CN1329749C - Sensitive black composition, black substrate using same and color filter - Google Patents
Sensitive black composition, black substrate using same and color filter Download PDFInfo
- Publication number
- CN1329749C CN1329749C CNB2004100600327A CN200410060032A CN1329749C CN 1329749 C CN1329749 C CN 1329749C CN B2004100600327 A CNB2004100600327 A CN B2004100600327A CN 200410060032 A CN200410060032 A CN 200410060032A CN 1329749 C CN1329749 C CN 1329749C
- Authority
- CN
- China
- Prior art keywords
- black
- composition
- black matrix
- photosensitive
- pigment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/23—Photochromic filters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
Abstract
The photosensitive black composition contains carbon black having a specific surface area of 50-200 m<2>/g, a dye derivative having a triazine-ring-containing basic substituent represented by formula (where Q is an organic dye residue), and an ethylenically unsaturated compound. The black matrix substrate has a black matrix formed from the photosensitive black composition. The color filter comprises at least two color filter segments other than black on the above black matrix substrate.
Description
Technical field
The present invention relates to employed photosensitive black composition in the manufacturing of black matrix (black matrix) of the color filter that is used in combination with liquid crystal indicator or solid-state imager etc., use the black matrix substrate and the color filter (being also referred to as colored filter, color filter) of said composition.
Background technology
Gap portion between the colour filter zone (filter segment) of the red, green, blue of color filter, in order to improve contrast, common situation is to form the cancellate black pattern that is referred to as black matrix with light-proofness.
In the past, black matrix is to be formed by metallic films such as chromium, nickel, but, attempting using the photosensitive black composition be dispersed with black colorant (black pigment such as mixed carbon black or several pigment and become the colorant of black) to form black matrix from the viewpoint of display quality and cost.The black matrix of using photosensitive black composition to form, the light reflectivity on surface is low, can shorten manufacturing process, and produces large-scale color filter and become possibility, so the black matrix that forms than metal materials such as using chromium has more advantage.
But, using photosensitive black composition to form the occasion of black matrix by photolithography, in order to obtain high light-proofness, need be in composition a large amount of black colorants such as carbon black of blending, but the content of black colorant is high more, be difficult to more black colorant is disperseed equably, the problem of generation is: photosensitive black composition through the time viscosity dispersion stabilization that increases and so on reduce.And along with photonasty increases, sensitivity obviously reduces, even carry out the irradiation of active energy ray, also is difficult to obtain hardened coating film.In order to obtain adequately hardened filming, need more exposure, can produce and cause throughput rate to reduce and the problem of the deterioration of black matrix shape and so on.
In order to solve such problem, proposed to form with blending in the composition with the pigment derivative of following general formula (B) expression (for example can with reference to Japanese kokai publication hei 3-153780 communique) at the color filter that contains black matrix.
General formula (B):
Wherein, Q represent the organic pigment residue,
X
1Expression hydrogen atom, carboxyl or sulfonic group,
X
2Expression is with formula
Or
The substituting group of expression,
I and j represent independently of one another 1～4 integer,
R
1, R
2Represent independently of one another hydrogen atom, maybe can have substituent alkyl, aryl or heterocycle residue,
Y represent hydrogen atom, halogen atom ,-NO
2,-NH
2Or-SO
3H,
K represent 1～4 integer,
N represent 1～4 integer,
A is two valence links with following general formula:
Z
1The expression Direct Bonding ,-CONH-R
3-,-SO
2NH-R
3-or-CH
2NHCOCH
3-R
3-,
Z
2Expression-NH-or-O-,
Z
3Expression hydroxyl, alkoxy or with following general formula:
Or
The substituting group of expression wherein, is 1 occasion at i, Z
3Can be-NH-Z1-Q.
The photosensitive black composition that contains the pigment derivative of representing with general formula (B) shows excellent characteristic at aspects such as thermotolerance, resistances to chemical reagents, but can not satisfy about dispersion stabilization, sensitivity, black matrix shape, the tack (adaptation) to substrate, the desired performance of light-proofness.
Summary of the invention
Therefore, the black matrix substrate and the color filter that the purpose of this invention is to provide a kind of photosensitive black composition, use said composition, described photosensitive black composition shows excellent characteristic at aspects such as thermotolerance, resistances to chemical reagents, and dispersion stabilization, sensitivity, black matrix shape, also good to tack, the light-proofness of substrate.
According to a first aspect of the invention, provide a kind of photosensitive black composition, it contains specific surface area is 50～200m
2The carbon black of/g, with the pigment derivative and the ethylenically unsaturated compounds (being also referred to as the ethene unsaturated compound) of following general formula (A) expression.
General formula (A):
Wherein, Q represent the organic pigment residue,
X represent Direct Bonding ,-CONH-Y
2-,-SO
2NH-Y
2-or-CH
2NHCOCH
2NH-Y
2-,
Y
2Expression can have substituent alkylidene or aryl,
Y
1Expression-NH-or-O-,
Z represents hydroxyl, alkoxy or the substituting group of representing with following general formula (i),
Wherein, be 1 occasion at n, Z can be-NH-X-Q,
Y
3Expression-NH-or-O-,
R
1And R
2Expression independently of one another has the alkyl or the R of substituting group or unsubstituted
1And R
2Mutually bonding with form the heterocycle contain nitrogen-atoms at least,
M represent 1～6 integer,
N represent 1～4 integer,
In photosensitive black composition of the present invention, the uptake of the dibutyl phthalate of carbon black is 120cm preferably
3/ 100g or following, the average primary particle diameter of carbon black is 20～50nm preferably.
