described black-colored resin composition of claim 8.
15. black matrix as claimed in claim 14 is characterized in that, the relative dielectric constant when dry film thickness is 1.0 μ m is below 8.0.
16. black matrix as claimed in claim 14 is characterized in that, the light transmission rate of the wavelength 780nm when dry film thickness is 1.0 μ m is more than 15% and less than 99%.
17. black matrix as claimed in claim 14 is characterized in that, the optical density when dry film thickness is 1.0 μ m is more than 2.50.
18. the driving substrate of a thin film transistor (TFT) mode color liquid crystal display arrangement is characterized in that, possesses each described black matrix in the claim 14～17.
19. black-colored resin composition, it is characterized in that, it is the black-colored resin composition that contains light-proofness black pigment, pigment dispersing agent, resin and solvent, and described light-proofness black pigment is that average primary particle diameter is that 50nm aspect ratio following and pigment particles is that 1: 1～1: 2 De perylene is a black pigment.
20. black-colored resin composition as claimed in claim 19 is characterized in that, Suo Shu perylene is that the average primary particle diameter of black pigment is 20～45nm.
21. black-colored resin composition as claimed in claim 19 is characterized in that, described pigment dispersing agent is the pigment derivative with precursor skeleton and alkali subtituent of organic pigment.
22. black-colored resin composition as claimed in claim 21 is characterized in that, the precursor skeleton Wei dioxazine series pigments of described organic pigment or in the diketopyrrolopyrrolecocrystals series pigments any.
23. black-colored resin composition as claimed in claim 21 is characterized in that, described pigment dispersing agent further contains the resin type spreading agent.
24. black-colored resin composition as claimed in claim 19 is characterized in that, further contains ethene unsaturated compound and Photoepolymerizationinitiater initiater.
25. a black matrix is formed by the described black-colored resin composition of claim 19.
26. black matrix as claimed in claim 25 is characterized in that, the relative dielectric constant when dry film thickness is 1.0 μ m is below 4.5.
27. black matrix as claimed in claim 25 is characterized in that, the transmitance of the wavelength 1000nm when dry film thickness is 1.0 μ m is more than 60% and less than 99%.
28. black matrix as claimed in claim 25 is characterized in that, the optical density when dry film thickness is 1.0 μ m is more than 1.30.
29. the driving substrate of a thin film transistor (TFT) mode color liquid crystal display arrangement is characterized in that, possesses each described black matrix in the claim 25～28.
CN201110159624.4A 2010-06-08 2011-06-08 Coloring composition for color filter and color filter Active CN102279522B (en)

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JP2010130587 2010-06-08
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CN102827526A (en) * 2012-08-23 2012-12-19 京东方科技集团股份有限公司 High-impedance material, and display substrate black matrix and liquid crystal display apparatus containing same
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10219167A (en) * 1997-01-31 1998-08-18 Sumitomo Rubber Ind Ltd Ink for black matrix layer
JP2005283950A (en) * 2004-03-30 2005-10-13 Jsr Corp Radiation-sensitive composition for color filter, color filter and color liquid crystal display
JP2007256865A (en) * 2006-03-24 2007-10-04 Fujifilm Electronic Materials Co Ltd Colored resin composition, color filter using the same, and manufacturing method for color filter
JP2010039060A (en) * 2008-08-01 2010-02-18 Mitsubishi Chemicals Corp Colored curable resin composition for color filter by ink-jet method, color filter, liquid crystal display and organic el display

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001214077A (en) 2000-01-31 2001-08-07 Fuji Photo Film Co Ltd Colored composition and color filter
JP2004168968A (en) * 2002-11-22 2004-06-17 Dainippon Ink & Chem Inc Method for modifying organic pigment and color filter using the organic pigment obtained by using the method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10219167A (en) * 1997-01-31 1998-08-18 Sumitomo Rubber Ind Ltd Ink for black matrix layer
JP2005283950A (en) * 2004-03-30 2005-10-13 Jsr Corp Radiation-sensitive composition for color filter, color filter and color liquid crystal display
JP2007256865A (en) * 2006-03-24 2007-10-04 Fujifilm Electronic Materials Co Ltd Colored resin composition, color filter using the same, and manufacturing method for color filter
JP2010039060A (en) * 2008-08-01 2010-02-18 Mitsubishi Chemicals Corp Colored curable resin composition for color filter by ink-jet method, color filter, liquid crystal display and organic el display

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