CN102279522B - 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
CN102279522B
CN102279522B CN201110159624.4A CN201110159624A CN102279522B CN 102279522 B CN102279522 B CN 102279522B CN 201110159624 A CN201110159624 A CN 201110159624A CN 102279522 B CN102279522 B CN 102279522B
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Prior art keywords
pigment
black
parts
resin
methyl
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CN102279522A (en
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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
Toyocolor Co Ltd
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Priority claimed from JP2011078189A external-priority patent/JP2012212054A/en
Priority claimed from JP2011078192A external-priority patent/JP5673302B2/en
Priority claimed from JP2011078191A external-priority patent/JP5741141B2/en
Application filed by Toyo Ink SC Holdings Co Ltd, Toyocolor Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Publication of CN102279522A publication Critical patent/CN102279522A/en
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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

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 color filter, black-colored resin composition, black matrix and thin film transistor (TFT) (TFT) the mode color liquid crystal display arrangement of filter section and/or black matrix.
Background technology
Liquid crystal indicator is to controlling by the polarisation of light degree of the 1st polaroid and to the display device of controlling to show 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 clipping in 2 polaroids.As other the mode of representative liquid crystal indicator, have on the substrate of a side, arrange pair of electrodes and the direction that is parallel to substrate apply electric field plane conversion (IPS) mode, make to have vertical orientated homeotropic alignment (VA) mode of the nematic crystal of negative dielectric anisotropy and make mutually orthogonal optical compensation curved arrangement (OCB) mode of carrying out optical compensation of optical axis of uniaxiality phase retardation film etc., and all practical.
Liquid crystal indicator can carry out colour demonstration by color filter is set between 2 polaroids, and in recent years, due to gradually, for TV and PC monitor etc., therefore the requirement of the high-contrast to color filter, high brightness has improved.
Color filter be parallel on the surface of the transparency carriers such as glass or configure across two or more different tone 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 the marshalling configuration in accordance with regulations of every kind of tone.
Conventionally, in color liquid crystal display arrangement, form by evaporation or sputter for the transparency electrode that drives liquid crystal on color filter, and then be formed for the 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 conventionally need to be more than 200 DEG C, preferably under the high temperature more than 230 DEG C, carry out.Therefore, at present, as the manufacture method of color filter, the method that is called Pigments method using the pigment of photostability, excellent heat resistance as colorant becomes main flow.
But the color filter that is conventionally dispersed with pigment exists the light scattering that causes due to pigment etc., there is chaotic problem in the polarization degree of liquid crystal control.That is, must interdict the light time (OFF state), light leaks, or, must see through the light time (ON state), see through light and decay, the low such problem of ratio (contrast) of the brightness in the display device while therefore there is ON state and OFF state.
In order to realize high brightness, the high-contrast of color filter, in large multipair filter section, contained pigment carries out miniaturization processing and uses.But, while pigment (the rough thing of what is called that is 10～100 μ m by the particle diameter of manufacturing by chemical reaction is processed by pigmentation until obtain the potpourri of the offspring that primary particle and gathering thereof form) being carried out to miniaturization by various miniaturization disposal routes simply, carry out the pigment of the miniaturization of primary particle or offspring and conventionally also easily assembled, in the time excessively carrying out miniaturization, also can form huge block pigment solids material.Further, be scattered in the pigment carrier that contains resin etc. even if carried out the pigment of miniaturization, thereby then make the offspring of pigment make its stabilization close to primary particle as far as possible, be also difficult to obtain stable coloured composition.
Known in addition, by the Pigments of having implemented miniaturization processing in the pigment carrier that contains resin etc. and the color composition for color filter forming is difficult to stable and high concentration ground dispersed color, thereby can cause variety of issue to manufacturing process and goods itself.
For example, the color compositions that contains the pigment being made up of minuteness particle often shows high viscosity, not only takes out and carries goods to become difficulty from dispersion machine, and bad situation is also included in and in preservation, gelation occurs and cause using and become difficulty.Further, about the surface of the color development thing of color compositions, can produce the states such as gloss declines, levelability is bad bad.In addition, in the time mixing different types of pigment use, due to the phenomenon such as color spot, sedimentation that gathering causes, sometimes on color development thing, there is the remarkable decline of color spot, colorability.
Therefore,, in order to make disperse state keep good, conventionally utilize resin type spreading agent.Resin type spreading agent has concurrently and is adsorbed in the position of pigment and the structure with the high position of solvent compatibility as dispersion medium, and performance is decided by the balance at the position of these 2 functions.Resin type spreading agent can use various materials according to the surface state of the pigment as being dispersed thing.
With regard to resin type spreading agent, the resin type spreading agent of the 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, due to the development of pigment miniaturization in recent years, the increase of surface area, therefore, in order to ensure dispersion stabilization, and there is the tendency of a large amount of interpolations.There is thus following situation: due to the increase of spreading agent, cause decreased solubility or the dissolubility variation of spreading agent self to developer solution to developer solution, thereby cannot develop in official hour; Or enable to develop, the also not dissolved matter of easy residual colored resin composition in the non-image portion after development.And then, if the not dissolved matter of residual colored resin composition in the non-image portion on substrate, can cause the lower degradation of transmitance and the contrast of gained color filter, in addition, in the situation that residuing in patterned sides edge, can cause that sealing in the peeling off of ITO film, liquid crystal cells chemical industry order is deteriorated etc., thereby become the situation that rear operation is impacted.
The in the situation that of comb shaped structure; the oriented polyamino compound grafting with primary amino radical or secondary amino group has the part of the formation broach of the functional group 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 as previously mentioned high-contrast, also require high brightness.In order to obtain high brightness, conventionally in pigment carrier, can make it close to primary particle when dispersed color, thereby improve the transparency of dispersion, because the spectrophotometric spectra that makes dispersion has high permeability, therefore obtain high brightness.
In order to address the above problem, do the trial (with reference to patent documentation 3,4,5) that improves structure, the acid number etc. of acrylic acid series segmented copolymer, improves pigment-dispersing with a small amount of interpolation.
In addition, at the gap portion of the red, green, blue filter section of color filter, to improve contrast as object, conventionally form there is black matrix of being called of the light-proofness cancellate black pattern of (following, BM made in brief note sometimes).
With regard to black matrix, in order to optimize the image quality of liquid crystal display, require its light-proofness excellence.
In addition, in recent years, in order to tackle fine, high brightness more, from such method that forms black matrix at filter substrate in the past, carry out in the research of BOA (Black Matrix on Array) mode that forms black matrix on substrate for the driving of thin film transistor (TFT) (TFT) mode color liquid crystal display arrangement.In this BOA method, do not need for such stickup operation in the past of element contraposition, and owing to significantly increasing pixel relative aperture (aperture opening ratio), shortening manufacturing process, also, owing to can improving display quality, cutting down cost, therefore advantage is many compared with the BM forming on filter substrate.
Because these BM also require high light-proofness, therefore require the decentralized stabilization under high pigment levels, be also necessary also to give high definition simultaneously.With colored resist similarly, with in coloured composition, also exist following problem: owing to tending to increase the addition of spreading agent for obtaining dispersion stabilization, therefore the dissolubility variation to developer solution can not be developed in official hour at black matrix; Even or can develop, also not dissolved matter of easy residual colored resin composition etc. in the non-pixel portion after development.
In addition, be in the time that array base palte one side form BM, because BM self is directly exposed in the driving electric field of liquid crystal, therefore the specific inductive capacity Gao Shihui of BM self causes that the demonstration of liquid crystal display is bad.In addition, the mask alignment that BM carries out while formation, owing to carrying out with infrared camera, therefore also needs the light transmission rate of the near infrared region of certain level.Therefore,, for being mainly 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, is therefore difficult to calibrate, and is 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 the combination of at least one organic pigment 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 perylene, but can not all meet from the light-proofness of black matrix component, electrical specification and for the sufficient light transmission rate of the near infrared region of mask alignment operation.
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, object is to provide also excellent color composition for color filter and 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 of a kind of excellent dispersion, good fluidity, stable and developability.
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 the pigment of 1: 1～1: 3.5, and use acrylic acid series segmented copolymer as resin type spreading agent, thereby solve above-mentioned problem, described acrylic acid series segmented copolymer is by having the A block of solvophilic and having A-B segmented copolymer or the B-A-B segmented copolymer that the B block of functional group of nitrogen atom forms, and amine value is scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent.
, 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 the pigment of 1: 1～1: 3.5 that this colorant contains average primary particle diameter, this resin type spreading agent contains acrylic acid series segmented copolymer, described acrylic acid series segmented copolymer is by having the A block of solvophilic and having A-B segmented copolymer or the B-A-B segmented copolymer that the B block of functional group of nitrogen atom forms, and 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 the A block with solvophilic, can contain the represented repetitive of following general formula (I) of 5～40 % by mole, in the B block of functional group with nitrogen atom, can contain the represented repetitive of following general formula (II).
[in general formula (I), n represents 1～5 integer, R 1represent hydrogen atom or methyl.]
[in general formula (II), R 4and R 5represent to have independently respectively substituent ring-type or chain alkyl, can there is substituent aryl and maybe can there is substituent aralkyl, R 3represent that carbon number is more than 1 alkylidene, R 2represent hydrogen atom or methyl.]
In addition, with regard to aforementioned acrylic acid series segmented copolymer, in the A block with solvophilic, can further contain the Component units using Component units represented general formula (I) (methyl) acrylic ester monomer in addition as presoma of 50～90 % by mole.
In addition, aforementioned colorant Ke is being black pigment as perylene.
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 substrate.
The related color composition for color filter of the 1st embodiment is the stable color composition for color filter of mobility and developability excellence, by using this color composition for color filter, can form the black matrix pattern of shades of colour filter section and the high light intensity of high-contrast.Therefore,, by using this color composition for color filter, can obtain the color filter of high-quality.
In the 2nd embodiment, it is a kind of for making the mobility of black matrix, the black-colored resin composition of excellent in stability that object is to provide, and use all excellent black matrixes of light transmission rate of its light-proofness, electrical specification and near infrared region, the black matrix especially for the driving of thin film transistor (TFT) (TFT) mode color liquid crystal display arrangement 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 by average primary particle diameter be 50nm aspect ratio following and primary particle be 1: 1～1: 2 perylene be black pigment and carbon black form Gai perylene of be black pigment content taking the total weight of light-proofness black pigment (A) during as benchmark as 78～95 % by weight, and solid component concentration is that 5 % by weight are above and be less than 40 % by 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 pigment derivative of precursor skeleton and the alkali subtituent with organic pigment.
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 being formed by aforementioned black-colored resin composition.
The relative dielectric constant of aforementioned black matrix in the time that 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 in the time that dry film thickness is 1.0 μ m can be more than 15% and is less than 99%.
The optical density of aforementioned black matrix in the time that 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 related black matrix of the 2nd embodiment is due to light-proofness excellence, therefore the display comparison degree excellence of color liquid crystal display arrangement, and due to low-k characteristic, therefore be difficult to produce the undesirable condition that the electrical specification of the so black matrix of the orientation interelectrode conducting chaotic or that form of liquid crystal causes on TFT substrate, and due to the light transmission rate excellence of near infrared region, therefore can also carry out 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, object is to provide all black matrixes of excellence of transmitance of a kind of light-proofness, electrical specification and near infrared region, use the black matrix of substrate especially for the driving of thin film transistor (TFT) (TFT) mode color liquid crystal display arrangement, and for making the mobility 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 perylene is 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 pigment derivative of precursor skeleton and the alkali subtituent with organic pigment.
The precursor skeleton of aforementioned organic pigment can be any in dioxazine series pigments or diketopyrrolopyrrolecocrystals series pigments.
Aforementioned pigment dispersing agent can further contain 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 being formed by aforementioned black-colored resin composition.
The relative dielectric constant of aforementioned black matrix in the time that dry film thickness is 1.0 μ m can be below 4.5.
The transmitance of the wavelength 1000nm of aforementioned black matrix in the time that dry film thickness is 1.0 μ m can be more than 60% and is less than 99%.
The optical density of aforementioned black matrix in the time that dry film thickness is 1.0 μ m can be more than 1.30.
In addition, the 3rd embodiment relates to one and is characterized as the driving substrate that possesses aforementioned black matrix film transistor (TFT) mode color liquid crystal display arrangement.
According to the 3rd embodiment, black matrix is due to light-proofness excellence, therefore the display comparison degree excellence of color liquid crystal display arrangement, and due to low-k characteristic, therefore be difficult to produce the undesirable condition that the electrical specification of the so black matrix of the orientation interelectrode conducting chaotic or that form of liquid crystal causes on TFT substrate, and due to the light transmission rate excellence of near infrared region, therefore can also carry out mask alignment operation, thereby also be suitable for the driving substrate of thin film transistor (TFT) (TFT) mode color liquid crystal display arrangement.
Embodiment
First, describe with regard to the various constituents of color composition for color filter of the present invention.
< colorant >
With regard to colorant, there are filter section colorant and black matrix colorant.
[filter section colorant]
As contained pigment in colorant for filter section, be not particularly limited, while considering pigment particles dispersed, preferably average primary particle diameter is more than 20nm.In addition, while considering contrast and brightness, preferably average primary particle diameter is below 50nm.,, along with average primary particle diameter increases, there is light leak while intersection in light scattering, polaroid backlight, therefore causes contrast to reduce.In addition, because transmitance declines, also impact causes brightness to decline.
In addition, when the aspect ratio of pigment particles is the scope of 1: 1～1: 3.5, fully preventing light scattering backlight, the decline of transmitance, is therefore preferred.
As the shape of pigment particles, not needle-like, but preferred spherical or ellipticity.When spherical, due to each pigment primary particle spacing homogenising more, be therefore difficult to occur scattering of light, contrast, brightness are very high.
As colorant, in the situation that for example forming shades of colour filter section, can use the 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 Azone system, benzimidazolone system, isoindolinone is the organic pigments such as, dioxazine is, indanthrene Xi, perylene system.Also can utilize in addition various inorganic pigments etc.
Illustrate the object lesson of spendable pigment." C.I. " below enumerating represents Colour Index.
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, preferably 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, preferably C.I. pigment blue 15,15:1,15:2,15:3,15:4 or 15:6, be more preferably 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, preferably 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, preferably 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, preferably C.I. pigment violet 19 or 23, is more preferably 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, preferably C.I. pigment orange 38 or 71.
Above-mentioned various pigment also can be used together multiple.For example, in order to adjust colourity, as pigment, can be used together viridine green and yellow uitramarine, or also with blue pigment and violet pigment.
[black matrix colorant]
In this instructions, sometimes the color composition for color filter that contains black matrix colorant is denoted as to " black colorant composition " or " black-colored resin composition ".
While forming black matrix, as colorant, can use the hybrid pigment of black pigment or above-mentioned redness, purple, yellow, green, blue pigment.
With regard to the average primary particle diameter of pigment, during about upper limit consideration light-proofness, about lower limit consideration pigment-dispersing, be preferably below 50nm, be more preferably 5～50nm, more preferably 20～50nm, is particularly preferably 20～45nm.,, along with average primary particle diameter increases, the filling of particle becomes dredges, and produce gap, thereby sheltering declines.On the other hand, by average primary particle diameter is suppressed at below 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 above-mentioned scope time, because the filling of particle becomes close, gap is few, therefore sheltering improves.
The shape of pigment particles is not needle-like but preferred spherical or ellipticity.Especially, when spherical, due to each pigment primary particle spacing homogenising more, be therefore difficult to produce gap, sheltering is very high.
As spendable black pigment, it can be light-proofness black pigment, for example can enumerate: 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 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 is black pigment, relative dielectric constant, dispersiveness, developability are excellent especially.