Secondly, according to a second aspect of the invention, provide black matrix substrate with the black matrix that forms by photosensitive black composition of the present invention.For the per 1 micron optical density of the dry film thickness of this black matrix be 3.0 or more than.
Moreover, according to a third aspect of the invention we, provide the color filter of going up the colour filter zone that forms black at least two kinds of colors in addition at black matrix substrate of the present invention (substrate).
Embodiment
At first, describe with regard to photosensitive black composition of the present invention.
Photosensitive black composition of the present invention, it contains specific surface area is 50～200m
2The carbon black of/g, with the pigment derivative and the ethylenically unsaturated compounds of following general formula (A) expression.
The carbon black that contains in photosensitive black composition of the present invention is the black pigment with light-proofness, as commercially available carbon black, for example can list: the system #260 of Mitsubishi chemical Co., Ltd, #25, #30, #32, #33, #40, #44, #45, #45L, #47, #50, #52, MA7, MA8, MA11, MA100, MA100R, MA100S, MA230, DEGUSSA corporate system Printex L, Printex P, Printex 30, Printex 35, Printex 40, and Printex 45, and Printex 55, Printex 60, Printex 300, and Printex 350, Special Black 4, SpecialBlack 350, Special Black 550 etc.Carbon black can be used alone, also can mix use two kinds or more than.
As carbon black, the use specific surface area is 50～200m
2/ g's.Its reason is, is using the not enough 50m of specific surface area
2The occasion of the carbon black of/g causes the deterioration of black matrix shape; And using specific surface area greater than 200m
2The occasion of the carbon black of/g is exceedingly adsorbed the pigment derivative by general formula (A) expression on carbon black, in order to show each physical characteristics, need the pigment derivative with general formula (A) expression of blending volume.
And,, consider that the uptake of preferred dibutyl phthalate (below be referred to as DBP) is 120cm as carbon black from the sensitivity aspect
3/ 100g or following person, this DBP uptake is few more good more.The DBP uptake can be measured (with reference to JIS JIS K6217-4) by using the oil suction meter.
In addition, the average primary particle diameter of carbon black 20～50 nanometers preferably.Its reason is, the carbon black of average primary particle diameter less than 20 nanometers is difficult to high concentration ground and disperses, and is difficult to obtain the good photosensitive black composition of ageing stability; And, can cause the deterioration of the shape of black matrix if use than the big carbon black of 50 nanometers.
The content of the carbon black in the photosensitive black composition is divided into benchmark with the solid shape of composition and is preferably 20～70 weight %, more preferably 30～60 weight %.Carbon black contain quantity not sufficient 20 weight % the time, can not obtain sufficient photonasty, and the content of carbon black is difficult to obtain dispersion stabilization when surpassing 70 weight %, causes sensitivity to reduce, and might be difficult to form black matrix.
The pigment derivative that contains in photosensitive black composition is with above-mentioned general formula (A) expression, plays a part to make carbon black to be dispersed in the unsaturated composition of ethylenic.
In general formula (A), Q represents the organic pigment residue.As the organic pigment that organic pigment residue Q is provided, for example can list: the phthalocyanine with phthalocyanine frame is a pigment, quinacridone pigment with quinacridone skeleton, quinacridone quinone with quinacridone quinone skeleton is a pigment, isoindoline ketone with isoindoline ketone skeleton is pigment, Kui phthalein ketone with Kui phthalein ketone skeleton is pigment, diketopyrrolopyrrolecocrystals with diketopyrrolopyrrolecocrystals skeleton is that pigment Ju You perylene skeleton De perylene is a pigment, ペ リ ノ Application with ペ リ ノ Application (perinone) skeleton is a pigment, having the indigo of indigo skeleton is pigment, thioindigo with thioindigo skeleton is a pigment, having dioxazine skeleton De dioxazine is pigment, anthraquinone with anthraquinone skeleton is a pigment, pyrrole anthracene dione pigment with pyrrole amerantrone (ピ ラ Application ス ロ Application) skeleton, anthracene anthrone with anthracene anthrone (ア Application ス ア Application ス ロ Application) skeleton is a pigment, yellow anthrone with yellow anthrone skeleton is a pigment, indanthrene with indanthrene skeleton is a pigment, fused polycyclic system organic pigments such as metal complex system, benzimidazolone with benzimidazolone skeleton is a pigment, insoluble azo is a pigment, the condensation azo is a pigment, the dissolubility azo is a pigment etc.Among these pigments, preferred phthalocyanine is that pigment, anthraquinone are that pigment and benzimidazolone are pigment.
In general formula (A), X represent Direct Bonding ,-CONH-Y
2-,-SO
2NH-Y
2-or-CH
2NHCOCH
2NH-Y
2-, wherein, Y
2Expression can have substituent alkylidene or aryl.Y
2Preferred example comprise that carbon number is 1～6 alkyl, phenyl etc.