When Bing Yong perylene is black pigment and carbon black, Zhong black pigment 100 % by weight, perylene is that the content of black pigment is preferably 78～95 % by weight, is more preferably 80～95 % by weight.Consider that obtaining in 1.0 μ m left and right the ratio that sufficient light-proofness Shi ， perylene is black pigment is preferably below 95 % by weight.Consider to prevent that transmitance that relative dielectric constant raise, improved wavelength 1000nm place is so that the infrared ray sensor of calibration while fully identifying, prevent in the time that BM forms to make liquid crystal molecular orientation confusion because of driving voltage, more than being preferably 78 % by weight.
With regard to the content of black pigment, about the upper limit consider sufficient dispersion stabilization, while considering sufficient light-proofness about lower limit, in all solids composition 100 % by weight of color composition for color filter, be preferably 20～70 % by weight, be more preferably 30～70 % by weight, more preferably 30～60 % by weight, are particularly preferably 40～60 % by weight.
In addition, make to use that to state perylene be black pigment, the black matrix that the black colorant composition that color mixture system forms forms is due to light-proofness excellence, therefore the display comparison degree excellence of color liquid crystal display arrangement, and due to low-k characteristic, therefore be difficult to produce the undesirable condition that the electrical specification of the so black matrix of the orientation interelectrode conducting chaotic or that form of liquid crystal causes on TFT substrate, and due to the transmitance excellence of near infrared region, therefore can also carry out mask alignment operation, thereby be also 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) manufactures, #25, #30, #32, #33, #40, #44, #45, #45L, #47, #50, #52, MA7, MA8, MA11, MA100, MA100R, MA100S, MA230, the PrIntex L that DEGUSSA company manufactures, 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 (being sometimes denoted as below OD), preferably #45.Black matrix can use separately a kind, also can mix two or more and use.
While containing average primary particle diameter in colorant of the present invention and be 20～50nm and its aspect ratio and be the pigment of 1: 1～1: 3.5, its content is preferably 30～100 % by weight in all coloring agent 100 % by weight, is more preferably 50～100 % by weight.
While containing average primary particle diameter in coloured composition of the present invention and be 20～50nm and its aspect ratio and be the pigment of 1: 1～1: 3.5, more than its content is conventionally preferably 1 % by weight in all solids composition, more than being more preferably 5 % by weight, in addition, be generally below 95 quality %, be particularly preferably below 85 % by weight.Be 5 % by weight when above, can not become excessive with respect to the thickness of colour saturation, the clearance control while not worrying liquid crystal cells etc. causes harmful effect.On the other hand, be 95 % by weight when following, can obtain sufficient dispersion stabilization.
[miniaturization of pigment]
The pigment using in the present invention can grind to process to wait by salt and carry out miniaturization.Carry out the pigment of miniaturization by use, can form the filter section that contrast is higher and can form the black matrix that light-proofness is high.
Salt mill is processed and is referred to that mixing rolls such as using kneader, two roller mills, three-roll grinder, bowl mill, attitor, sand mill heat also after mechanically milling the potpourri of pigment, water-soluble inorganic salt and water-miscible organic solvent, the processing of removing water-soluble inorganic salt and water-miscible organic solvent by washing.Water-soluble inorganic salt works as grinding aid, when salt mill, utilizes the high rigidity of inorganic salts that pigment is pulverized.By making pigment carry out the constrained optimization while processing of salt mill, can obtain the very fine and narrow distribution range of primary particle size, there is the pigment of 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).From the viewpoint for the treatment of effeciency and production efficiency two, 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, is not particularly limited in water and the material that do not dissolve in fact used inorganic salts as long as dissolving (mixing).But temperature rise while mill due to salt, solvent are in holding evaporable state, therefore from the viewpoint of security, preferably boiling point is 120 DEG C of above high boiling solvents.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, aqueous polyglycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, dipropylene glycol, dipropylene glycol monomethyl ether, DPE, 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 to the processing of salt mill, can add as required resin.Spendable resin kind is not particularly limited, and can use the synthetic resin of natural resin, modified natural resin, synthetic resin, the modification of use natural resin etc.Spendable resin is at room temperature preferably solid, water-insoluble, and further preferably partly dissolves in 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.The dispersion excellence of spreading agent to pigment, and prevent that the pigment after dispersion from reassociating.
[resin type spreading agent]
As resin type spreading agent, can contain acrylic acid series segmented copolymer, described acrylic acid series segmented copolymer is by having the A block of solvophilic and having A-B segmented copolymer that the B block of functional group of nitrogen atom forms or B-A-B segmented copolymer and amine value are scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent.
Resin type spreading agent comprises having and is adsorbed in the colorant compatibility position of colorant character and has the position of compatibility with colorant carrier, and have and be adsorbed in colorant and make the effect of colorant towards the stably dispersing in toner carrier, but because the spreading agent of random randomly disposes pigment adsorption base, therefore easily pass through to be cross-linked and tackify.On the other hand, because pigment adsorption base high density in segmented copolymer is arranged, 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 amine value is below the above 99mgKOH/g of 10mgKOH/g, the favorable solubility in developer solution, can development at the appointed time in developing procedure, in addition, and the not dissolved matter of residual colored resin composition not in the non-image portion on substrate.
As the monomer of presoma of A block with solvophilic, as long as do not have the amino functional group that waits nitrogen atom and can with the material of monomer copolymerization that forms B block, be not particularly limited.
As A block, for example, can enumerate the polymer architecture that following comonomer copolymerization is formed: the styrenic monomers such as styrene, α-methyl styrene, (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, 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 monomer, the glycidol ethers such as allyl glycidyl ether, crotonic acid glycidol ether are monomer etc.
Wherein, as A block, preferably contain poly alkylene glycol (methyl) acrylate such as polyglycol (methyl) acrylate, polypropylene glycol (methyl) acrylate as copolymer composition (, contain the part-structure from poly alkylene glycol (methyl) acrylate) material, particularly preferably there is the represented part-structure of following general formula (I).
[in general formula (I), n represents 1～5 integer, R 1represent hydrogen atom or methyl.]
The represented part-structure of general formula (I) particularly preferably contains 5～40 % by mole in A block.
In addition, from improving the viewpoint of dispersion stabilization, in A block, preferably further contain the Component units taking (methyl) acrylic ester monomer as presoma beyond the represented part-structure of the general formula (I) of 50～90 % by mole, be more preferably 60～80 % by mole.Wherein, owing to being used as (methyl) acrylic ester monomer by use (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) 2-ethyl hexyl acrylate, the dispersiveness of coloured composition, excellent in stability, therefore preferred above-mentioned substance.
In A block, by containing the represented part-structure of general formula (I), thus the water wettability of giving and the dissolubility in developer solution is improved.On the other hand, by further containing the Component units taking (methyl) acrylic ester monomer as presoma beyond the represented part-structure of general formula (I), improve and dispersion stabilization rising with the compatibility of adhesive resin.
As the B block of functional group with nitrogen atom, preferably there is primary～tertiary amino as functional group.The more than 10 % by mole of functional group that contain ratio and be preferably whole nitrogen atoms of primary～tertiary amino, are more preferably more than 40 % by mole.
Amino preferably use-NR 4r 5(wherein, R 4and R 5respectively independently represent can have substituent ring-type or chain alkyl, can there is substituent aryl or can there is substituent aralkyl) represent, as the part-structure that contains it, preference is as the structure representing with following formula.
[in general formula (II), R 4and R 5represent to have independently respectively substituent ring-type or chain alkyl, can there is substituent aryl and maybe can there is substituent aralkyl, R 3represent that carbon number is more than 1 alkylidene, R 2represent 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, preference is as the structure representing with following formula.
As abovely can in 1 B block, contain two or more containing amino part-structure.In this case, contain two or more amino part-structure can random copolymerization in this B block or the either type of block copolymerization contain.In addition, not damaging in the scope of effect of the present invention, can in B block, part contain not containing amino part-structure, as the example of such part-structure, can enumerate the part-structure from (methyl) acrylic ester monomer.Related containing amino part-structure, the content in B block is not preferably 0～60 % by mole, is more preferably 0～20 % by mole, most preferably is in B block containing related not containing amino part-structure.
In addition, as the B block of functional group with nitrogen atom, while using quaternary ammonium salt group,, do not carry out the absorption to colorant, thereby likely produce tackify or gelation with other resin-phase interactions because its polarity is strong.Therefore, as the functional group of nitrogen atom, preferred primary, secondary or tertiary amine.Wherein, tertiary amine, due to the absorption affinity and stability two aspects that have both colorant, is therefore preferred.
; from improving the viewpoint of dispersed and developing solution dissolution, the represented repetitive of general formula (I) that acrylic acid series segmented copolymer preferably contains 5～40 % by mole in the A block with solvophilic, have in the B block of functional group of nitrogen atom and containing the represented repetitive of general formula (II).
In addition, when acrylic acid series segmented copolymer contains the acid groups such as carboxylic acid, phosphoric acid, due to B block in amine position etc. there is soda acid and interact, thereby dispersion stabilization is declined, the therefore low material of preferred acid number, is 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.More than the use level of acrylic acid series segmented copolymer is preferably 1 weight portion from the viewpoint of pigment-dispersing.In addition, with this coloured composition, while making the pattern of pixels of color filter by photoetching process, from obtaining the viewpoint of high alkalinity developability, be preferably below 70 weight portions.
In addition, color composition for color filter of the present invention can be used alone or with above-mentioned resin type spreading agent use, also can contain other resin type spreading agent.
As other resin type spreading agent, can use polyurethane, the polycarboxylates such as polyacrylate, unsaturated polyester acid amides, poly carboxylic acid, poly carboxylic acid (part) amine salt, poly carboxylic acid ammonium salt, poly carboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, the polycarboxylate that contains hydroxyl and the modifier of these materials, poly-(rudimentary alkyleneimines) and the oiliness such as acid amides and salt thereof the spreading agent forming with the pet reaction of free carboxy, (methyl) acrylic acid-styrol copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol (PVA), the water soluble resins such as polyvinylpyrrolidone and water-soluble high-molecular compound, polyester system, modified polyacrylate system, ethylene oxide/propylene oxide additive compound, phosphate system etc.
As spendable commercially available resin type spreading agent in the present invention, can enumerate the DIsperbyk-101 that Bi Ke chemical company manufactures, 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 Japanese Lubrizol Corp. manufactures, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, the EFKA-46 that 76500 etc., EFKA chemical company manufactures, 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 manufactures, PB711, PB821, PB822, PB824 etc.
The pigment dispersing agent of using as black pigment, in the time using pigment derivative, preferably use has the precursor skeleton of organic pigment and the pigment derivative of alkali subtituent, because electrical specification becomes better, is therefore preferred.By further containing resin type spreading agent, owing to further improving electrical specification, taking into account mobility and stability, be therefore preferred.
Resin type spreading agent comprises having and is adsorbed in the pigment compatibility position of light-proofness black pigment character and has the position of compatibility with black pigment carrier, and has the effect that makes the stably dispersing to black pigment carrier by being adsorbed in light-proofness black pigment.With aforementioned pigment derivative similarly, resin type spreading agent is given with the compatibility of black pigment and pigment derivative, is made the molecules align in black-colored resin composition more even, further reducing the skew of electric charge, therefore also contribute to electrical specification to improve, is preferred thus.
Especially, use black pigment, while thering is the precursor skeleton of organic pigment and the pigment derivative of alkali subtituent and acidic resins type spreading agent, because performance takes into account mobility and the so excellent effect of electrical specification, be therefore preferred.This is due to by acidic resins type spreading agent with have an interaction between the soda acid substituting group that the pigment derivative of alkali subtituent has, can in and electric charge, as a result of, owing to can suppressing partial charge skew, therefore electrical specification improves.
In these materials, in order to improve and the interaction of 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 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 be owing to can further promoting the pigment adsorption of pigment and resin type spreading agent and improving the dispersiveness of pigment, therefore prevents that the effect that the pigment after disperseing reassociates is large.Therefore, with the acid derivant with organic pigment or its slaine, Pigments, in pigment carrier and when the coloured composition forming, can be obtained to the color filter of excellent in stability.Further, by be used as by thering is the A block of solvophilic and thering is A-B segmented copolymer that the B block of functional group of nitrogen atom forms or the resin type spreading agent of B-A-B segmented copolymer simultaneously, thereby more improve dispersed.Thereby the soda acid that can this is presumably because the alkali subtituent of acidic substituent by being disposed near derivant pigment and spreading agent interacts and promotes the pigment adsorption of spreading agent.
As acid derivant or its slaine of organic pigment, can enumerate the compound that following general formula (1) represents.
P-Lx general formula (1)
(wherein, P: organic pigment residue, L: acidic substituent, x: hydrogen atom or metallic ion)
As the organic pigment of organic pigment residue that forms P, for example, can enumerate: diketopyrrolopyrrolecocrystals series pigments; The azo pigments such as azo, bisdiazo, polyazo; The phthualocyanine pigments such as copper phthalocyanine, copper halide phthalocyanine, ZnPc, zinc halide phthalocyanine, metal-free phthalocyanine; Amino anthraquinones, diamido DIANTHRAQUINONE, anthracene pyrimidine, flavanthrone, anthracene are formed the anthraquione pigmentss such as anthrone, indanthrene, pyranthrone, violanthrone; Quinoline Azone series pigments; Dioxazine series pigments; Purple cyclic ketones series pigments; Perylene pigment; The accurate indigo series pigments of sulphur; Isoindoline series pigments; Isoindolinone pigment; Intellectual circle's series pigments; Quinophthalone series pigments; Dioxazine series pigments; Metal complex series pigments etc.
Wherein, quinophthalone series pigments, particularly quinophthalone are yellow uitramarine C.I. pigment yellow 13 8, due to excellences such as the throughput rate of coloured composition, dispersion stabilization, thermotolerance, photostability, solvent resistances, are therefore preferred.
As the substituting group of acidic substituent that forms L, for example, can enumerate sulfonic acid, carboxylic acid, phosphoric acid etc.
As the metallic ion of x, can enumerate the alkali metal ion such as sodium, potassium, the alkaline-earth metal ions such as magnesium, calcium, barium, the amphoteric metal ions such as aluminium, zinc, the transition metal ions such as iron, nickel etc.
Wherein, preferred transition metal ions such as amphoteric metal ion, iron, nickel such as alkaline-earth metal ion, aluminium, zinc such as calcium, barium etc.Wherein aluminium ion has high-fire resistance and dispersiveness, thereby particularly preferably.
As acid derivant or its slaine of organic pigment, the particularly preferably sulfonic acid of quinophthalone or its aluminium salt.The dispersion of the sulfonic acid of quinophthalone or its aluminium salt pair colorant excellent and prevent from disperseing after the effect that reassociates of colorant large.Therefore, use the sulfonic acid of quinophthalone or its aluminium salt to make colorant be scattered in that resin, organic solvent are waited in toner carrier and the excellent in stability of the coloured composition forming.
For example, the sulfonic acid that is the quinophthalone that forms of yellow uitramarine C.I. pigment yellow 13 8 by quinophthalone is the represented compound of following formula (2), and its aluminium salt is the represented compound of following formula (3).
The aluminium salt of the sulfonic acid of quinophthalone can synthesize 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 to 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, uses sodium hydrate aqueous solution that pH is adjusted to after alkalescent, slowly add aluminum sulfate aqueous solution and make 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 with the acid derivant of this organic pigment or its slaine the pigment derivative using and for example can enumerate the material that 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, Japanese Patent Publication 5-9469 communique etc. are recorded.
In addition, color composition for color filter of the present invention can be by compound represented following general formula (1 ') as pigment derivative.The pigment derivative of particularly preferably using as black colorant composition.
P '-L ' n general formula (1 ')
[wherein, P ': organic pigment residue, anthraquinone residue, acridone residue or three zin residues, L ': alkali subtituent, acidic substituent maybe can have substituent phthalimide methyl, the integer of n:1～4.]
As the organic pigment residue that forms P ', for example, can enumerate diketopyrrolopyrrolecocrystals series pigments; The azo pigments such as azo, bisdiazo, polyazo; The phthualocyanine pigments such as copper phthalocyanine, copper halide phthalocyanine, metal-free phthalocyanine; Amino anthraquinones, diamido DIANTHRAQUINONE, anthracene pyrimidine, flavanthrone, anthracene are formed the anthraquione pigmentss such as anthrone, indanthrene, pyranthrone, violanthrone; Quinoline Azone series pigments; Dioxazine series pigments; Purple cyclic ketones series pigments; Perylene pigment; The accurate indigo series pigments of sulphur; Isoindoline series pigments; Isoindolinone pigment; Quinophthalone series pigments; Intellectual circle's series pigments; Metal complex series pigments etc.
Wherein, the pigment derivative that preferably precursor skeleton is organic pigment, from the low viewpoint of dielectric loss tangent, can be more preferably and use dioxazine series pigments and diketopyrrolopyrrolecocrystals series pigments.
Can preferably use L ' in general formula (1 ') is the alkaline derivant of alkali subtituent.Wherein, have the precursor skeleton of organic pigment and the pigment derivative of alkali subtituent owing to giving compatibility that Yu perylene is black pigment, make molecules align homogenising in black-colored resin composition, reduce the skew of electric charge, and contribute to improve electrical specification, be therefore preferred.
In addition, the preferred substituting group of L ' for selecting from the represented group of general formula (2 '), (3 ') and (4 ').
[wherein,, in general formula (2 ')～(4 '), X is-SO 2-,-CO-,-CH 2-,-CH 2nHCOCH 2-,-CH 2nHSO 2cH 2-or Direct Bonding; Y is-NH-,-O-or Direct Bonding; N is 1～10 integer; Y 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 has 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 57for the represented substituting group of above-mentioned general formula (2 ') 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, 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-1,2-dimethyl propylamine, N, 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, N-diethylamino-ethylamine, N, N-diethylaminopropylamine, N, N-lignocaine hexylamine, N, N-lignocaine butylamine, N, N-lignocaine amylamine, N, the amino butylamine of N-dipropyl, N, N-dibutylaminopropylamine, N, N-dibutylamino ethamine, N, N-dibutylamino butylamine, N, the amino amylamine of N-bis-isobutyls, N, the amino propylamine of N-methyl-bay, N, N-ethyl-own aminoethyl, N, N-distearyl aminoethyl, N, the oily aminoethyl of N-bis-, N, the amino butylamine of N-distearyl, piperidines, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidine carbinols, nipecotic acid, isonipecotic acid, isonipecotic acid methyl esters, ethyl isonipecotate, 2-piperidines ethanol, pyrrolidine, 3-hydroxyl pyrrolidine, N-aminoethyl piperidine, N-aminoethyl-4-pipecoline, N-aminoethyl morpholine, N-aminopropyl piperidines, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropyl morpholine, N methyl piperazine, N-butyl piperazine, N-methyl homopiperazine, 1-cyclopentyl-based piperazine, 1-amino-4-methyl piperazine, 1-cyclopentyl-based piperazine etc.
Pigment derivative, anthraquinone derivative and the acridone derivatives with alkali subtituent can synthesize by various synthesis paths.For example, in organic pigment, anthraquinone or acridone after represented substituting group of introducing-type (5 ')～(8 '), by making to form represented such as N of substituent above-mentioned amine component of formula (2 ')～(4 ') with above-mentioned substitution reaction, N-dimethylaminopropylamine, N methyl piperazine, diethylamine or 4-[4-hydroxyl-6-[3-(dibutylamino) the third amino]-1,3,5-triazine-2-base amino] aniline etc. reacts to obtain.
Formula (5 ') :-SO 2cl
Formula (6 ') :-COC1
Formula (7 ') :-CH 2nHCOCH 2cl
Formula (8 ') :-CH 2cl
When the substituting group of formula (5 ')～(8 ') reacts with above-mentioned amine component, can be mixed with make formula (5 ')～(8 ') thus substituting group part occur hydrolysis and by chlorine be substituted by hydroxyl form material.In this case, formula (5 ') and formula (6 ') become respectively sulfonic group and carboxylic acid group, and they all can form free acid, also can be the salt forming with metal or the above-mentioned monoamine of 1～3 valency.
In addition, organic pigment is azo while being pigment, also can in advance the substituting group represented general formula (2 ')～(4 ') be imported to bisdiazo composition or coupling agent composition, manufacture azo pigment derivant afterwards by carrying out coupling reaction.
While considering prevent the decline of contrast and obtain good electrical specification, more than the total amount of pigment derivative is preferably 0.5 weight portion with respect to weight 100 weight portions of colorant, more preferably more than 1 weight portion, more than most preferably being 3 weight portions.In addition, while considering sufficient photostability and the good electrical specification 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 alone, but also two or more mixes use.
[surfactant]
As surfactant, can enumerate alkali metal salt, odium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl base ether sodium disulfonate, dodecyl sulphate monoethanolamine, dodecyltriethanolamine sulfate, ammonium lauryl sulfate, the stearic acid monoethanolamine of lauryl sodium sulfate, polyoxyethylene alkyl ether sulfate salt, neopelex, styrene-propene acid copolymer, the anionic surfactant such as monoethanolamine, polyoxyethylene alkyl ether phosphate of styrene-propene acid copolymer; The 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 surfactant such as ethylene oxide adduct; The amphoteric surfactantes such as alkyl betaine, alkyl imidazoline such as alkyl-dimethyl aminoacetic acid betaine, these surfactants can use separately or two or more mixes 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 >
In color composition for color filter of the present invention, can contain resin.The resin containing in 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 full wavelength region may of 400～700nm that aforementioned resin is preferably in visible region is more than 80%, be more preferably more than 95% transparent resin.In addition, while use with the form of alkali-developable photosensitive color composition, preferably use the alkali solubility vinyl resin forming containing the ethylene unsaturated monomer copolymerization of acidic-group.In addition, in order further to improve light sensitivity, also can use the active energy ray-curable resin with ethene unsaturated double-bond.
Especially, by using the active energy ray-curable resin on side chain with ethene unsaturated double-bond, can improve the stability of erosion resistant, 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 series 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.
As the ethene base system alkali soluble resins that makes to form containing the ethylene unsaturated monomer copolymerization of acidic-group, for example, can enumerate the resin with the acidic-group such as carboxyl, sulfo group.As alkali soluble resins, particularly, can enumerate acryl resin, alpha-olefin/maleic acid (acid anhydride) multipolymer, styrene/Styrene Sulfonic Acid Copolymer, ethene/(methyl) acrylic copolymer or isobutylene/maleic acid (acid anhydride) multipolymer etc. with acidic-group.Wherein, thermotolerance, the transparency particularly due at least one resin of the acryl resin from having acidic-group and the selection of styrene/Styrene Sulfonic Acid Copolymer with the acryl resin of acidic-group are high, therefore preferably use.
As the active energy ray-curable resin with ethene unsaturated double-bond, for example, can enumerate by method shown below (i) or method (ii) and import the resin that ethene unsaturated double-bond forms.
[method (i)]
As method (i), for example there is following methods: make by the unsaturated monacid carboxyl that has the side group epoxy base of the multipolymer that the ethylene unsaturated monomer of epoxy radicals and another above monomer copolymerization obtain and have an ethene unsaturated double-bond is carried out to addition reaction, make again the hydroxyl generating react with multi-anhydride, thereby import ethene unsaturated double-bond and carboxyl.
As the 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 be used alone, but also two or more is also used.From considering with unsaturated monacid reactive viewpoint of subsequent processing, preferably (methyl) glycidyl acrylate.
As unsaturated monoacid, can enumerate: (methyl) acrylic acid, crotonic acid, adjacent,, to vinyl benzoic acid, the monocarboxylic acids such as (methyl) acrylic acid α position alkylhalide group, alkoxy, halogen, nitro, cyano group substituent etc.These materials can be used alone, but also two or more is also used.
As multi-anhydride, can enumerate tetrabydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride etc.These materials can be used alone, but also two or more is also used.According to needs such as the numbers of increase carboxyl, also can use the tricarboxylic acid anhydrides such as trimellitic anhydride or use the tetracarboxylic dianhydrides such as pyromellitic acid anhydride to make residual anhydride group hydrolysis etc.In addition, as multi-anhydride, use while thering is the tetrabydrophthalic anhydride of ethene unsaturated double-bond or maleic anhydride, can further increase ethene unsaturated double-bond.
As the similar approach of method (i), for example there is following method: make by a part with the ethylene unsaturated monomer of carboxyl and the side chain carboxyl group of the multipolymer that another above monomer copolymerization obtains is carried out to addition reaction with the ethylene unsaturated monomer with epoxy radicals, thereby import ethene unsaturated double-bond and carboxyl.
[method (ii)]
As method (ii), there is following method: there are the ethylene unsaturated monomer of hydroxyl and other by use and there is the unsaturated monacid monomer of carboxyl or other monomers and carry out copolymerization and obtain multipolymer, then the pendant hydroxyl group of this multipolymer is reacted with the isocyanate group of the ethylene unsaturated monomer with isocyanate group.
As the 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 class such as 4-hydroxy butyl ester, (methyl) acrylic acid glyceride or cyclohexanedimethanol list (methyl) acrylate, these materials can be used alone, but also two or more is also used.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 to 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 suppressing the viewpoint of film foreign matter, preferably (methyl) acrylic acid-2-hydroxyl ethyl ester or (methyl) acrylic acid glyceride.
As the 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 two or more also 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, from dispersiveness, stability, developability and the stable on heating viewpoint of colorant, carboxyl that alkali soluble groups when considering as colorant absorption base and developing works, during with the balance of aliphatic group as working facing to the affinity groups of toner carrier and solvent and aromatic group, acid number is preferably 20～300mgKOH/g.While considering the formation of dissolubility to developer solution, fine pattern, more than acid number is preferably 20mgKOH/g.In addition, while considering the residual degree of fine pattern, be preferably below 300mgKOH/g.
Consider from film forming and the good angle of various patience, resin-phase preferably uses with amounts more than 30 weight portions for 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.In order easily to make colorant be well-dispersed in resin, and by dye compositions of the present invention according to dry film thickness be preferably 0.1～10 μ m, the mode that is more preferably 0.2～20 μ m coats shaping filter joint on the transparency carriers such as glass substrate, and uses solvent.
As solvent, can enumerate: 1,2,3-trichloropropane, 1,3-BDO, 1,3-BDO diacetate, Isosorbide-5-Nitrae-dioxs, 2-HEPTANONE, 2-methyl isophthalic acid, ammediol, Isophorone, 3,3,5-trimethylcyclohexanone, 3-ethoxyl ethyl propionate, 3-methyl isophthalic acid, 3-butylene glycol, MMB, 3-methoxyl-3-methyl butyl acetate, 3-methoxybutanol, 3-methoxyl butylacetic acid ester, 4-heptanone, m-xylene, between diethylbenzene, m-dichlorobenzene, DMA, DMF, normal butyl alcohol, n-butyl benzene, n-pro-pyl acetate, 1-METHYLPYRROLIDONE, o-xylene, ortho-chlorotolu'ene, adjacent diethylbenzene, o-dichlorobenzene, parachlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl benzene, gamma-butyrolacton, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, butyl cellosolve, ethylene glycol list isopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, the tertiary butyl ether of ethylene glycol list, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol ether, ethylene glycol ether, glycol monoethyl ether, 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, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetic ester, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, DPE, Dipropylene glycol mono-n-butyl Ether, dipropylene glycol list propyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetyl glycerine, Tri(propylene glycol)butyl ether,mixture of isomers, Tripropylene glycol monomethyl Ether, PGDA, propylene glycol phenylate, dihydroxypropane single-ether, dihydroxypropane single-ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 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 separately a kind, or mix two or more with arbitrary proportion as required and use.
Wherein, consider from the angle of the favorable dispersibility of colorant of the present invention, preferably use the ketones such as aromatic series alcohols or cyclohexanone such as glycol acetates, benzylalcohol such as propylene glycol monomethyl ether acetate, dihydroxypropane single-ether acetate, glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate.
From coloured composition being adjusted to suitable viscosity, forming as the filter section of the homogeneous film thickness of target, solvent phase preferably uses with the amount of 800～4000 weight portions for 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 photosensitive coloring composition for color filter (erosion resistant) use.
< photopolymerization monomer >
Color composition for color filter of the present invention can contain photopolymerization monomer.In photopolymerization monomer, comprise by ultraviolet ray or hot etc. and solidify the monomer or the oligomer that generate resin, these materials can use separately or two or more mixes 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 developability, is more preferably 10～300 weight portions, more preferably 10～200 weight portions.As photopolymerization monomer, be preferably the compound with more than 1 or 2 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) β-acryloxypropionic acid, 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, ester acrylate, (methyl) acrylate of methylolation melamine, epoxy (methyl) acrylate, the various acrylate such as urethane acrylate and methacrylate, (methyl) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinethene, ethylene glycol bisthioglycolate vinethene, pentaerythrite triethylene ether, (methyl) acrylamide, N-methylol (methyl) acrylamide, 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.Irradiate when said composition being solidified and utilizing photoetching process shaping filter joint or black matrix by ultraviolet ray, add Photoepolymerizationinitiater initiater etc. to modulate 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)-acetophenone based compounds such as butane-1-ketone, the 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, propylene acidifying benzophenone, 4-benzoyl group-4 '-methyldiphenyl base sulfide or 3,3 ', the benzophenone based compounds such as 4,4 '-tetra-(tert-butyl peroxy carbonyl) benzophenone, thioxanthones, CTX, 2-methyl thioxanthones, isopropyl thioxanthone, 2, the thioxanthones based compounds such as 4-diisopropyl thioxanthones or 2,4-diethyl thioxanthone, 2, 4, 6-trichloro-triazine, 2-phenyl-4, 6-bis-(trichloromethyl) s-triazine, 2-(p-methoxyphenyl)-4, 6-bis-(trichloromethyl) s-triazine, 2-(p-methylphenyl)-4, 6-bis-(trichloromethyl) s-triazine, 2-piperonyl-4, 6-bis-(trichloromethyl) s-triazine, 2, 4-bis-(trichloromethyl)-6-styryl s-triazine, 2-(naphtho--1-yl)-4, 6-bis-(trichloromethyl) s-triazine, 2-(4-methoxyl-naphtho--1-yl)-4, 6-bis-(trichloromethyl) s-triazine, 2, 4-trichloromethyl-(piperonyl)-6-triazine or 2, the triazine based compounds such as 4-trichloromethyl-(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] the oxime ester based compound such as-1-(O-acetyl oxime), the phosphine based compounds such as two (2,4,6-trimethylbenzoyl) phenyl phosphine oxides or TMDPO, the quinone based compounds such as 9,10-phenanthrenequione, camphorquinone, EAQ, borate based compound, carbazole based compound, imidazole compound, or luxuriant titanium sub-group compound etc.
These Photoepolymerizationinitiater initiaters can use separately a kind, 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 developability, is more preferably 10～150 weight portions.
< sensitizer >
In color composition for color filter of the present invention, also can contain sensitizer.