In general formula (A), Y
1Expression-NH-or-O-,
In general formula (A), Z represents hydroxyl, alkoxy or the substituting group of representing with general formula (i),
Wherein, be 1 occasion at n, Z can be-NH-X-Q.Wherein, Y
3Expression-NH-or-O-.As the alkoxy of being represented by Z, preferred carbon number is 1～6 alkoxy.
In general formula (A) (also identical in general formula (i)), R
1And R
2Expression independently of one another has the alkyl and the R of substituting group or unsubstituted
1And R
2Bonding is to form the heterocycle that contains nitrogen-atoms at least mutually.As by R
1Or R
2The alkyl of expression, preferred carbon number are 1～6 alkyl.As the substituting group of alkyl, preferred hydroxyl, carbon number are 1～6 alkoxy.As R
1And R
2The heterocycle that mutually combines and form, preferably imidazole radicals, imino group, piperidyl, pyrrolidinyl.
In general formula (A) (also identical in general formula (i)), m represents 1～6 integer.
In general formula (A) (also identical in general formula (i)), n represents 1～4 integer.
As the represented pigment derivative of general formula (A), for example can list: following general formula (1)～(10) represented pigment derivative.
Pigment derivative in general formula (A) can be used alone, also can mix use two kinds or more than.
The content of the pigment derivative that general formula (A) is represented is more preferably 0.5～20 weight portion with respect to 100 weight portion carbon blacks, 0.1～30 weight portion preferably.When the content of pigment derivative is less than 0.1 weight portion, can not bring into play the effect of carbon blacks fully, and when the content of pigment derivative surpassed 30 weight portions, it is unstable that the dispersion of carbon black becomes, and is not preferred therefore.
The ethylenically unsaturated compounds that contains in photosensitive black composition is to have one, the compound of two or more ethylenic unsaturated double-bond, can use monomer, oligomer, photoresist.As monomer, can list: for example 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, cyclohexyl (methyl) acrylate, polyglycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.In addition, as oligomer, can list: epoxy (methyl) acrylate, carbamate (methyl) acrylate, ester (methyl) acrylate etc.As photoresist, can list: in polyester, polyurethane, epoxy resin, acryl resin etc., import those of ethylenic unsaturated double-bond by known method.Ethylenically unsaturated compounds can be used alone, also can mix use two kinds or more than.As ethylenically unsaturated compounds, preferred trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate.Ethylenically unsaturated compounds thinks that preferably 5%～30% ratio of weight that the solid shape of composition is divided uses.
In addition, making the photosensitive black composition sclerosis form the occasion of black matrix, in photosensitive black composition, contain Photoepolymerizationinitiater initiater by the ultraviolet ray irradiation.As Photoepolymerizationinitiater initiater; can use 4-phenoxy group ww-dichloroacetophenone; the 4-tert-butyl group-ww-dichloroacetophenone; the diethoxy acetophenone; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone; the 1-hydroxycyclohexylphenylketone; 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-Ding-acetyl benzene series Photoepolymerizationinitiater initiaters such as 1-ketone; benzoin; benzoin methylether; benzoin ethyl ether; the benzoin isopropyl ether; benzoins such as benzyldimethylketal are Photoepolymerizationinitiater initiater; benzophenone; benzoylbenzoic acid; the benzoylbenzoic acid methyl esters; 4-phenyl benzophenone; hydroxy benzophenone; propylene acidylate benzophenone; 4-benzoyl-4 '-benzophenone such as dimethyl diphenyl sulfide are Photoepolymerizationinitiater initiater; thioxanthones (チ オ キ サ Application ソ Application); the 2-clopenthixal ketone; 2-methyl thioxanthones; isopropyl thioxanthone; 2; thioxanthones such as 4-diisopropyl thioxanthones are Photoepolymerizationinitiater initiater; 2; 4; 6-three chloro-s-triazines; 2-phenyl-4; 6-two (trichloromethyl)-s-triazine; 2-(p-methoxyphenyl)-4; 6-two (trichloromethyl)-s-triazine; 2-(p-methylphenyl)-4; 6-two (trichloromethyl)-s-triazine; 2-piperonyl-4; 6-two (trichloromethyl)-s-triazine; 2; 4-two (trichloromethyl)-6-styryl-s-triazine; 2-(naphthalene-1-acyl group)-4; 6-two (trichloromethyl)-s-triazine; 2-(4-methoxyl-naphthalene-1-acyl group)-4; 6-two (trichloromethyl)-s-triazine; 2; 4-trichloromethyl-(piperonyl)-6-triazine; 2,4-trichloromethyl (4 '-methoxyl-styrene)-triazines such as 6-triazine are Photoepolymerizationinitiater initiater; carbazole is a Photoepolymerizationinitiater initiater; imidazoles is a Photoepolymerizationinitiater initiater.Photoepolymerizationinitiater initiater can use individually, or mix to use two kinds or more than.5～25% the ratio that these Photoepolymerizationinitiater initiaters are preferably weight that the solid shape of composition divides uses.