As sensitizer, can enumerate: the unsaturated ketone taking chalcone derivative, dibenzalacetone derivatives etc. as representative, taking dibenzoyl, camphorquinone etc. as representative 1, the 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 derivatives, indoline derivative thing, azulene derivatives, Azulene (azulenium) derivant, side acid derivative, derivatives of porphyrin, Tetraphenyl porphyrin derivative, triarylmethane derivatives, Tetrabenzoporphyrin derivant, four pyrazine porphyrin (Tetrapyrazinoporphyrazine) derivants, phthalocyanine derivates, tetraazatetradecane porphyrin (tetraazaporphyrazine) derivant, four quinoline promises porphyrin (tetra (quinoxalino) porphyrazine) derivant, naphthalocyanine derivative, sub-phthalocyanine derivates, pyran derivate, sulfo-pyran derivate, cyanogen glucoside (Tetraphyllin) derivant, wheel ene derivative, spiropyran derivatives, spiro oxazone derivative, sulfo-spiro-pyrans (Thio Spiropyran) derivant, metal arene complex compound, organic ruthenium complex compound, or michler's ketone derivant, alpha-acyloxy ester, two acyl group hydroxide phosphines, methyl benzoylformate, dibenzoyl, 9,10-phenanthrenequione, camphorquinone, EAQ, 4,4 '-diethyl isophthalic 3,5-dimethylphenyl ketone, 3,3 '-or 4,4 '-tetra-(tert-butyl peroxy carbonyl) benzophenone, 4,4 '-lignocaine benzophenone etc.
These sensitizers can use separately a kind, or are mixed with two or more with arbitrary proportion as required.
More specifically, sensitizer of recording in " specific function material (special different Machine can material) " (, CMC in 1986) that " functional pigmented chemistry (Machine can property pigment chemistry) " (, CMC in 1981) and gloomy loyal three youths in pond etc. that can enumerate that " pigment handbook (pigment Ha Application De Block Star Network) " (, talk society in 1986), the former letter in great river etc. that the former letter in great river etc. writes write write, but be not limited to these.The light to from ultraviolet near infrared region that in addition, 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 coloured composition, is preferably 3～60 weight portions, from the viewpoint of photo-curable, developability, is more preferably 5～50 weight portions.
< levelling agent >
In order to make the levelability of the composition on transparency carrier good, in color composition for color filter of the present invention, preferably add levelling agent.As levelling agent, preferably on main chain, there is the dimethyl siloxane of polyether structure or polyester construction.As the object lesson of dimethyl siloxane on main chain with polyether structure, can enumerate FZ-2122, the BYK-333 that Bi Ke chemical company manufactures etc. that Dong Li Dow Corning Corporation manufactures.As the object lesson of dimethyl siloxane on main chain with polyester construction, can enumerate BYK-310, BYK-370 etc. that Bi Ke chemical company manufactures.On main chain, having the dimethyl siloxane on the dimethyl siloxane of polyether structure and main chain with polyester construction also can be used together.With regard to the content of levelling agent, conventionally in total weight 100 % by weight of coloured composition, preferably use 0.003～0.5 % by weight.
As the particularly preferred material of levelling agent, can preferably use material as described below: it is for having the one of the so-called surfactant of hydrophobic group and hydrophilic group in molecule, although there is hydrophilic group, but the dissolubility to water is little, and while making an addition in coloured composition, it reduces the feature that capillary ability is low, in addition, though reduce capillary ability low to the wetting state of glass plate all good characteristic be useful, and fully inhibition zone is electrical while adding with the addition of the defect of the caused film that do not occur spuming.As the levelling agent with such preferred characteristics, can preferably use the dimethyl polysiloxane with polyalkylene oxides unit.As 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: polyalkylene oxides unit be incorporated into the repetitive of dimethyl polysiloxane hanging type, be incorporated into the terminal-modified type of the end of dimethyl polysiloxane, alternately repeat the block polymer type of the straight chain shape of combination with dimethyl polysiloxane.The dimethyl polysiloxane with polyalkylene oxides unit can be enumerated for example FZ-2110, the FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, the FZ-2207 that are sold by Dong Li Dow Corning Corporation, but is not limited to these.
In levelling agent, can also supplement the surfactant that adds anionic property, cationic, nonionic or both sexes.Surfactant can two or more mix use.
As supplement the anionic surfactant that adds in levelling agent, can enumerate 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, the lauryl sodium sulfate of polyoxyethylene alkyl ether sulfate salt, neopelex, styrene-propene acid copolymer, monoethanolamine, the polyoxyethylene alkyl ether phosphate etc. of styrene-propene acid copolymer.
As supplement the cationic surfactant adding in levelling agent, can enumerate alkyl quaternary ammonium salts and ethylene oxide adduct thereof.As supplement the nonionic surfactant adding in levelling agent, 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 the amphoteric surfactantes such as alkyl betaine, alkyl imidazoline such as alkyl-dimethyl aminoacetic acid betaine and fluorine system and silicon-type.
< amine compound >
In addition, in color composition for color filter of the present invention, can contain the amine compound of the effect of the oxygen 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 solidifying of auxiliary heat thermosetting resin, in color composition for color filter of the present invention, can contain as required hardening agent, curing accelerator etc.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 to these, as long as can react with thermoset resin, can use any hardening agent.In addition, in these hardening agent, preferably enumerating compound, the amine in 1 molecule with more than 2 phenolic hydroxyl group is hardening agent.As aforementioned curing accelerator, can use for example amines (for example, dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, N-dimethyl benzyl amine etc.), quarternary ammonium salt compound (such as triethyl benzyl ammonia chloride etc.), block isocyanate compound (such as dimethylamine etc.), imdazole derivatives bicyclic amidine compound and salt thereof (for example, imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole etc.), phosphorus compound (for example, triphenylphosphine etc.), guanidine amines (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 preferably 0.01～15 weight portion taking the total weight of thermoset resin as benchmark (100 weight portion).
Other additive components of < >
For make composition through time viscosity stabilization, in color composition for color filter of the present invention, can contain storage-stable agent.In addition, in order to improve and the adaptation of transparency carrier, can also contain the closely sealed improving agents such as silane coupling agent.
As storage-stable agent, for example, can enumerate organic phosphine, the phosphites etc. such as the organic acids such as the aliquat such as benzyl trimethyl chloride, diethyl hydramine, lactic acid, oxalic acid and methyl ether thereof, tert-butyl catechol, tetraethyl phosphine, tetraphenyl phosphine.Storage-stable agent can 0.1～10 weight portion with respect to total weight 100 weight portions of colorant amount use.
As closely sealed improving agent, can enumerate: the 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-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, β-(3,4-epoxycyclohexyl) methyltrimethoxy silane, β-(3,4-epoxycyclohexyl) the epoxy silane class such as ethyl triethoxysilane, β-(3,4-epoxycyclohexyl) methyl triethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane; The amino silane classes such as N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl) γ aminopropyltriethoxy silane, N-β (amino-ethyl) gamma-amino propyl group methyldiethoxysilane, γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, N-phenyl-gamma-amino propyl trimethoxy silicane, N-phenyl-γ aminopropyltriethoxy silane; The silane coupling agents such as Thiosilicane class such as γ mercaptopropyitrimethoxy silane, γ-sulfydryl propyl-triethoxysilicane etc.Closely sealed improving agent can 0.01～10 weight portion with respect to total weight 100 weight portions of colorant, preferably the amount of 0.05～5 weight portion is used.
The manufacture method > of < coloured composition
Color composition for color filter of the present invention can carry out together fine dispersion by each composition with various diverting devices such as three-roll grinder, two roller mills, sand mill, kneader or attitors and manufacture (pigment dispersion).
In addition, as for color filter when photosensitive coloring composition (erosion resistant), adjustable solvent develop type or the alkali-developable coloured composition of being made for.Solvent develop type or alkali-developable coloured composition can, by mixing aforementioned pigment dispersion, photopolymerization monomer and/or Photoepolymerizationinitiater initiater, also can have solvent, other pigment dispersing agent and adjuvant etc. to modulate as required.Photoepolymerizationinitiater initiater can add in the stage of modulation coloured composition, also can add having modulated after coloured composition.
While considering viscosity, thickness, mobility and coating, it is above and be less than 40 % by weight that the solid component concentration of color composition for color filter is preferably 5 % by weight.
Color composition for color filter preferably utilizes the methods such as centrifuging, sintered filter, film filter that corase particleses more than 5 μ m, the corase particles, more preferably corase particles more than 0.5 μ m and the dust of sneaking into that are preferably more than 1 μ m are removed.As above the color composition for color filter obtaining is not preferably containing corase particles.Be more preferably below 0.3 μ m.
In addition, while making the color composition for color filter in the 1st embodiment, can mix following material: as colorant, for the average primary particle diameter aspect ratio that is 20～50nm and pigment particles is the pigment of 1: 1～1: 3.5; As resin type spreading agent, be by thering is the A block of solvophilic and thering is A-B segmented copolymer that the B block of functional group of nitrogen atom forms or B-A-B segmented copolymer and amine value are scaled the acrylic acid series segmented copolymer below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent; Solvent; And other compositions as required.
In addition, especially, when color composition for color filter of the present invention forms the black-colored resin composition as black colorant composition (the 2nd embodiment), can mix following material: as light-proofness black pigment, for average primary particle diameter is that 50nm aspect ratio following and primary particle is that 1: 1～1: 2 perylene is black pigment and carbon black; Resin; Solvent; And other compositions as required, and Gai perylene of Shi be black pigment content taking the total weight of light-proofness black pigment (A) during as benchmark as 78～95 % by weight and black-colored resin composition solid component concentration are more than 5 % by weight and be less than 40 % by weight.
In addition, while forming the black-colored resin composition as the coloured composition of black with color composition for color filter of the present invention (the 3rd embodiment), can mix following composition: as light-proofness black pigment, for average primary particle diameter is that 50nm aspect ratio following and primary particle is that 1: 1～1: 2 perylene is 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 the filter section and/or the black matrix that are 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 shaping filter joint and/or black matrix to carry out as follows.,, with coating processes such as spraying, spin coating, slot coated, roller coat, on transparency carrier, coating is as the colored resin composition of solvent develop type or alkali-developable colored resin composition (erosion resistant) modulation.To the film after dried if necessary, by contact with this film or contactless state under the mask with predetermined pattern that arranges carry out active energy beam exposure.Afterwards, be impregnated in solvent or alkaline-based developer or by spraying and wait developer solution spraying, remove 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 the filter section higher than print process precision and/or black matrix.
As the substrate of color filter, can use the resin plates such as the glass plates such as the soda-lime glass high to visible light transmissivity, low alkali borosilicate glass, alkali-free alumina borosilicate glass or polycarbonate, polymethylmethacrylate, polyethylene terephthalate.In addition, in order to drive the liquid crystal after panelization, can on the surface of glass plate or resin plate, form the transparency electrode being formed by indium oxide, tin oxide etc.
When development, can use the aqueous solution such as sodium carbonate, NaOH as alkaline-based developer, also can use the organic base such as dimethyl benzyl amine, triethanolamine.Also can in developer solution, add in addition defoamer, surfactant.
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 ultraviolet exposure sensitivity, also can be after above-mentioned color composition for color filter coating be dry, be coated with water-soluble or alkali soluble resins, such as polyvinyl alcohol (PVA) or water soluble acrylic resin etc. are also dried, after the film that formation prevents from inhibiting due to oxygen, carry out active energy beam exposure.
As active energy beam, can use the visible ray of electron ray, ultraviolet ray, 400～500nm.With regard to the radiographic source of the electron ray from the one side irradiation of composition coated face, 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 ray of 400～500nm, can use such as 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.The active energy beam energy irradiating from composition coated face one side can be set in the scope of 5～1000mJ, the scope of 20 manageable～300mJ in preferable process in good time.
Be pre-formed black matrix before shaping filter joint on transparency carrier or reflection substrate time, 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), afterwards shaping filter joint.By the joint of shaping filter on TFT substrate and/or black matrix, can improve the aperture opening ratio of display panels and improve brightness.
Herein, the method that forms dyed layer on TFT substrate is described.First, on the surface of TFT substrate or formed on the surface of this driving substrate on the substrate surface of the passivating films such as silicon nitride film, form as required light shield layer to divide the part that forms pixel, on this substrate, be coated with and be dispersed with after the coloured composition of pigment again, carry out prebake and make solvent evaporation, thereby form film.Then, on this film, after photomask exposes, use alkaline-based developer to develop, the unexposed portion of film dissolved and removed, afterwards by after cure and formed with the alignment arrangements of regulation the pel array of pattern of pixels.Now, on used photomask, except being used to form the pattern of pixel, also can be provided for the pattern of the pit that forms through hole or コ font.
As the TFT substrate using in the time forming dyed layer, can use the substrate same with the substrate of aforementioned color filter, also can be on these substrates implement in advance to utilize the suitable pre-treatment such as chemical reagent processing, plasma treatment, ion plating, sputter, gas-phase reaction method, vacuum evaporation of silane coupling agent etc.Be coated with coloured composition on substrate time, can use the method with the substrate same way 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 easily average out.
In addition, consider from the viewpoint of insulativity, the relative dielectric constant of the every 1.0 μ m dry film thickness of black 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 is less than 99%.The transmitance of wavelength 1000nm is preferably more than 60% and is 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 more high better, but in the situation that active energy beam is ultraviolet ray, visible ray, owing to being difficult to obtain cured coating film, is therefore preferably general below 4.5.
When drying coating film, can use pressure Reduction Dryer, convection oven, IR baking oven, hot plate etc.
On color filter, can form as required cuticula or cylindrical gasket, nesa coating, liquid crystal orientation film etc.
By using sealant by the laminating of color filter and counter substrate, inject liquid crystal from being arranged at the inlet of hermetic unit, seal inlet, and as required light polarizing film or phase retardation film are fitted in to the outside of substrate, can manufacture display panels.
Related display panels can be used in color filters such as using twisted nematic (TN), STN Super TN (STN), plane conversion (IPS), homeotropic alignment (VA), optical compensation curved (OCB) carries 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 be by after utilizing the coating process such as spin coating, slot coated, roller coat to form for example red, blue, green chromatic filter to save with substrate on the substrate at thin film transistor (TFT) (TFT), then form black matrix and make.
In addition, also can on the substrate of aforementioned thin film transistor (TFT) (TFT), form black matrix, then form chromatic filter joint thereon.
Embodiment
Based on embodiment, the present invention is described below, but the present invention can't help these embodiment and limit.In addition, in embodiment, " part " and " % " represents respectively " weight portion " and " % by weight ".In addition, the assay method of the thickness of the contrast 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, film, film is as described below.
Weight-average molecular weight (Mw) > of < resin
The weight-average molecular weight (Mw) of acryl resin is to use TSKgel chromatographic column (manufacture of Dong Cao company), utilization to be equipped with the GPC (manufacture of Dong Cao company, HLC-8120GPC) of RI detecting device, the weight-average molecular weight (Mw) that eluent uses the polystyrene conversion of THF mensuration.
The acid number > of < resin or resin type spreading agent
Acid number is with the NaOH ethanolic solution of 0.1N, obtain by potential difference titration.Acid number represents the acid number of solid constituent.
The amine value > of < resin type spreading agent
Amine value use 0.1N aqueous hydrochloric acid solution, obtain by potential difference titration after, then be converted into the equivalent of potassium hydroxide.The amine value of amine value representation solid constituent.
The specific surface area > of < pigment
The automatic steam adsorbance determinator (" BELSORP18 " that Japanese BEL company manufactures) of the BET method of the mensuration of the specific surface area of pigment by utilizing nitrogen absorption 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 primary particle size from electron micrograph.Particularly, measure minor axis diameter and the major diameter of the primary particle of each pigment, the particle diameter using average as this pigment particles.Then,, to 100 above pigment particles, obtain the volume (weight) of each particle according to the approximate cube of obtaining particle diameter, using volume average particle size as average primary particle diameter.In addition, as previously mentioned, the ratio of the minor axis diameter when measuring the minor axis diameter of primary particle of each pigment and major diameter and the mean value of major diameter, obtains the aspect ratio that minor axis diameter is made as at 1 o'clock.In addition, electron microscope uses transmission-type (TEM).