In addition, in photosensitive black composition, also can contain sensitizer.As sensitizer; can list: for example alpha-acyloxy ester, acylphosphine oxide, aminomethyl phenyl glyoxalic acid, benzyl, 9; 10-phenanthrenequione, camphorquinone (カ Application Off ア one キ ノ Application), EAQ, 4; phenyl-diformyl base benzophenone, 3 between 4 '-diethyl; 3 '; 4,4 '-four (butyl peroxy carbonyl) benzophenone, 4,4 '-diethylamino benzophenone etc.Above-mentioned sensitizer can use individually, or mix to use two kinds or more than.Sensitizer thinks that preferably 3%～60% ratio of the weight of Photoepolymerizationinitiater initiater uses.
In addition, in order to make that photosensitive black composition is an alkali developable, can contain alkali soluble resins in said composition.And, in photosensitive black composition, do not have alkali-soluble resin according to giving purposes such as thermotolerance and tack, can containing together yet with alkali soluble resins.
As alkali soluble resins, can list: (methyl) acrylic copolymer and styrene-maleic anhydride copolymer and have vibrin of carboxyl etc. for example.
According to giving the thermotolerance and the various purposes such as solvent resistance, resistance to chemical reagents of filming, alkali soluble resins also can be used in combination two kinds or more than.
The content of alkali soluble resins is divided into benchmark with the solid shape of photosensitive black composition and is preferably 3～70 weight %, more preferably 5～60 weight %.Alkali soluble resins contain quantity not sufficient 3 weight % the time, alkali-developable step-down, and the content of alkali soluble resins is when surpassing 70 weight %, the hardening of photosensitive black composition and light-proofness step-down when being used to form black matrix.
In order to make carbon black disperse fully, to form black matrix, in photosensitive black composition, can contain solvent with desirable thickness.As solvent, for example can list: cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxyl-2-propyl-acetic acid ester, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, dimethylbenzene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, methyl alcohol, ethanol, isopropyl alcohol, butanols, isobutyl ketone, oil series solvent etc.These solvents use separately, perhaps mix and use.Solvent thinks that preferably the ratio of 60～95 weight % of photosensitive black composition total amount uses.
In photosensitive black composition,, can add chain-transferring agent, surfactant, silane coupling agent, other adjuvant etc. in order to improve purposes such as coating (coating), sensitivity, tack.
By mixed carbon black, with the pigment derivative shown in the general formula (A), ethylenically unsaturated compounds and the Photoepolymerizationinitiater initiater, alkali soluble resins, solvent and other adjuvant that use as required, use various diverting devices such as three roller mixing rolls, two roller mixing rolls, sand mill, kneader and second reduction machine to disperse and can make photosensitive black composition.
For photosensitive black composition, preferably, by means such as centrifuging, sintered filter, film filters, remove in the photosensitive black composition 5 microns or above oversize grain, preferred 1 micron or above oversize grain, be more preferably 0.5 micron or above oversize grain and the dust of sneaking into.
Describe with regard to black matrix substrate below.
Black matrix substrate is to make by following step: be coated with after coating processes such as method (slit coating), the rolling method coating photosensitive black compositions by spin-coating method, seam on transparency carriers such as glass plate, via photomask from composition coated face side irradiation active energy ray, be immersed in solvent or the alkaline developer or by spraying developer solutions such as sprayings, remove not that illuminated portion is unhardened part, develop, form the black matrix of required form.
The scope of preferably 0.2～5 micron of the thickness of photosensitive black composition when dry () more preferably is easy to obtain 0.5～2 micron scope of the balance of coating and light-proofness.
From having the viewpoint of high light-proofness, the per 1 micron optical density of the dry film thickness of black matrix be preferably 3.0 or more than.Optical density is high more good more, but be ultraviolet ray at active energy ray, during visible light, be difficult to obtain hardened coating film, so optical density preferably roughly be 4.5 or below.
As alkaline-based developer, use the aqueous solution of sodium carbonate, NaOH etc., also can use organic bases such as dimethyl benzylamine, triethanolamine.And, in developer solution, also can add defoamer or surfactant.
In addition, in order to improve the exposure sensitivity of active energy ray, also can be after coating photosensitive black composition and drying, be coated with water-soluble or alkali soluble resins for example polyvinyl alcohol (PVA) or water soluble acrylic resin etc. and dry, after formation prevents from produce to stop the film of polymerization by oxygen, from composition coated face side irradiation active energy ray.
As active energy ray, can use the visible light of electronics line, ultraviolet ray, 400～500 nanometers.Line source for the electronics line that shines from composition coated face side can use thermionic emission rifle, field emission rifle etc.In addition, the line source (light source) for the ultraviolet ray and the visible light of 400～500 nanometers for example can use high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, sow lamp, xenon lamp, carbon arc lamp etc.Specifically, as pointolite, have the viewpoint of stability from making briliancy, majority uses extra-high-pressure mercury vapour lamps, xenon mercury vapor lamps.When the line amount from the active energy ray of composition coated face side irradiation is can in time be set in the scope of 5～1000mJ, the scope of the 50～300mJ that is easy to manage on the engineering preferably.
At last, describe with regard to color filter.
Color filter is on above-mentioned black matrix substrate, forms the colour filter zone of black at least two kinds of colors in addition.The color in colour filter zone is about 2～6 looks that can select among blueness, green, redness, cyan, yellow, magneta colour (magneta), orange, the purple etc.With the color of colour system, can form the different colour filter zone of concentration.