The contrast > of < film
The light sending from backlight for liquid crystal display unit is deflected by polaroid, then by the dry coating of the coloured composition that is coated with on glass substrate, arrives polaroid.If two polaroids are parallel, light transmission polaroid, and the vertical time of plane of polarisation is polarized sheet blocking.But, when the light being deflected by polaroid passes through the dry coating of coloured composition, the scattering that generation pigment particles causes etc., if produce skew in a part for plane of polarisation, the light quantity that sees through polaroid when polaroid is parallel reduces, part light printing opacity polaroid when polaroid is vertical.Measure this and see through light as the brightness on polaroid, calculate the ratio (contrast) of the brightness of the brightness of polaroid when parallel when vertical.
(contrast)=when parallel (brightness)/when vertical (brightness)
In addition, use chroma luminance meter (opening up " BM-5A " of the manufacture of general Kanggong department) as nitometer, to use polaroid (" NPF-G1220DUN " that Dong electrician company manufactures) as polaroid.When mensuration, in order to interdict unwanted light, spread in mensuration part the black mask that offers the square hole of 1cm.
The thickness G reatT.GreaT.GT of < film
The determining film thickness of film uses surface-profile measuring instrument (Dektak6M that (strain) Ai Fake company manufactures) to measure.
First,, about the 1st embodiment, illustrate with embodiment and comparative example.
The manufacture method > of < resin type spreading agent
(resin type dispersant solution A)
In 4 mouthfuls of detachable flasks that possess thermometer, stirring machine, distillation cascade, refrigeratory, pack 80 parts of methyl ethyl ketones, 86.7 parts of butyl acrylates, 11.8 parts of Block レ Application マ mono-(Blenmer) PME-200 (methoxy polyethylene glycol methacrylate-styrene polymer), 2.8 parts of sparteine, 1.9 parts of isobutyl ethyl bromides into, under nitrogen circulation, be warming up to 40 DEG C.Drop into 1.1 parts of stannous chlorides, be warming up to 75 DEG C and start polymerization.After polyase 13 hour, sample polymeric solution, confirm that by the solid constituent of polymerization polymerization yield is more than 95%, weight-average molecular weight (Mw) is 6860, add 20.0 parts of 1.4 parts of dimethylaminoethyl methacrylates and methyl ethyl ketones, further carry out polymerization.Confirm that by the solid constituent of the polymeric solution after 2 hours polymerization yield is more than 97%, to be cooled to room temperature, stop polymerization.100 parts of the resin solutions of gained are diluted with 100 parts of methyl ethyl ketones, add Zeo-karb " DIAION PK228LH (Mitsubishi Chemical Ind's manufacture) " 60 parts, at room temperature stir 1 hour, further add 6 parts of Kyowaad 500SN (consonance chemical industrial company manufactures) as neutralizing agent, and carry out stirring for 30 minutes.Thereby remove by filter Zeo-karb and adsorbent and remove the residue of polymerization catalyst by utilization.Further, concentrated resin type dispersant solution also replaces with glycol monoethyl ether acetate by solvent, be the resin type dispersant solution A (dispersant A) (amine value is 5mgKOH/g, and acid number is 0mgKOH/g) of 50 % by weight thereby obtain solid constituent ratio.
(resin type dispersant solution B)
In 4 mouthfuls of detachable flasks that possess thermometer, stirring machine, distillation cascade, refrigeratory, pack 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 into, under nitrogen circulation, be warming up to 40 DEG C.Drop into 1.1 parts of stannous chlorides, be warming up to 75 DEG C and start polymerization.After polyase 13 hour, sample polymeric solution, confirm that by the solid constituent of polymerization polymerization yield is more than 95%, weight-average molecular weight (Mw) is 6860, add 20.0 parts of 2.9 parts of dimethylaminoethyl methacrylates and methyl ethyl ketones, further carry out polymerization.Confirm that by the solid constituent of the polymeric solution after 2 hours polymerization yield is more than 97%, to be cooled to room temperature, stop polymerization.100 parts of the resin solutions of gained are diluted with 100 parts of methyl ethyl ketones, add Zeo-karb " DIAION PK228LH (Mitsubishi Chemical Ind's manufacture) " 60 parts, at room temperature stir 1 hour, further add 6 parts of Kyowaad 500SN (consonance chemical industrial company manufactures) as neutralizing agent, and carry out stirring for 30 minutes.Thereby remove by filter Zeo-karb and adsorbent and remove the residue of polymerization catalyst by utilization.Further, concentrated resin type dispersant solution also replaces with glycol monoethyl ether acetate by solvent, be the resin type dispersant solution B (dispersant B) (amine value is 10mgKOH/g, and acid number is 0mgKOH/g) of 50 % by weight thereby obtain solid constituent ratio.
(resin type dispersant solution C)
In 4 mouthfuls of detachable flasks that possess thermometer, stirring machine, distillation cascade, refrigeratory, pack 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 into, under nitrogen circulation, be warming up to 40 DEG C.Drop into 1.1 parts of stannous chlorides, be warming up to 75 DEG C and start polymerization.After polyase 13 hour, sample polymeric solution, confirm that by the solid constituent of polymerization polymerization yield is more than 95%, weight-average molecular weight (Mw) is 6860, add 20.0 parts of 20.0 parts of dimethylaminoethyl methacrylates and methyl ethyl ketones, further carry out polymerization.Confirm that by the solid constituent of the polymeric solution after 2 hours polymerization yield is more than 97%, to be cooled to room temperature, stop polymerization.100 parts of the resin solutions of gained are diluted with 100 parts of methyl ethyl ketones, add Zeo-karb " DIAION PK228LH (Mitsubishi Chemical Ind's manufacture) " 60 parts, at room temperature stir 1 hour, further add 6 parts of Kyowaad 500SN (consonance chemical industrial company manufactures) as neutralizing agent, and carry out stirring for 30 minutes.Thereby remove by filter Zeo-karb and adsorbent and remove the residue of polymerization catalyst by utilization.Further, concentrated resin type dispersant solution also replaces with glycol monoethyl ether acetate by solvent, be the resin type dispersant solution C (dispersing agent C) (amine value is 70mgKOH/g, and acid number is 0mgKOH/g) of 50 % by weight thereby obtain solid constituent ratio.
(resin type dispersant solution D)
In 4 mouthfuls of detachable flasks that possess thermometer, stirring machine, distillation cascade, refrigeratory, pack 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 into, under nitrogen circulation, be warming up to 40 DEG C.Drop into 1.1 parts of stannous chlorides, be warming up to 75 DEG C and start polymerization.After polyase 13 hour, sample polymeric solution, confirm that by the solid constituent of polymerization polymerization yield is more than 95%, weight-average molecular weight (Mw) is 6860, add 20.0 parts of 27.1 parts of dimethylaminoethyl methacrylates and methyl ethyl ketones, further carry out polymerization.Confirm that by the solid constituent of the polymeric solution after 2 hours polymerization yield is more than 97%, to be cooled to room temperature, stop polymerization.100 parts of the resin solutions of gained are diluted with 100 parts of methyl ethyl ketones, add Zeo-karb " DIAION PK228LH (Mitsubishi Chemical Ind's manufacture) " 60 parts, at room temperature stir 1 hour, further add 6 parts of Kyowaad 500SN (consonance chemical industrial company manufactures) as neutralizing agent, and carry out stirring for 30 minutes.Thereby remove by filter Zeo-karb and adsorbent and remove the residue of polymerization catalyst by utilization.Further, concentrated resin type dispersant solution also replaces with glycol monoethyl ether acetate by solvent, be the resin type dispersant solution D (spreading agent D) (amine value is 95mgKOH/g, and acid number is 0mgKOH/g) of 50 % by weight thereby obtain solid constituent ratio.
(resin type dispersant solution E)
In 4 mouthfuls of detachable flasks that possess thermometer, stirring machine, distillation cascade, refrigeratory, pack 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 into, under stream of nitrogen gas, be warming up to 40 DEG C.Drop into 1.1 parts of stannous chlorides, be warming up to 75 DEG C and start polymerization.After polyase 13 hour, sample polymeric solution, confirm that by the solid constituent of polymerization polymerization yield is more than 95%, weight-average molecular weight (Mw) is 6860, add 20.0 parts of 34.3 parts of dimethylaminoethyl methacrylic acids and methyl ethyl ketones, further carry out polymerization.Confirm that by the solid constituent of the polymeric solution after 2 hours polymerization yield is more than 97%, to be cooled to room temperature, stop polymerization.100 parts of the resin solutions of gained are diluted with 100 parts of methyl ethyl ketones, add Zeo-karb " DIAION PK228LH (Mitsubishi Chemical Ind's manufacture) " 60 parts, at room temperature stir 1 hour, further add 6 parts of Kyowaad 500SN (consonance chemical industrial company manufactures) as neutralizing agent, and carry out stirring for 30 minutes.Thereby remove by filter Zeo-karb and adsorbent and remove the residue of polymerization catalyst by utilization.Further, concentrated resin type dispersant solution also replaces with glycol monoethyl ether acetate by solvent, be the resin type dispersant solution E (spreading agent E) (amine value is 120mgKOH/g, and acid number is 0mgKOH/g) of 50 % by weight thereby obtain solid constituent ratio.
(resin type dispersant solution F)
In 4 mouthfuls of detachable flasks that possess thermometer, stirring machine, distillation cascade, refrigeratory, pack 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 into, under stream of nitrogen gas, be warming up to 40 DEG C.Drop into 1.1 parts of stannous chlorides, be warming up to 75 DEG C and start polymerization.After polyase 13 hour, sample polymeric solution, confirm that by the solid constituent of polymeric solution polymerization yield is more than 97%, to be cooled to room temperature, stop polymerization.100 parts of the resin solutions of gained are diluted with 100 parts of methyl ethyl ketones, add Zeo-karb " DIAION PK228LH (Mitsubishi Chemical Ind's manufacture) " 60 parts, at room temperature stir 1 hour, further add 6 parts of Kyowaad 500SN (consonance chemical industrial company manufactures) as neutralizing agent, and carry out stirring for 30 minutes.Thereby remove by filter Zeo-karb and adsorbent and remove the residue of polymerization catalyst by utilization.Further, concentrated resin type dispersant solution also replaces with glycol monoethyl ether acetate by solvent, be the resin type dispersant solution F (spreading agent F) (amine value is 70mgKOH/g, and acid number is 0mgKOH/g) of 50 % by weight thereby obtain solid constituent ratio.
The resin structure of each resin type spreading agent and the amine value that effectively solid constituent converts are summarized in table 1.
Table 1
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))
Be that 30 parts of yellow uitramarines (C.I. pigment yellow 13 8) are dissolved in 300 parts, 98% sulfuric acid by quinophthalone, stir 8 hours at 70 DEG C, carry out sulfonating reaction.The terminal of reaction is the point that does not observe spectrum change while measuring the spectrophotometric spectra of sulfuric acid solution.Then, this reaction solution is injected to 3000 parts of frozen water, the sulfonation pigment derivative of separating out is filtered, wash, be dried, obtain the 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%.
The slurry of quinophthalone skeleton sulfonic acid is scattered in 10000 parts, 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 occur precipitate from the place dripping, and along with interpolation, pH declines, adding pH while end is 3.6.Do not observe and fade.Filter out the slurry that contains this precipitate, wash, obtain the 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%.
The manufacture method > of < miniaturization pigment
(viridine green PG-1)
Be that 250 parts of 500 parts of viridine green C.I. pigment green 36s (Toyo Ink Manufacturing Co., Ltd. manufacture " Lionol green 6YK "), 1500 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by phthalocyanine, mixing 8 hours at 80 DEG C.Then,, by the warm water of 5 liters of this mixing thing inputs, limit is heated to 70 DEG C of limits and stirs 1 hour, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, at 80 DEG C of dry diels, obtains viridine green PG-1.
(viridine green PG-2)
Be that 250 parts of 500 parts of viridine green C.I. pigment green 36s (Toyo Ink Manufacturing Co., Ltd. manufacture " Lionol green 6YK "), 1500 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by phthalocyanine, mixing 2 hours at 80 DEG C.Then,, by the warm water of 5 liters of this mixing thing inputs, limit is heated to 70 DEG C of limits and stirs 1 hour, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, at 80 DEG C of dry diels, obtains viridine green PG-2.
(viridine green PG-3)
Be that 250 parts of 500 parts of viridine green C.I. pigment green 36s (Toyo Ink Manufacturing Co., Ltd. manufacture " Lionol green 6YK "), 1500 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by phthalocyanine, mixing 12 hours at 40 DEG C.Then,, by the warm water of 5 liters of this mixing thing inputs, limit is heated to 70 DEG C of limits and stirs 1 hour, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, at 80 DEG C of dry diels, obtains viridine green PG-3.
(viridine green PG-4)
Be that 250 parts of 500 parts of viridine green C.I. pigment green 36s (Toyo Ink Manufacturing Co., Ltd. manufacture " Lionol green 6YK "), 1500 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by phthalocyanine, mixing 2 hours at 80 DEG C.Then,, by the warm water of 5 liters of this mixing thing inputs, limit is heated to 70 DEG C of limits and stirs 1 hour, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, at 80 DEG C of dry diels, obtains viridine green PG-4.
(viridine green PG-5)
Be that 250 parts of 500 parts of viridine green C.I. pigment green 36s (Toyo Ink Manufacturing Co., Ltd. manufacture " Lionol green 6YK "), 1500 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by phthalocyanine, mixing 4 hours at 80 DEG C.Then,, by the warm water of 5 liters of this mixing thing inputs, limit is heated to 70 DEG C of limits and stirs 1 hour, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, at 80 DEG C of dry diels, obtains viridine green PG-5.
(yellow uitramarine PY-1)
Be that 360 parts of 200 parts of yellow uitramarine C.I. pigment yellows 150 (Lanxess Corporation manufacture " E-4GN "), 1400 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by nickel complex, mixing 8 hours at 80 DEG C.Then,, by the warm water of 8000 parts of this mixing thing inputs, limit is heated to 80 DEG C of limits and stirs 2 hours, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, at 85 DEG C of dry diels, obtains yellow uitramarine PY-1.
(yellow uitramarine PY-2)
Be that 360 parts of 200 parts of yellow uitramarine C.I. pigment yellow 13s 8 (BASF AG manufacture " K0961HD "), 1400 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by quinophthalone, mixing 8 hours at 80 DEG C.Then,, by the warm water of 8000 parts of this mixing thing inputs, limit is heated to 80 DEG C of limits and stirs 2 hours, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, at 85 DEG C of dry diels, obtains yellow uitramarine PY-2.
(yellow uitramarine PY-3)
Be that 360 parts of 200 parts of yellow uitramarine C.I. pigment yellows 185 (BASF AG manufacture " PalIotolYellow L1155 "), 1400 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by isoindoline, mixing 8 hours at 80 DEG C.Then,, by the warm water of 8000 parts of this mixing thing inputs, limit is heated to 80 DEG C of limits and stirs 2 hours, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, at 85 DEG C of dry diels, obtains yellow uitramarine PY-3.
(black pigment PBLK-2)
Be that 250 parts of 500 parts of black pigment C.I. pigment blacks 32 (BASF AG manufacture " PalIogen Black L0086 "), 2500 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by perylene, mixing 12 hours at 80 DEG C.Then,, by the warm water of 5 liters of this mixing thing inputs, limit is heated to 70 DEG C of limits and stirs 1 hour, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, at 80 DEG C of dry diels, obtains black pigment PBLK-2.
(black pigment PBLK-3)
Be that 250 parts of 500 parts of black pigments (BASF AG manufacture " Lumogen Black FK4281 "), 2500 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by perylene, mixing 12 hours at 40 DEG C.Then,, by the warm water of 5 liters of this mixing thing inputs, limit is heated to 70 DEG C of limits and stirs 1 hour, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, at 80 DEG C of dry diels, obtains black pigment PBLK-3.
(black pigment PBLK-4)
Be that 250 parts of 500 parts of black pigment C.I. pigment blacks 31 (BASF AG manufacture " PalIogen Black S0084 "), 2500 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by perylene, mixing 5 hours at 80 DEG C.Then,, by the warm water of 5 liters of this mixing thing inputs, limit is heated to 70 DEG C of limits and stirs 1 hour, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, at 80 DEG C of dry diels, obtains black pigment PBLK-4.
(black pigment PBLK-5)
Be that 250 parts of 500 parts of black pigments (BASF AG manufacture " Lumogen Black FK4281 "), 2500 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by perylene, mixing 5 hours at 80 DEG C.Then,, by the warm water of 5 liters of this mixing thing inputs, limit is heated to 70 DEG C of limits and stirs 1 hour, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, at 80 DEG C of dry diels, obtains black pigment PBLK-5.
Table 2
Pigment No. Pigment Average primary particle diameter Aspect ratio
PG-1 Phthalocyanine is viridine green 25nm 1∶2.3
PG-2 Phthalocyanine is viridine green 48nm 1∶2.3
PG-3 Phthalocyanine is viridine green 15nm 1∶2.6
PG-4 Phthalocyanine is viridine green 95nm 1∶2.6
PG-5 Phthalocyanine is viridine green 45nm 1∶4.5
PY-1 Metal complex system yellow uitramarine 23nm 1∶1.6
PY-2 Quinophthalone is yellow uitramarine 26nm 1∶1.6
PY-3 Isoindoline is yellow uitramarine 35nm 1∶1.6
PY-4 Metal complex system yellow uitramarine 150nm 1∶4.3
PY-5 Quinophthalone is yellow uitramarine 120nm 1∶5.0
PY-6 Isoindoline is yellow uitramarine 98nm 1∶4.7
PBLK-1 Perylene is black pigment 30nm 1∶1.5
PBLK-2 Perylene is black pigment 45nm 1∶1.5
PBLK-3 Perylene is black pigment 15nm 1∶1.5
PBLK-4 Perylene is black pigment 100nm 1∶1.5
PBLK-5 Perylene is 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 manufactures)
PY-5: quinophthalone is yellow uitramarine C.I. pigment yellow 13 8 (" K0961HD " that BASF AG manufactures)
PY-6: isoindoline is yellow uitramarine C.I. pigment yellow 185 (" PalIotolYellow L1155 " that BASF AG manufactures)
PBLK-1: perylene is black pigment (" Lumogen Black FK4281 " that BASF AG manufactures)
PBLK-6: " #45 " that Tan Xi black pigment Mitsubishi Chemical Ind manufactures
PBLK-7: " MA220 " that Tan Xi black pigment Mitsubishi Chemical Ind manufactures
The manufacture method > of < acrylic resin soln
(modulation of acrylic resin soln 1)
In detachable 4 mouthfuls of flasks, be provided with in the reaction vessel of thermometer, cooling tube, nitrogen ingress pipe, stirring apparatus and pack 70.0 parts of cyclohexanone into, be warming up to 80 DEG C, to in reaction vessel, carry out after nitrogen replacement, with buret with within 2 hours, dripping 7.4 parts of 13.3 parts of n-BMAs, 4.6 parts of methacrylic acid-2-hydroxy methacrylates, 4.3 parts of methacrylic acids, p-Cumenylphenol oxirane modification acrylate (" ARONIX M110 " that Toagosei Co., Ltd manufactures), 2, the potpourri that 2 '-azoisobutyronitrile is 0.4 part.After dropping finishes, then continue reaction 3 hours, obtain the solution of the acryl resin that weight-average molecular weight (Mw) is 26000.Be cooled to after room temperature, the about 2g of sample tree lipoprotein solution, after 20 minutes, measure nonvolatile component at 180 DEG C of heat dryings, in synthetic before resin solution, add dihydroxypropane single-ether acetate according to the mode that makes nonvolatile component become 20 % by weight, thereby obtain acrylic resin soln 1.
(modulation of acrylic resin soln 2)
In the detachable 4 mouthfuls of flasks that possess thermometer, cooling tube, nitrogen ingress pipe, buret and stirring apparatus, pack 370 parts of cyclohexanone into, be warming up to 80 DEG C, to in flask, carry out after nitrogen replacement, with buret with within 2 hours, dripping 25 parts of 18 parts of p-Cumenylphenol oxirane modification acrylates (" ARONIX M110 " that Toagosei Co., Ltd manufactures), 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 dropping finishes, then, after 3 hours, add with 1.0 parts of solution that obtain of 50 parts of dissolving azoisobutyronitriles of cyclohexanone 100 DEG C of reactions, further continue reaction 1 hour at 100 DEG C.Then, air displacement will be replaced with in container, in said vesse, drop into 0.1 part of 9.3 parts, acrylic acid (glycidyl 100%), 0.5 part of three-dimethyl p-aminophenol and quinhydrones, 120 DEG C of sustained responses 6 hours, in the time that 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, 120 DEG C of reactions 3.5 hours, obtain the acrylic resin soln that weight-average molecular weight (Mw) is 19000.Be cooled to after room temperature, the about 2g of sample tree lipoprotein solution, after 20 minutes, measure nonvolatile component at 180 DEG C of heat dryings, in synthetic before resin solution, add cyclohexanone according to the mode that makes nonvolatile component become 20 % by weight, thereby obtain the acrylic resin soln 2 as active energy ray-curable resin.
[embodiment 1]
(pigment dispersion (D-1))
After following potpourri is uniformly mixed, use the zirconium oxide bead that diameter is 0.5mm, disperse after 3 hours with Eiger mill (Eiger Japanese firm manufacture " MINI MODEL M-250MKII "), with the filtrator filtration of 5.0 μ m, thereby make pigment dispersion (DP-11).
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 are changed to the composition shown in table 3, table 4 and use level, similarly operate conditioned pigment dispersion (D-2～30) with pigment dispersion (D-1).
Table 3
Table 4
The evaluation > of < pigment dispersion
About viscosity characteristics, contrast (CR) or the optical density (OD) of the pigment dispersion of gained, evaluate by following method.The results are shown in table 5,6.
(viscosity characteristics)
The initial viscosity when viscosity of pigment dispersion is used E type viscosity meter (" ELD type viscosity meter " that Dong Ji industry company manufactures) to be determined at 25 DEG C.In addition, this pigment dispersion 25g is left standstill after 7 days with air-tight state in glass container, at 40 DEG C, measures viscosity by method similar to the above, using this as through time viscosity.In addition, be divided into 3 grade evaluations according to following benchmark.
Zero: viscosity is less than 20mPas
△: viscosity is more than 20mPas and is less than 40mPas
×: viscosity is more than 40mPas
(contrast (CR))
Use spin coater to change the pigment dispersion (D-1～17) of revolution ground coating gained, make dry film thickness reach 1 μ m left and right, make 3 coated substrates.After coating, use hot-air oven dry after 30 minutes at 80 DEG C, measures each thickness and contrast, the contrast (CR) while using linear dependence method to obtain thickness to be 1 μ m from the data of 3.In addition, be divided into 3 grade evaluations according to following benchmark.
Zero: CR is more than 8000
△: CR is more than 6000 and is less than 8000
×: CR is less than 6000
(optical density (OD))
Use spin-coating method on the glass substrate of 100mm × 100mm, to be coated with after the pigment dispersion of gained, making dry film thickness is the film of 1.0 μ m, heats 20 minutes at 230 DEG C.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 is less than 1.5
×: OD is less than 1.3
Table 5
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 the pigment of 1: 1～1: 3.5 that described colorant contains average primary particle diameter, described resin type spreading agent contains acrylic acid series segmented copolymer, described acrylic acid series segmented copolymer is by having the A block of solvophilic and having A-B segmented copolymer or the B-A-B segmented copolymer that the B block of functional group of nitrogen atom forms, and its amine value is scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent, it is low and stable that color composition for color filter of the present invention has all obtained viscosity, also high good result (embodiment 1～8) of CR.
Wherein, further added the pigment dispersion (D-3) of embodiment 3 of the slaine of quinophthalone skeleton sulfonic acid for the pigment dispersion (D-1) of embodiment 1 compared with embodiment 1, CR and viscosity are better.
On the other hand, comparative example 1 tackify significantly that the average primary particle diameter of pigment particles is 15nm.The average primary particle diameter of pigment particles is that in the aspect ratio of comparative example 2, the pigment particles of the 95nm comparative example 3 that is 1: 4.5, CR is variation greatly.
In addition, the amine value of resin type spreading agent be less than the pigment dispersion (D-13) of the comparative example 5 of 10mgKOH/g, for the pigment dispersion (D-12) of more than 99mgKOH/g comparative example 4 be high viscosity, especially, the CR of pigment dispersion (D-13) that is less than the comparative example 5 of 10mgKOH/g is also low, uses the viscosity of pigment dispersion (D-14) of the comparative example 6 of the spreading agent of random high.
Table 6
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 the pigment of 1: 1～1: 3.5 that described colorant contains average primary particle diameter, described resin type spreading agent contains acrylic acid series segmented copolymer, described acrylic acid series segmented copolymer is by having the A block of solvophilic and having A-B segmented copolymer or the B-A-B segmented copolymer that the B block of functional group of nitrogen atom forms, and its amine value is scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent, it is low and stable that color composition for color filter of the present invention has all obtained viscosity, also high good result (embodiment 9～14) of OD.
Especially, add pigment dispersion (D-20) viscosity of embodiment 11 of the slaine of quinophthalone skeleton sulfonic acid better for the pigment dispersion (D-18) of embodiment 9.
On the other hand, contain pigment dispersion (D-24) tackify significantly that average primary particle diameter is the comparative example 10 of the pigment particles of 15nm.Containing average primary particle diameter is the OD variation greatly of the pigment dispersion (D-25) of the comparative example 11 of the pigment particles of 100nm.Further containing aspect ratio is the OD variation greatly of the pigment dispersion (D-26) of the comparative example 12 of the pigment particles of 1: 4.0.
In addition, the amine value of resin type spreading agent is less than the pigment dispersion (D-28) of the comparative example 14 of 10mgKOH/g, uprises for the viscosity of the pigment dispersion (D-127) of more than 99mgKOH/g comparative example 13.Especially, the OD of pigment dispersion (D-28) that is less than the comparative example 14 of 10mgKOH/g is also low, uses the viscosity of pigment dispersion (D-29) of the comparative example 15 of the spreading agent of random high.
[embodiment 15]
(photosensitive coloring composition (R-1))
After following potpourri is uniformly mixed, with the filtrator filtration of 1.0 μ m, obtain photosensitive coloring composition (R-1).
(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 chemical company of Xin Zhong village manufactures)
Photoepolymerizationinitiater initiater (" IRGACURE 907 " that Ciba company manufactures): 1.2 parts
Sensitizer (" EAB-F " that hodogaya chemical company manufactures): 0.4 part
Silane coupling agent (" KBM-803 " that chemical industrial company of SHIN-ETSU HANTOTAI manufactures): 0.4 part
Glycol monoethyl ether acetate: 23.2 parts
[embodiment 16～31, comparative example 17～31]
(photosensitive coloring composition (R-2～32))
Except pigment dispersion being become to the kind and use level of the pigment dispersion shown in table 7, table 8, similarly obtain photosensitive coloring composition (R-2～32) with photosensitive coloring composition (R-1).In photosensitive coloring composition and used pigment dispersion 1,2, but as the total of pigment dispersion, in whole whole photosensitive coloring compositions, it is 50 parts.
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 optical density (OD) and the developing powder of the photosensitive coloring composition of gained, evaluate by following method.The results are shown in table 9～10.
(viscosity characteristics)
The viscosity of photosensitive coloring composition is used E type viscosity meter (" ELD type viscosity meter " that Dong Ji industry company manufactures) to be determined at the initial viscosity of 25 DEG C.In addition, this pigment dispersion 25g is left standstill after 7 days with air-tight state in glass container, at 40 DEG C, measures viscosity by method similar to the above, as through time viscosity.
Zero: viscosity is less than 4.0mPas
△: viscosity is more than 4.0mPas and is less than 7.0mPas
×: viscosity is more than 7.0mPas
(contrast (CR))
Use spin coater to change the photosensitive coloring composition (R-1～18) of revolution ground coating gained, make dry film thickness reach approximately 2 μ m left and right, make 3 coated substrates.After coating, use hot-air oven dry after 30 minutes at 80 DEG C, measures each thickness and contrast, the contrast (CR) when obtaining thickness and be 1 μ m by linear dependence method from the data of 3.In addition, be divided into 3 grade evaluations according to following benchmark.
Zero: CR is more than 8000
△: CR is more than 6000 and is less than 8000
×: CR is less than 6000
(optical density (OD))
Use spin-coating method on the glass substrate of 100mm × 100mm, to be coated with after the photosensitive coloring composition (R-19～32) of gained, making dry film thickness is the film of 1.0 μ m, heats 20 minutes at 230 DEG C.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 is less than 1.5
×: OD is less than 1.3
(developing powder)
Use spin-coating method to be coated with after photosensitive coloring composition on the glass substrate of 10cm × 10cm, in cleaning oven, at 70 DEG C, heat 15 minutes and except desolventizing, obtain the film of approximately 2 μ m.Then, utilize high-pressure mercury-vapor lamp across mask pattern with 60mJ/cm 2after this base board to explosure, use 0.04 % by weight potassium hydroxide aqueous solution (developer temperatur is 26 DEG C) to carry out the spray development that pressure is 0.25MPa, measure painted film and dissolve until the time (development dissolution time) that substrate surface exposes.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
△: 20 seconds above and be less than 30 seconds
×: more than 30 seconds
Table 9
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 the pigment of 1: 1～1: 3.5 that described colorant contains average primary particle diameter, described resin type spreading agent contains acrylic acid series segmented copolymer, described acrylic acid series segmented copolymer is by having the A block of solvophilic and having A-B segmented copolymer or the B-A-B segmented copolymer that the B block of functional group of nitrogen atom forms, and its amine value is scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent, it is low and stable that color composition for color filter of the present invention has all obtained viscosity, CR is also fast good result (embodiment 15～19 and 23～24) of high and developing powder also.
Wherein, further add CR and the viscosity of photosensitive coloring composition (R-3) of the embodiment 17 of the slaine of quinophthalone skeleton sulfonic acid better for the photosensitive coloring composition (R-1) of embodiment 15, therefore the result for being more preferably.
On the other hand, the average primary particle diameter of pigment particles is that the initial viscosity of photosensitive coloring composition (R-11) of the comparative example 17 of 15nm and 150nm is high, passes in time and tackify significantly.On the other hand, the average primary particle diameter of pigment particles is the CR variation greatly of the 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 the 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 meet the whole of CR, viscosity and developing powder.
Table 10
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 the pigment of 1: 1～1: 3.5 that described colorant contains average primary particle diameter, described resin type spreading agent contains acrylic acid series segmented copolymer, described acrylic acid series segmented copolymer is by having the A block of solvophilic and having A-B segmented copolymer or the B-A-B segmented copolymer that the B block of functional group of nitrogen atom forms, and its amine value is scaled below the above 99mgKOH/g of 10mgKOH/g with effective solid constituent, it is low and stable that color composition for color filter of the present invention has all obtained viscosity, OD is also fast good result (embodiment 25～31) of high and developing powder also.
Wherein, added the viscosity of photosensitive coloring composition (R-21) of the embodiment 27 of the slaine of quinophthalone skeleton sulfonic acid better for the photosensitive coloring composition (R-19) of embodiment 25, therefore the result for being more preferably.