Method as form the colour filter zone on black matrix substrate can list: the photolithography of intaglio offset print process, driography print process, silk screen print method, use solvent develop type or the painted resist of alkali developable, the electrophoresis by colloidal particle electro-deposition on the nesa coating form coloured material electrodeposition process, make preformed colour filter area level on the surface at transfer film be transferred to transfer printing on the black matrix substrate etc.
Because print process only by repeat print and dry just can patterning, print process as manufacturing method of color filter be cheaply and the property produced in batches good.In addition, with the development of printing technology, can carry out printing high dimensional accuracy and fine pattern smoothness.In the occasion of making color filter by print process, the control of the flowability of the printing ink on the printing machine is important, also can adjust ink viscosity by spreading agent or extender pigment.
Use the photolithography of solvent develop type or the painted resist of alkali developable to be, on black matrix substrate, be coated with painted resist by coating processes such as rotary coating, slot coated, roller coat, secondly carry out ultraviolet exposure via photomask, form after the required pattern with unexposed of solvent or alkaline developer flushing, other color is repeated same operation and makes the method for color filter.This manufacture method can be made than the higher color filter of above-mentioned print process precision.
Painted resist (coloring resist) is, replaces the black pigment that contains in photosensitive black composition of the present invention, and the resist that can use the colorant of required color to be prepared from can contain the pigment derivative shown in the general formula (A).As colorant, can use the good colorant of various tolerances, but, especially preferably use organic pigment from looking down upon greatly of light absorption energy from the preferred use pigment of the viewpoint of photostability, thermotolerance and solvent resistance.Below, show the concrete example of representational pigment with color index (CI).
As the colorant of yellow, can list: Pigment Yellow 12,13,14,20, and 24,83,86,93,94,109,110,117,125,137,138,139,147,148,153,154,166,173 etc.
As orange colorant, can list: Pigment Orange 13,31,36,38, and 40,42,43,51,55,59,61,64,65 etc.
As the colorant of red and magneta colour, can list: Pigment Red 9,97,122,123, and 144,149,166,168,177,190,192,215,216,224,254,255 etc.
As the colorant of purple, can list: Pigment Violet 19,23,29,32, and 33,36,37,38 etc.
6 etc.), 21,22,60,64 etc. colorant as blue and cyan can list: Pigment Blue 15 (15,15: 1,15: 2,15: 3,15: 4,15:.
As the colorant of green, can list Pigment Green 7,10,36,47 etc.
These colorants can be used in combination two kinds or above to obtain required color.
Below, based on embodiment the present invention is described, but the present invention is not restricted to this.In addition, among the following embodiment and comparative example, " part " expression weight portion, " % " expression weight %.
(preparation of acrylic resin soln)
800 parts of cyclohexanone are added in the reaction vessel, one side nitrogen injection in reaction vessel, be heated to 100 ℃ on one side, under this temperature, dripping by 60.0 parts of methacrylic acids, 65.0 parts of butyl methacrylates, 65.0 parts of methyl methacrylates, 60.0 parts of styrene and 10.0 parts of potpourris that azoisobutyronitrile is formed within an hour, further after 100 ℃ are reacted 3 hours down, add 2.0 parts of azoisobutyronitriles and be dissolved in the potpourri of gained in 50 parts of cyclohexanone, further continue reaction 1 hour down at 100 ℃, thus synthetic resin solution.Be cooled to after the room temperature, extract about 2 gram resin solutions,, measure nonvolatile component 180 ℃ of following heat dryings 20 minutes, formerly the addition of cyclohexanone is to make that nonvolatile component is 20% in the He Cheng resin solution, thereby is prepared into required acrylate resin solution.In addition, the weight-average molecular weight of acrylate resin is 40000.
(preparation of carbon black dispersion)
The carbon black put down in writing in following embodiment and the comparative example and pigment derivative are mixed equably with 24 parts of above-mentioned acrylate resin solution and 40 parts of cyclohexanone, to adopt diameter be 1 millimeter beaded glass, disperseed 5 hours with sand mill after, make carbon black dispersion.
The physics value of employed carbon black is shown in Table 1 in embodiment and the comparative example.
Table 1
| Carbon black | Average primary particle diameter | DBP uptake (cm 3/100g) | Specific surface area (m 2/g) |
| #40 | 24nm | 110 | 115 |
| #260 | 40nm | 74 | 79 |
| MA77 | 23nm | 68 | 130 |
| Block ラ Star Network パ one Le ズ 800 | 17nm | 68 | 210 |
| MONARCH?120 | 75nm | 71 | 25 |
And the pigment derivative that will use in following embodiment and comparative example is shown in as follows.
Pigment derivative 1.
Pigment derivative 2.
(CuPc: the copper phthalocyanine residue)
Pigment derivative 3.