The significantly tackify of photosensitive coloring composition (R-26) of the comparative example 25 that on the other hand, the average primary particle diameter of pigment particles is 15nm.The average primary particle diameter of pigment particles is the OD variation greatly of the photosensitive coloring composition (R-27) of the comparative example 26 of 100nm.The OD variation greatly of the photosensitive coloring composition (R-28) of the comparative example 27 that further, the aspect ratio of pigment particles is 1: 4.0.
In addition, the amine value of resin type spreading agent be less than the photosensitive coloring composition (R-30) of the comparative example 29 of 10mgKOH/g, for the viscosity of the photosensitive coloring composition (R-29) of more than 99mgKOH/g comparative example 28 high.In addition, the photosensitive coloring composition of comparative example 28 (R-29) is due to high amine value, and therefore developing powder is slow.In addition, the viscosity of the photosensitive coloring composition (R-31) of the comparative example 30 of use random spreading agent is high.
The manufacture > of < color filter
First, 5.0 parts of the totals of the viridine green in photosensitive coloring composition (R-1) and yellow uitramarine are replaced: in black photosensitive colouration composition 1, replacing with carbon is 5.0 parts of black pigments (PBLK-7), in red photosensitive coloring composition 1, replace with C.I. paratonere 254/C.I. paratonere 177=3.0 part/2.0 part, in green photosensitive coloured composition 1, replace with C.I. naphthol green 58/C.I. pigment yellow 150=3.0 part/2.0 part, in blue photosensitive coloring composition 1, replace with 5 parts of C.I. pigment blue 15s: 3, in addition, similarly modulate shades of colour photosensitive coloring composition with photosensitive coloring composition (R-1), thereby obtain black photosensitive colouration composition 1, red photosensitive coloring composition 1, green photosensitive coloured composition 1, blue photosensitive coloring composition 1.
[manufacture of color filter 1]
Use extrusion coater on the glass substrate of 100mm × 100mm, to be coated with the black photosensitive colouration composition 1 that approximately 1.0 μ m are thick, within 20 minutes, remove desolventizing at the baking oven inner dryings of 70 DEG C.Then, use exposure device utilization ultraviolet ray to carry out candy strip exposure.Exposure is made as 100mJ/cm 2.Further utilize the developer solution that comprises aqueous sodium carbonate carry out spray development and remove after unexposed portion, clean with ion exchange water, at 230 DEG C to this base plate heating 20 minutes, thereby form the black matrix of live width approximately 10 μ m.
Then, on the glass substrate that has formed black matrix, be coated with the red photosensitive coloring composition 1 that approximately 2 μ m are thick, within 20 minutes, remove desolventizing at the baking oven inner dryings of 70 DEG C.Then, use exposure device utilization ultraviolet ray to carry out candy strip exposure.Exposure is made as 100mJ/cm 2.Further utilize the developer solution that comprises aqueous sodium carbonate carry out spray development and remove after unexposed portion, clean with ion exchange water, at 230 DEG C to this base plate heating 30 minutes, thereby form the red filter joint of live width approximately 50 μ m.Then, by same operation, use photosensitive coloring composition (R-1) to form green filter joint on the side of red filter joint, then use blue photosensitive coloring composition 1 to form blue electric-wave filter joint, thereby obtain possessing on same glass substrate the color filter 1 of 3 color filter joints.
[manufacture of color filter 2]
Use extrusion coater on the glass substrate of 100mm × 100mm, to be coated with the photosensitive coloring composition (R-24) that approximately 1.0 μ m are thick, within 20 minutes, remove desolventizing at the baking oven inner dryings of 70 DEG C.Then, use exposure device utilization ultraviolet ray to carry out candy strip exposure.Exposure is made as 100mJ/cm 2.Further utilize the developer solution that comprises aqueous sodium carbonate carry out spray development and remove after unexposed portion, clean with ion exchange water, at 230 DEG C to this base plate heating 20 minutes, thereby form the black matrix of live width approximately 10 μ m.
Then, on the glass substrate that has formed black matrix, be coated with the red photosensitive coloring composition 1 that approximately 2 μ m are thick, within 20 minutes, remove desolventizing at the baking oven inner dryings of 70 DEG C.Then, use exposure device utilization ultraviolet ray to carry out candy strip exposure.Exposure is made as 100mJ/cm 2.Further utilize the developer solution that comprises aqueous sodium carbonate carry out spray development and remove after unexposed portion, clean with ion exchange water, at 230 DEG C to this base plate heating 30 minutes, thereby form the red filter joint of live width approximately 50 μ m.Then, by same operation, use green photosensitive coloured composition 1 to form green filter joint on the side of red filter joint, then use blue photosensitive coloring composition 1 to form blue electric-wave filter joint, thereby obtain possessing on same glass substrate the color filter 2 of 3 color filter joints.
In color filter 1,2 owing to all possessing the filter section that formed by color composition for color filter of the present invention and at least one of black matrix, therefore can be in developing procedure not residual residue and form at short notice pattern, again because contrast is high and color reproduction area field width, therefore use the liquid crystal indicator of this color filter can show to have and strengthen and weak chromatic colour.
In addition, although 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 simplifying 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.
First be, that the physics value of black pigment, the structural formula of pigment derivative, the manufacture of black pigment dispersion describe about the modulation, perylene of the acryl resin for embodiment and comparative example.
[modulation of acrylate solution]
In detachable 4 mouthfuls of flasks, be provided with in the reaction vessel of thermometer, cooling tube, nitrogen ingress pipe, stirring apparatus and pack 70.0 parts of cyclohexanone into, be warming up to 80 DEG C, to carrying out in reaction vessel after nitrogen replacement, with buret with within 2 hours, dripping 7.4 parts of 13.3 parts of n-BMAs, 4.6 parts of methacrylic acid-2-hydroxy methacrylates, 4.3 parts of methacrylic acids, p-Cumenylphenol oxirane modification acrylate (" ARONIX M110 " that Toagosei Co., Ltd manufactures), 2, the potpourri that 2 '-azoisobutyronitrile is 0.4 part.After dropping finishes, then continue reaction 3 hours, obtain weight-average molecular weight and be the solution of 26000 acryl resin.Be cooled to after room temperature, the about 2g of sample tree lipoprotein solution, after 20 minutes, measure nonvolatile component at 180 DEG C of heat dryings, in synthetic before resin solution, add methoxy-propyl acetate according to the mode that makes nonvolatile component become 30 % by weight, thus modulation acrylic resin soln.
[perylene is the physics value of black pigment]
Table 1 '
Perylene is black pigment Average primary particle diameter Aspect ratio Shape of particle
Perylene is black pigment 1 ' 30nm 1∶1.5 Spherical
Perylene is black pigment 2 ' 200nm 1∶4.0 Needle-like
Perylene is black pigment 3 ' 200nm 1∶7.5 Sharp-pointed needle-like
Perylene is black pigment 4 ' 100nm 1∶7.5 Sharp-pointed needle-like
Perylene is black pigment 5 ' 100nm 1∶1.5 Spherical
Perylene is black pigment 6 ' 45nm 1∶4.0 Needle-like
Perylene is black pigment 7 ' 15nm 1∶1.5 Spherical
Perylene is black pigment 8 ' 45nm 1∶1.5 Spherical
Perylene is black pigment 1 '
" the Lumogen Black FK4280 " that PeryleneXi black pigment BASF AG manufactures
Perylene is black pigment 2 '
Perylene be black pigment C.I. pigment black 31 (BASF AG manufacture " Paliogen Black S0084 "),
Perylene is black pigment 3 '
Perylene is black pigment C.I. pigment black 32 (" Paliogen Black L0086 " that BASF AG manufactures)
Perylene is black pigment 4 '
" the Lumogen Black FK4281 " that PeryleneXi black pigment BASF AG manufactures
Perylene is black pigment 5 '
Be that 250 parts of 500 parts of black pigment C.I. pigment blacks 31 (BASF AG manufacture " Paliogen Black S0084 "), 2500 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by perylene, mixing 5 hours at 80 DEG C.Then, by the warm water of 5 liters of this mixing thing inputs, limit is heated to 70 DEG C of limits and stirs 1 hour, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, and at 80 DEG C of dry diels, get is black pigment 5 ' Dao perylene.
Perylene is black pigment 6 '
Be that 250 parts of 500 parts of black pigments (BASF AG manufacture " Lumogen Black FK4281 "), 2500 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by perylene, mixing 5 hours at 80 DEG C.Then, by the warm water of 5 liters of this mixing thing inputs, limit is heated to 70 DEG C of limits and stirs 1 hour, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, and at 80 DEG C of dry diels, get is black pigment 6 ' Dao perylene.
Perylene is black pigment 7 '
Be that 250 parts of 500 parts of black pigments (BASF AG manufacture " Lumogen Black FK4281 "), 2500 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by perylene, mixing 12 hours at 40 DEG C.Then, by the warm water of 5 liters of this mixing thing inputs, limit is heated to 70 DEG C of limits and stirs 1 hour, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, and at 80 DEG C of dry diels, get is black pigment 7 ' Dao perylene.
Perylene is black pigment 8 '
Be that 250 parts of 500 parts of black pigment C.I. pigment blacks 32 (BASF AG manufacture " Paliogen Black L0086 "), 2500 parts, sodium chloride and diethylene glycols pack 1 gallon of kneader of stainless steel (aboveground manufacturing company manufactures) into by perylene, mixing 12 hours at 80 DEG C.Then, by the warm water of 5 liters of this mixing thing inputs, limit is heated to 70 DEG C of limits and stirs 1 hour, thereby forms pulpous state, repeatedly filters, washes, and removes after sodium chloride and diethylene glycol, and at 80 DEG C of dry diels, obtaining table 1 ’ perylene is black pigment 8 '.
[structural formula of pigment derivative]
Table 2 '
[making of black pigment dispersion]
(black pigment dispersion 1 ')
After the potpourri of following composition is uniformly mixed, use the zirconium oxide bead that diameter is 0.5mm, disperse after 5 hours with Eiger mill (Eiger Japanese firm manufacture " MINI MODEL M-250MKII "), with the filtrator filtration of 5.0 μ m, thereby make black pigment dispersion 1 '.
Carbon black: 14.4 parts " #45 " (Mitsubishi Chemical's (strain) manufacture)
1 ': 0.6 part of pigment derivative
1 ': 1.5 parts of " BYK-110 " (Bi Ke chemistry Japanese firm manufactures) (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 changing to table 3 ' shown in composition and use level, similarly make black pigment dispersion 2 '～25 ' with black pigment dispersion 1 '.
Table 3 '
About table 3 ' in abbreviation and compound, be expressed as follows.
Pigment
R/B/Y pigment color mixture 1: the black pigment mixing with the weight rate of PR177/PB15:6/PY139=50/40/10
R/B/Y pigment color mixture 2: the black pigment mixing 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 '
Resin type spreading agent
Resin type spreading agent 1 ': acidic resins type spreading agent " BYK-110 " (Bi Ke chemistry Japanese firm manufactures) (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 manufactures) (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 manufactures) (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 manufactures) (nonvolatile component is 60%)
Solvent: cyclohexanone
[embodiment 1 '～22 ', comparison 1 '～11 ']
(black-colored resin composition 1 '～33 ')
By 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 content (%) taking the total weight of light-proofness black pigment (A) as benchmark perylene pigment
Solid constituent weight (%): the solid component concentration in 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 the viscosity of second day of the black-colored resin composition of making, use TVE-20L type viscosity meter (manufacture of Dong Ji industry company) to measure at 25 DEG C, as initial viscosity (η 0:mPas).In addition, as estimation of stability, be similarly determined at 40 DEG C of viscosity (η 7:mPas) of preserving after 7 days, calculate rate of change according to following formula.
Rate of change (%)=at 40 DEG C of viscosity (η 7)/initial viscosities (η 0) × 100 of preserving after 7 days
In addition, rheological parameters' change with time rate is divided into 3 grade evaluations according to following benchmark.
Zero: rheological parameters' change with time rate is less than 110%
△: rheological parameters' change with time rate is more than 110% and is less than 140%
×: rheological parameters' change with time rate is more than 140%
[optical density]
Use spin-coating method is on the glass substrate of 100mm × 100mm after painting black resin combination, and making dry film thickness is the film of 1.0 μ m, heats 20 minutes at 230 DEG C.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 is less than 2.70
×: OD is less than 2.50
[light transmission rate]
Use spin-coating method after painting black pigment dispersion, through the firing process of 20 minutes, is the film of 1.0 μ m thereby make dry film thickness on the glass substrate of 100mm × 100mm at 230 DEG C.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 is less than 30%
×: light transmission rate (wavelength is 1000nm) is less than 15%
Table 5 '
As the light-proofness black pigment in the 2nd embodiment, the black pigment dispersion that contains specified quantitative perylene and be black pigment and carbon black is the dispersion of mobility, excellent in stability.In addition, be made as below 95 % by weight by the ratio that contains that is black pigment by light-proofness black pigment Zhong perylene, thereby show also high good light-proofness of optical density.In addition, the light transmission rate during about 780nm, also all meets the more than 15% of mask alignment when operation needs level.
By pigment derivative is used as to pigment dispersing agent, initial viscosity declines, mobility also can be observed ageing stability when improvement and improves (embodiment 1 '～17 ', 19 '～25 ').In addition, by use pigment derivative and resin type spreading agent simultaneously, thereby show good ageing stability (embodiment 1 '～5 ', 10 '～17 ', 20 '～25 '), while particularly using acidic resins type spreading agent, mobility is more good (embodiment 1 '～5 ', 10 ', 11 ', 13 '～17 ', 20 '～25 ') also.
Light-proofness black pigment Zhong perylene is the ratio of black pigment when few, and the light transmission rate of near infrared region is variation (comparative example 1 ', 9 '～11 ') greatly, and in addition, most cases is the poor result of light-proofness (comparative example 2 ').Outside another, perylene is black pigment while not meeting 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 % by weight, be high viscosity, do not there is the mobility (comparative example 8 ') that is suitable for coating.
While using the combination of organic pigment as colorant, light transmission rate, ageing stability that result is near infrared region are 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 is uniformly mixed, with the filtrator filtration 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 " (manufacture of Qi Ba Japanese firm) of Photoepolymerizationinitiater initiater
Ethene unsaturated compound: 2.00 parts " ARONIX M-402 " (manufacture 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 manufactures) (nonvolatile component is 50 % by 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 '
About table 6 ' in abbreviation and compound, be expressed as follows.
Photoepolymerizationinitiater initiater
Initiating agent 1 ': " IRGACURE OXE-02 " (manufacture of Qi Ba Japanese firm)
Initiating agent 2 ': the material that " IRGACURE 379EG " (manufacture of Qi Ba Japanese firm)/" EAB-F " (manufacture of hodogaya chemical company) formed with 90/10 cooperation
Initiating agent 3: the material that " IRGACURE 379EG " (manufacture of Qi Ba Japanese firm)/" IRGACURE 907 " (manufacture of Qi Ba Japanese firm)/" DETX-S " (Japanese chemical drug company manufacture) formed with 45/45/10 cooperation
Ethene unsaturated compound: " ARONIX M-402 " (manufacture 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 manufactures) (nonvolatile component is 50 % by 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 to be coated with after erosion resistant on the glass substrate of 100mm × 100mm, carry out vacuum drying.Afterwards, use extra-high-pressure mercury vapour lamp with 100mJ/cm 2exposure ultraviolet ray.Then, use aqueous sodium carbonate to carry out after spray development unexposed portion, thereby clean and remove unexposed portion with ion exchange water, at 230 DEG C, heat 20 minutes.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 is less than 2.70
×: OD is less than 2.50
[light transmission rate]
Use spin-coating method to be coated with after erosion resistant on the glass substrate of 100mm × 100mm, through the firing process of 20 minutes, be the film of 1.0 μ m thereby make dry film thickness at 230 DEG C.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 is 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, making thickness after following heating process is the thickness of 1.0 μ m, thereby obtains coated substrates.Then,, after drying under reduced pressure, use extra-high-pressure mercury vapour lamp taking accumulated light as 100mJ/cm 2, illumination is 25mW/cm 2carry out ultraviolet exposure.At 230 DEG C 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, makes and clamps cured coating film and the sample that forms with aluminium electrode.Using electric impedance analyzer (" 1260 type " electric impedance analyzer that Solartron company manufactures), is the mensuration of carrying out the relative dielectric constant of the sample of gained under 100mV at impressed voltage.Relative dielectric constant is according to 3 grade evaluations of following basis point.
Zero: relative dielectric constant is below 8.0
△: relative dielectric constant exceedes 8.0 and be below 9.0
×: relative dielectric constant exceedes 9.0
Table 7 '
As table 7 ' as shown in, contain 78～95 % by weight be black pigment as light-proofness black pigment perylene time, optical density is more than 2.5, in addition, light transmission rate when 780nm is also more than 15%, and relative dielectric constant is also below 9.0, all meet the characteristic that requires of the BM that possess as the TFT colour display device of BOA mode.
Light-proofness black pigment Zhong perylene is that the ratio of black pigment is when few, the light transmission rate of relative dielectric constant and near infrared region is variation (comparative example 12 ') greatly, in addition, most cases is the result (comparative example 13 ') that does not meet light-proofness.
Outside another, perylene is black pigment while not meeting arbitrary value of specific mean grain size and aspect ratio, and result is light-proofness and all poor (comparative example 14 '～18 ') of electrical specification.While using the combination of organic pigment as colorant (comparative example 19 ', 20 '), result is that 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 meet 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 TOHKEMY 2000-162643 is made.
Use possesses the driving substrate of thin film transistor (TFT) (TFT) the mode color liquid crystal display arrangement of the black matrix being formed by the related black-colored resin composition of the 2nd embodiment and makes.
First, on the surface on (the 1st) glass substrate, by TFT and transparent ITO electrode layer pattern, then form the color filter of RGB thereon.On aforementioned color filter, form the ITO film as pixel electrode, be etched into after the pattern of regulation, between rgb pixel, form black matrix, thereby make array base palte.
On the other hand, on the surface on other (the 2nd) glass substrate, by ITO electrode layer patterning, then form polyimide alignment layers thereon, thereby make counter substrate.
Make array base palte and the counter substrate as above prepared opposed, make electrode layer toward each other, use every pearl the interval of two substrates is kept necessarily carrying out contraposition simultaneously, inject around the mode sealant sealing with peristome with Liquid Residue crystal composite.From peristome injection liquid crystal composite, sealed open portion.Thereby 3 wavelength CCFL combination of light sources of the liquid crystal indicator of making like this and back light unit are made to colour display device.
Its result is: the colour display device of the driving substrate 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 because light-proofness is all excellent, therefore the display comparison degree excellence of color liquid crystal display arrangement, in addition due to low-k characteristic, therefore very little to the harmful effect of the chaotic such electrical specification of the orientation of liquid crystal, and due to the light transmission rate excellence of near infrared region, therefore also can carry out mask alignment operation.
Next,, about the 3rd embodiment, describe with embodiment and comparative example.
[modulation of acryl resin]
In reaction vessel, pack 800.0 parts of cyclohexanone into, nitrogen is injected to container and be heated to 100 DEG C, synthermal lower use 1 hour drips the potpourri of 10.0 parts of 60.0 parts of methacrylic acids, 65.0 parts of butyl methacrylates, 65.0 parts of methyl methacrylates, 60.0 parts of styrene and azoisobutyronitriles, and then react after 3 hours at 100 DEG C, add the solution that dissolves 2.0 parts of gained of azoisobutyronitrile with 50.0 parts of cyclohexanone, and then continue reaction 1 hour at 100 DEG C, thereby synthetic resin solution.Be cooled to after room temperature, the about 2.0g of sample tree lipoprotein solution, after 20 minutes, measure nonvolatile component at 180 DEG C of heat dryings, in synthetic before resin solution, add cyclohexanone according to the mode that makes nonvolatile component become 20 % by weight, thus modulation acrylic resin soln.In addition, the weight-average molecular weight of acrylic resin soln is 40000.
[perylene is black pigment]
Prepare with table 1 ' shown in perylene be that black pigment 1 '～8 ' Tong Yang perylene is 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 is uniformly mixed, use the zirconium oxide bead that diameter is 0.5mm, disperse after 5 hours with Eiger mill (Eiger Japanese firm manufacture " MINI MODEL M-250MKII "), with the filtrator filtration of 5.0 μ m, thereby 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 Japanese firms of resin type spreading agent manufacture (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 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 recorded is identical.
[comparative example 3 "]
After following potpourri is uniformly mixed, use the zirconium oxide bead that diameter is 0.5mm, after 5 hours, with the filtrator filtration of 5.0 μ m, thereby make black pigment dispersion 14 with Eigermill (" MINI MODEL M-250MKII " that Eiger Japanese firm manufactures) dispersion ".
Carbon black (Mitsubishi Chemical's (strain) manufactures #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 Japanese firms of resin type spreading agent manufacture (acid number is 53mgKOH/g)
Solvent: cyclohexanone: 57.8 parts
[the viscosity evaluation of black pigment dispersion and rheological parameters' change with time rate]
With regard to the viscosity of black pigment dispersion, at 25 DEG C of pigment dispersion modulation same day, the viscosity (initial viscosity) while using E type viscosity meter (TVE-20L type viscosity meter (manufactures of Dong Ji industry company)) mensuration revolution to be 20rpm.
Then, for counting the same day from black pigment dispersion modulation, at 40 DEG C, place the black pigment dispersion of 7 days, will make specimen temperature get back to after 25 DEG C, according to above-mentioned viscosity measurement measure through time viscosity, obtain rheological parameters' change with time rate by following formula.
Rheological parameters' change with time rate (%)=(through time viscosity)/(initial viscosity) × 100
In addition, rheological parameters' change with time rate is according to 3 grade evaluations of following basis point.
The results are shown in table 4 ".
Zero: rheological parameters' change with time rate is less than 110%
△: rheological parameters' change with time rate is more than 110% and is less than 140%
×: rheological parameters' change with time rate is more than 140%
[optical density]
Use spin-coating method after painting black pigment dispersion, to carry out vacuum drying on the glass substrate of 100mm × 100mm, at 230 DEG C, heat 20 minutes.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]
Use spin-coating method after painting black pigment dispersion, through the firing process of 20 minutes, is the film of 1.0 μ m thereby make dry film thickness on the glass substrate of 100mm × 100mm at 230 DEG C.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 is less than 80%
×: transmitance (wavelength is 1000nm) is less than 60%
Table 4 "
As the light-proofness black pigment of feature of the present invention, be that to have particular value perylene be that mobility, the stability of the black pigment dispersion that forms of black pigment, pigment dispersing agent, resin and solvent is all excellent to 50nm aspect ratio following and pigment particles by average primary particle diameter, and OD value is high, show good light-proofness, transmitance is excellent (embodiment 1 "～13 ") also.
In addition, by use pigment derivative and resin type spreading agent simultaneously, thereby show good ageing stability (embodiment 1 "～4 ", 9 "～13 "), especially, more good while using acidic resins types spreading agent (embodiment 1 "～4 ", 9 ", 10 ", 12 ", 13 ").
[embodiment 14 "]
(erosion resistant 1 ")
Then, after the potpourri of following composition is uniformly 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 Qi Ba Japanese firm manufactures)
Ethene unsaturated compound: 2.9 parts (" ARONIX M-402 " that East Asia Synesis Company manufactures)
Surface conditioner: 1.0 parts (2 parts of solution that form of " BYK-330 " (nonvolatile component is 50 % by weight) of manufacturing with 98 parts of dilution Bi Ke chemistry Japanese firms of propylene glycol monomethyl ether acetate)
Solvent: cyclohexanone: 30.5 parts
[embodiment 15 "～26 ", comparative example 10 "～18 "]
[erosion resistant 2 "～22 "]
Except changing to table 5 " shown in black pigment dispersion, with embodiment 14 " (erosion resistant 1 ") similarly make erosion resistant 2 "～22 ".
[optical density]
Use spin-coating method to be coated with after 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, using aqueous sodium carbonate to carry out after spray development unexposed portion, thereby clean and remove unexposed portion with ion exchange water, heat 20 minutes at 230 DEG C, 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]
Use spin-coating method to be coated with after erosion resistant on the glass substrate of 100mm × 100mm, through the firing process of 20 minutes, be the film of 1.0 μ m thereby make dry film thickness at 230 DEG C.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 is 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, making thickness after following heating process is the thickness of 1.0 μ m, thereby obtains coated substrates.Then,, after drying under reduced pressure, use extra-high-pressure mercury vapour lamp taking accumulated light as 100mJ/cm 2, illumination is 25mW/cm 2carry out ultraviolet exposure.At 230 DEG C 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, makes the sample with aluminium electrode clamping cured coating film.Using electric impedance analyzer (" 1260 type " electric impedance analyzer that Solartron company manufactures), is the relative dielectric constant of sample and the mensuration of tan δ of carrying out gained under 100mV at impressed voltage.Relative dielectric constant is according to 3 grade evaluations of following basis point.
Zero: relative dielectric constant is less than 3.5
△: relative dielectric constant is more than 3.5, below 4.5
×: relative dielectric constant exceedes 4.5
Tan δ is according to 3 grade evaluations of following basis point.
Zero: tan δ is less than 0.1
△: tan δ is more than 0.1 and is less than 0.2
×: tan δ is more than 0.2
The results are shown in table 5 ".
Table 5 "
As table 5 " as shown in; used have average primary particle diameter for 50nm is following, aspect ratio is that the crystal particles perylene of 1: 1～1: 2 is that black pigment, pigment dispersing agent, resin and solvent are as the result of the related erosion resistant of the 3rd embodiment of light-proofness black pigment: optical density is high, light-proofness is excellent, low-k, and also excellent (embodiment 14 "～26 ") of the transmitance of near infrared region.On the other hand, when perylene pigment does not meet arbitrary value of specific mean grain size and aspect ratio, result is: not only optical density is low, light-proofness is poor, and electrical specification is poor (comparative example 13 "～17 ") also.
Wherein, use has the precursor skeleton of organic pigment and the pigment derivative of alkali subtituent and shows the result that electrical specification is more excellent (embodiment 24 ") as the erosion resistant of pigment dispersing agent, that the tan δ of the precursor skeleton Wei dioxazine of organic pigment or the erosion resistant of diketopyrrolopyrrolecocrystals also becomes is better (embodiment 19 ", 21 "～23 ").
In addition, used pigment derivative and acid number is that the tan δ of the erosion resistant of the acidic resins type spreading agent of 100～200mgKOH/g becomes better simultaneously, initial viscosity also can be suppressed to one low-level, stability is good (embodiment 22 ") also.
In addition, form the comparative example 10 of black-colored resin composition for the mixing of the organic pigment by as light-proofness black pigment ", 11 " (erosion resistant 12 ", 13 "), relative dielectric constant and transmitance are realistic scale, but optical density is low, and using 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.
Outside another, be the comparative example 13 of mineral black arbitrary value of not meeting specific mean grain size and aspect ratio with regard to perylene "～17 " (erosion resistant 15 "～19 ") with regard to, 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 meet 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 TOHKEMY 2000-162643 is made.
Use possesses the driving substrate of thin film transistor (TFT) (TFT) the mode color liquid crystal display arrangement of the black matrix being formed by the related black-colored resin composition of the 3rd embodiment and makes.
First, on the surface on (the 1st) glass substrate, by TFT and transparent ITO electrode layer pattern, then form the color filter of RGB thereon.On aforementioned color filter, form the ITO film as pixel electrode, be etched into after the pattern of regulation, between rgb pixel, form black matrix, thereby make array base palte.
On the other hand, on the surface on other (the 2nd) glass substrate, by transparent ITO electrode layer pattern, then form polyimide alignment layers thereon, thereby make counter substrate.
Make array base palte and the counter substrate arranged opposite as above prepared, make electrode layer toward each other, use every pearl the interval of two substrates is kept necessarily carrying out contraposition simultaneously, inject around the mode sealant sealing with peristome with Liquid Residue crystal composite.From peristome injection liquid crystal composite, sealed open portion.Thereby 3 wavelength CCFL combination of light sources of the liquid crystal indicator of making like this and back light unit are made to colour display device.
Its result is: the colour display device of the driving substrate 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 because light-proofness is all excellent, therefore the display comparison degree excellence of colour display device, in addition due to low-k characteristic, therefore the harmful effect of the electrical specification such as orientation confusion to liquid crystal is very little, and due to the transmitance excellence of near infrared region, therefore also can carry out mask alignment operation.

Claims (17)

1. a 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, described light-proofness black pigment by average primary particle diameter for 50nm is following and the aspect ratio of pigment primary particle for 1:1～1:2 perylene be black pigment and carbon black form Suo Shu perylene be black pigment content taking the total weight of light-proofness black pigment during as benchmark as 78～95 % by weight, and solid component concentration is more than 5 % by weight and is less than 40 % by weight
Described pigment dispersing agent is to comprise the pigment dispersing agent with the precursor skeleton of organic pigment and the pigment derivative of alkali subtituent and acidic resins type spreading agent.
2. black-colored resin composition as claimed in claim 1, is characterized in that, Suo Shu perylene is that the average primary particle diameter of black pigment is 20～45nm.
3. black-colored resin composition as claimed in claim 1, is characterized in that, further contains ethene unsaturated compound and Photoepolymerizationinitiater initiater.
4. a black matrix, is formed by the black-colored resin composition described in any one in claim 1～3.
5. black matrix as claimed in claim 4, is characterized in that, the relative dielectric constant in the time that dry film thickness is 1.0 μ m is below 8.0.
6. black matrix as claimed in claim 4, is characterized in that, the light transmission rate of the wavelength 780nm in the time that dry film thickness is 1.0 μ m is more than 15% and is less than 99%.
7. black matrix as claimed in claim 4, is characterized in that, the optical density in the time that dry film thickness is 1.0 μ m is more than 2.50.
8. a driving substrate for thin film transistor (TFT) mode color liquid crystal display arrangement, is characterized in that, possesses the black matrix described in any one in claim 4～7.
9. a 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, 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 perylene is black pigment, and solid component concentration is that 5 % by weight are above and be less than 40 % by weight, and described pigment dispersing agent is to comprise the pigment dispersing agent with the precursor skeleton of organic pigment and the pigment derivative of alkali subtituent and acidic resins type spreading agent.
10. black-colored resin composition as claimed in claim 9, is characterized in that, Suo Shu perylene is that the average primary particle diameter of black pigment is 20～45nm.
11. black-colored resin compositions as claimed in claim 9, is characterized in that, any in precursor skeleton Wei dioxazine series pigments or the diketopyrrolopyrrolecocrystals series pigments of described organic pigment.
12. black-colored resin compositions as claimed in claim 9, is characterized in that, further contain ethene unsaturated compound and Photoepolymerizationinitiater initiater.
13. 1 kinds of black matrixes, are formed by the black-colored resin composition described in any one in claim 9～12.
14. black matrixes as claimed in claim 13, is characterized in that, the relative dielectric constant in the time that dry film thickness is 1.0 μ m is below 4.5.
15. black matrixes as claimed in claim 13, is characterized in that, the transmitance of the wavelength 1000nm in the time that dry film thickness is 1.0 μ m is more than 60% and is less than 99%.
16. black matrixes as claimed in claim 13, is characterized in that, the optical density in the time that dry film thickness is 1.0 μ m is more than 1.30.
17. a driving substrate for thin film transistor (TFT) mode color liquid crystal display arrangement, is characterized in that, possesses the black matrix described in any one in claim 13～16.
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