Embodiment 1
10.0 parts of carbon blacks (Mitsubishi Chemical Ind's system " #40 ")
1. 0.5 part of pigment derivative
Embodiment 2
8.0 parts of carbon blacks (Mitsubishi Chemical Ind's system " #260 ")
2. 0.3 part of pigment derivative
Embodiment 3
12.0 parts of carbon blacks (Mitsubishi Chemical Ind's system " MA77 ")
3. 1.0 parts of pigment derivatives
Comparative example 1
8.0 parts of carbon blacks (CABOT corporate system " Block ラ Star Network パ one Le ズ 800 ")
1. 0.2 part of pigment derivative
Comparative example 2
10.0 parts of carbon blacks (CABOT corporate system " MONARCH 120 ")
2. 0.8 part of pigment derivative
The ageing stability evaluation of＜carbon black dispersion 〉
Viscosity after the dispersion of black dispersion just the finished viscosity of preserving after 7 days that coexists 40 ℃ compares, and estimates ageing stability.The results are shown in the table 2.
The preparation of＜photosensitive black composition 〉
After will mixing equably by the potpourri that 60 parts of carbon black dispersion, 4.3 part of three acrylic acid (trihydroxy methyl third) ester (Xin Zhong village chemistry society's system " NK エ ス テ Le ATMPT "), 1.4 parts of Photoepolymerizationinitiater initiaters (Ciba Geigy corporate system " Irgacure 907 "), 0.2 part of sensitizer (protecting native ケ paddy chemistry society's system " EAB-F ") and 21.6 parts of cyclohexanone are formed, be prepared into photosensitive black composition with 1 micron filtrator filtration.To the photosensitive black composition that obtains, estimate sensitivity, black matrix shape, glass attachment, optical density with following method.The result is recorded in the table 2 in the lump.
[sensitivity]
By spin-coating method application photosensitive black composition on the glass substrate of 10cm * 10cm, afterwards by being 1 micron filming to make dry film thickness in 15 minutes 70 ℃ of dryings.Then, use extra-high-pressure mercury vapour lamp,, use 100mJ/cm via photomask
2Ultraviolet exposure.Then, use aqueous sodium carbonate spraying unexposed portion to develop, afterwards with the ion-exchange water washing to remove unexposed portion, the thickness after the development of mensuration exposed portion.The result is recorded in the table 2 in the lump.
[black matrix shape]
Make black matrix substrate with said method.Observe by optical microscope and to estimate the linear good of the black matrix shape that forms at exposed portion or not.The result is recorded in the table 2 in the lump.
[glass attachment]
By said method photosensitive black composition is coated with and is contained on the glass substrate, use extra-high-pressure mercury vapour lamp,, use 300mJ/cm via photomask
2Ultraviolet exposure.Then, use aqueous sodium carbonate spraying unexposed portion to develop, remove unexposed portion with the ion-exchange water washing afterwards, 230 ℃ of heating 1 hour.Then, estimate glass attachment, calculate the number of peeling off in 100 basal disc orders based on the basal disc order tack test method of JIS K5400.The result is recorded in the table 2 in the lump.
[optical density]
By said method with photosensitive black composition be coated be contained on the glass substrate after, 230 ℃ the heating 1 hour.Measure the optical density (OD) of the photosensitive black composition application substrate obtain like this with マ Network ベ ス densimeter (GRETAG D200-II), try to achieve thickness and be 1.0 microns optical density (OD).The result is recorded in the table 2 in the lump.
Table 2
| Carbon black dispersion | The ageing stability of carbon black dispersion | Sensitivity | The black matrix shape | Glass attachment | Optical density |
| Embodiment 1 | ○ | △ | ○ | ○ | 3.6/ micron |
| Embodiment 2 | ○ | ○ | △ | ○ | 3.6/ micron |
| Embodiment 3 | ○ | ○ | ○ | ○ | 3.8/ micron |
| Comparative example 1 | × | × | × | × | 2.9/ micron |
| Comparative example 2 | △ | × | × | × | 3.5/ micron |
In table 2,
Ageing stability: zero: viscosity＜1.3 of the viscosity after 40 ℃ are preserved 7 days/after just having made
△: viscosity＜1.8 of 1.3≤viscosity after 40 ℃ are preserved 7 days/after just having made
*: viscosity 〉=1.8 of the viscosity after 40 ℃ are preserved 7 days/after just having made
Sensitivity: zero: thickness 〉=0.95 micron
△: 0.90 micron≤thickness＜0.95 micron
*: thickness＜0.90 micron
Black matrix shape: zero: rectilinearity is good
△: local rectilinearity is good
*: rectilinearity is bad
Glass attachment: zero: the basal disc purpose is peeled off number＜3
△: 3≤basal disc purpose is peeled off number＜10
*: the basal disc purpose is peeled off number 〉=10
As shown in table 2, be 50～200m not using specific surface area
2The occasion of the carbon black of/g can not get ageing stability, the sensitivity of carbon black dispersion, causes the shape of black matrix bad, can not get glass attachment.Relative therewith, be 50～200m using specific surface area
2The occasion of the carbon black of/g, the ageing stability of carbon black dispersion is good, sensitivity is good, and black matrix shape, glass attachment are good.
As noted above, according to the present invention, can be with high-concentration stable ground carbon blacks.And, photosensitive black composition exhibiting excellent stability with time of the present invention, reached high sensitivityization; By photosensitive black composition of the present invention, black matrix shape, glass attachment, optical density are also good, obtain having the black matrix substrate of desired performance when constituting black matrix.
Claims (8)
1, a kind of photosensitive black composition, it contains:
(a) specific surface area is 50～200m
2/ g and average primary particle diameter are the carbon black of 20～50nm, and wherein the content ratio of this carbon black is, are that benchmark is 20～70 weight % with total shape branch weight admittedly of described composition,
(b) pigment derivative of representing with following general formula (A),
Wherein, Q represent the organic pigment residue,
X represent Direct Bonding ,-CONH-Y
2-,-SO
2NH-Y
2-or-CH
2NHCOCH
2NH-Y
2-,
Y
2Expression can have substituent alkylidene or aryl,
Y
1Expression-NH-or-O-,
Z represents hydroxyl, alkoxy or the substituting group of representing with following general formula (i),
Wherein, Y
3Expression-NH-or-O-,
R
1And R
2Expression independently of one another has the alkyl or the R of substituting group or unsubstituted
1And R
2Mutually bonding with form the heterocycle contain nitrogen-atoms at least,
M represent 1～6 integer,
N represents 1～4 integer, and
(c) ethylenically unsaturated compounds.
2, photosensitive black composition according to claim 1, the uptake of the dibutyl phthalate of wherein said carbon black is 120cm
3/ 100g or following.
3, photosensitive black composition according to claim 1, wherein the n in general formula (A) is 1 occasion, Z is-NH-X-Q.
4, photosensitive black composition according to claim 1, the content ratio of the pigment derivative that wherein said general formula (A) is represented are to be 0.1～30 weight portion with respect to 100 weight portion carbon blacks.
5, photosensitive black composition according to claim 4, wherein said ethylenically unsaturated compounds think that 5%～30% ratio of weight that the solid shape of composition is divided contains.
6, a kind of black matrix substrate, it has the black matrix that is formed by each described photosensitive black composition of claim 1 to 5.
7, black matrix substrate according to claim 6, wherein the per 1 micron optical density of the dry film thickness of black matrix be 3.0 or more than.
8, on the described black matrix substrate of claim 6, form the color filter in the colour filter zone of black at least two kinds of colors in addition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003176274A JP4601267B2 (en) | 2003-06-20 | 2003-06-20 | Photosensitive black composition, black matrix substrate and color filter using the same |
| JP176274/2003 | 2003-06-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1573369A CN1573369A (en) | 2005-02-02 |
| CN1329749C true CN1329749C (en) | 2007-08-01 |
Family
ID=34099206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100600327A Expired - Fee Related CN1329749C (en) | 2003-06-20 | 2004-06-21 | Sensitive black composition, black substrate using same and color filter |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4601267B2 (en) |
| KR (1) | KR101072425B1 (en) |
| CN (1) | CN1329749C (en) |
| TW (1) | TWI287694B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5489386B2 (en) * | 2005-03-03 | 2014-05-14 | 富士フイルム株式会社 | Photocurable composition for antireflection film of solid-state image sensor, antireflection film for solid-state image sensor using the same, method for producing anti-reflection film for solid-state image sensor, and solid-state image sensor |
| JP2006301101A (en) * | 2005-04-18 | 2006-11-02 | Fujifilm Electronic Materials Co Ltd | Light-shielding/antireflection multilayer film, method for forming the same, solid-state imaging element having the same, and manufacturing method therefor |
| KR101276737B1 (en) * | 2005-11-30 | 2013-06-19 | 토요잉크Sc홀딩스주식회사 | Black composition and production method thereof |
| JP5151126B2 (en) * | 2005-11-30 | 2013-02-27 | 東洋インキＳｃホールディングス株式会社 | Black composition and color filter using the same |
| JP4848936B2 (en) * | 2006-01-27 | 2011-12-28 | 東洋インキＳｃホールディングス株式会社 | Photosensitive black composition and color filter |
| JP5115046B2 (en) | 2007-06-14 | 2013-01-09 | 東洋インキＳｃホールディングス株式会社 | Photosensitive black composition and color filter |
| KR101032275B1 (en) * | 2007-11-08 | 2011-05-06 | 주식회사 엘지화학 | Colored dispersions, photoresist resin composition and black matrix |
| CN102099947A (en) * | 2008-06-04 | 2011-06-15 | 东洋油墨制造股份有限公司 | Composition for battery |
| JP5991040B2 (en) * | 2012-06-22 | 2016-09-14 | 凸版印刷株式会社 | Black photosensitive resin composition, black matrix and color filter |
| KR101907220B1 (en) * | 2013-06-20 | 2018-10-11 | 동우 화인켐 주식회사 | Photosensitive resin composition for black matrix, black matrix by the composition and display device including the black matrix |
| JP6217404B2 (en) * | 2014-01-17 | 2017-10-25 | 東洋インキＳｃホールディングス株式会社 | Black composition and black coating film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03153780A (en) * | 1989-11-10 | 1991-07-01 | Toyo Ink Mfg Co Ltd | Colored composition for color filter |
| CN1165304A (en) * | 1995-04-28 | 1997-11-19 | 东丽株式会社 | Resin black matrix for liquid crystal display device |
| WO2002093255A2 (en) * | 2001-05-15 | 2002-11-21 | Showa Denko K. K. | Photosensitive coloring compositon, color filter using the compositon and method of producing the same |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60250052A (en) * | 1984-05-28 | 1985-12-10 | Mitsubishi Chem Ind Ltd | Colorant for resin |
| JPH01247467A (en) * | 1988-03-30 | 1989-10-03 | Toyo Ink Mfg Co Ltd | Pigment dispersant and pigment composition |
| JPH07100764B2 (en) * | 1990-07-03 | 1995-11-01 | 宇部興産株式会社 | Black photocurable polymer composition and method for forming black photocurable film |
| JP3132314B2 (en) * | 1994-06-03 | 2001-02-05 | 東洋インキ製造株式会社 | Method for producing aqueous pigment dispersion |
| JP3674086B2 (en) * | 1995-07-03 | 2005-07-20 | 三菱化学株式会社 | Black matrix for color filter and resist composition for black matrix |
| JP3268748B2 (en) * | 1996-12-16 | 2002-03-25 | 大日精化工業株式会社 | Pigment dispersant, pigment dispersion, pigment dispersion for color filter |
| JP3998304B2 (en) * | 1997-02-28 | 2007-10-24 | 三菱化学株式会社 | Color filter |
| JP2000292615A (en) * | 1999-04-07 | 2000-10-20 | Mitsubishi Chemicals Corp | Color filter and liquid crystal display using it |
| JP2002287335A (en) * | 2001-03-28 | 2002-10-03 | Fuji Photo Film Co Ltd | Method for forming planographic printing plate |
| JP3878451B2 (en) * | 2001-10-22 | 2007-02-07 | 富士フイルムホールディングス株式会社 | Photosensitive resin transfer material, image forming method, color filter and manufacturing method thereof, photomask and manufacturing method thereof |
| KR100481014B1 (en) * | 2002-10-04 | 2005-04-07 | 주식회사 동진쎄미켐 | Photosensitive resin composition using photopolymer |
-
2003
- 2003-06-20 JP JP2003176274A patent/JP4601267B2/en not_active Expired - Fee Related
-
2004
- 2004-06-16 KR KR1020040044347A patent/KR101072425B1/en not_active IP Right Cessation
- 2004-06-18 TW TW093117595A patent/TWI287694B/en not_active IP Right Cessation
- 2004-06-21 CN CNB2004100600327A patent/CN1329749C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03153780A (en) * | 1989-11-10 | 1991-07-01 | Toyo Ink Mfg Co Ltd | Colored composition for color filter |
| CN1165304A (en) * | 1995-04-28 | 1997-11-19 | 东丽株式会社 | Resin black matrix for liquid crystal display device |
| WO2002093255A2 (en) * | 2001-05-15 | 2002-11-21 | Showa Denko K. K. | Photosensitive coloring compositon, color filter using the compositon and method of producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI287694B (en) | 2007-10-01 |
| JP4601267B2 (en) | 2010-12-22 |
| TW200506521A (en) | 2005-02-16 |
| JP2005010604A (en) | 2005-01-13 |
| CN1573369A (en) | 2005-02-02 |
| KR101072425B1 (en) | 2011-10-11 |
| KR20040110101A (en) | 2004-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4627617B2 (en) | Coloring composition, method for producing color filter, and method for producing black matrix substrate | |
| JP5836126B2 (en) | Coloring composition and color filter | |
| CN101595406B (en) | Colored composition, color filter, and method for production of the color filter | |
| JP5573435B2 (en) | Triarylmethane dyes and uses thereof | |
| JP4553128B2 (en) | COLORING COMPOSITION, COLOR FILTER USING THE SAME, AND METHOD FOR PRODUCING THE SAME | |
| JP5573019B2 (en) | Coloring composition for color filter, color filter and color display device | |
| JP5577647B2 (en) | Color filter coloring composition and color filter | |
| JP5151126B2 (en) | Black composition and color filter using the same | |
| CN1329749C (en) | Sensitive black composition, black substrate using same and color filter | |
| CN103869612B (en) | Photosensitive Resin Composition for Color Filter and Color Filter Using the Same | |
| JP2012229344A (en) | Azo pigment, coloring composition, and color filter | |
| JP2011022237A (en) | Photosensitive blue colored composition, color filter using the same and color display device | |
| JP2015096913A (en) | Coloring composition for solid-state image sensors, and color filter | |
| CN100487500C (en) | Black composition and its production method | |
| CN101876788B (en) | Photosensitive colored composition and color filter | |
| JP2017190295A (en) | Compound, and pigment dispersant, coloring composition and color filter which contain that compound | |
| JP6256127B2 (en) | Rhodamine dye for color filter and use thereof | |
| JP5493576B2 (en) | Coloring composition for color filter, color filter and color display device | |
| JP2008038061A (en) | Fuchsine-colored composition for color filter, and color filter to be set on color image pickup tube device using the composition | |
| JP2005275218A (en) | Photosensitive black composition, and black matrix substrate and color filter using the same | |
| JP4151249B2 (en) | Coloring composition for color filter and color filter | |
| JP2005189561A (en) | Photosensitive black composition, black matrix substrate using the same and color filter | |
| JPH0968607A (en) | Color composition for color filter and color filter | |
| JP2007233230A (en) | Photosensitive black composition and color filter | |
| KR19980015678A (en) | Pigment dispersion photoresist composition for color filter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070801 Termination date: 20150621 |
|
| EXPY | Termination of patent right or utility model |