CN102129094A - Heat resistant flexible color filter - Google Patents
Heat resistant flexible color filter Download PDFInfo
- Publication number
- CN102129094A CN102129094A CN2010100021813A CN201010002181A CN102129094A CN 102129094 A CN102129094 A CN 102129094A CN 2010100021813 A CN2010100021813 A CN 2010100021813A CN 201010002181 A CN201010002181 A CN 201010002181A CN 102129094 A CN102129094 A CN 102129094A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- heat
- colored filter
- group
- resisting flexible
- 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.)
- Pending
Links
Images
Landscapes
- Paints Or Removers (AREA)
- Optical Filters (AREA)
Abstract
The invention discloses a heat resistant flexible color filter, which comprises a flexible transparent substrate and a thermally stable color photo-resistance material coated on the flexible transparent substrate, wherein the forming material of the substrate comprises silicon dioxide and polyimide, and the silicon dioxide accounts for 20 to 70 weight percent of the forming material; and the thermally stable color photo-resistance material comprises 30 to 90 weight percent of alkali-soluble resin system, 5 to 60 weight percent of photosensitive system and 10 to 50 weight percent of inorganic alkoxide coated pigment.
Description
Technical field
The present invention relates to a kind of colored filter, and be particularly related to and a kind ofly blend together substrate and the formed heat-resisting flexible colored filter of thermal stability chromatic photoresist material by silicon dioxide and polyimide.
Background technology
The colored filter manufacturing of Thin Film Transistor-LCD comprises the formation black surround and prevents the black photosensitive resin of mixed light and the red, green, blue three color coloured light resistance of optical filtering usefulness, and wherein, chromatic photoresist must have good penetrability and saturation degree.Use dyestuff in traditional colored filter, can reach the requirement of high light transmittance and color saturation, but the anti-optical activity and the thermotolerance of dyestuff are bad.For overcoming this problem, pigment dispersing method photoresist has replaced dye method becomes main flow; Development along with large scale TV panel, it requires high brightness to make panel temperature improve, must reduce the photoresistance pigment particles to prevent scattering for pursuing high color saturation, these make that the thermotolerance of the pigment of colored filter grade was not enough to reach the requirement of TV with process for manufacturing liquid crystal display in the past.
The exploitation of active flexible liquid crystal display mainly can be divided into flexible colored filter, two parts of flexible thin-film transistor, no matter be that flexible colored filter or flexible thin-film transistor all still have many difficulties to remain to be broken through on material and manufacture craft, how develop flexible base, board and be one of wherein emphasis with high transparent, high heat-resisting and low thermal coefficient of expansion; In addition, in flexible colored filter is made, need the regulation and control of collocation high heat-resisting, low-thermal-expansion color type photoresistance, especially substrate and photoresistance interface property value, develop the important topic of flexible colored filter especially.
Summary of the invention
The invention provides a kind of heat-resisting flexible colored filter, comprising: bendable transparency carrier, it forms material and comprises silicon dioxide and polyimide, and wherein the ratio of this formation material of this silica comprises is about 20-70wt%; And coat thermally-stabilised chromatic photoresist material on this bendable transparency carrier, wherein, this thermally-stabilised chromatic photoresist material comprises the alkali soluble resin system of about 30-90wt%, the photosensitive system of about 5-60wt%, and the pigment with inorganic alkoxide coating of about 10-50wt%.
For above and other objects of the present invention, feature and advantage can be become apparent more, below enumerate preferred embodiment, and cooperate appended diagram, be described in detail below.
Description of drawings
Figure 1A and Figure 1B represent embodiment 2 and the optical microscope photograph of comparative example 2 after developing respectively.
The embodiment of invention
It is as described below to constitute heat-resisting flexible colored filter of the present invention.
At first, provide bendable transparency carrier and thermally-stabilised chromatic photoresist material.Wherein, the formation material of bendable transparency carrier comprises silicon dioxide and polyimide, and wherein silicon dioxide more has the ultra low heat expansion coefficient except having high transparent, high heat-resistant quality, and polyimide then has high transparent, high heat-resisting and good flexibility.
Blend together in the formation step of substrate at silicon dioxide and polyimide, at first with particulate silica (SiO
2) be dissolved in the organic solvent, wherein, be dissolved in the silicon dioxide (SiO in the organic solvent
2) solid content less than 40%.Organic solvent can be N,N-dimethylacetamide (DMAC), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), r-butyrolactone (r-butyrolactone).Silicone surfactant with polar functional group can comprise amino silicone (aminosilane), isocyanic acid siloxane (isocyanatesilane).
Then, add polyimide solution, wherein, the ratio that silica comprises forms material is about 20-70wt%, preferably about 30-60wt%.
It is synthetic that above-mentioned polyimide can utilize typical polycondensation reaction (polycondensation), its synthetic method has two kinds, first method is to be divided into two stages to carry out, at first diamines (diamine) and dicarboxylic anhydride (dianhydride) monomer are reacted in polar solvent, form precursor (precursor) polyamic acid (poly (amic acid) of polyimide, PAA), and then carry out imidizate (midization) with high temperature method (300-400 ℃) or chemical method and react, make its dehydration closed-loop transform into polyimide.Second method is that diamines (diamine) and dicarboxylic anhydride (dianhydride) monomer are reacted in phenol solvent (metacresol (m-cresol), chlorophenol (Cl-phenol)), is warming up to the reflux temperature reaction and forms polyimide.
The molecular formula of above-mentioned polyimide is suc as formula shown in (I):
Wherein, n can be the integer of about 15-10000.
The A of formula (I) is naphthenic base, heterocyclic radical, the naphthenic base with one or more unsaturated links and heterocyclic radical, aryl, heteroaryl, fatty group, ring grease dialkylene, aralkyl or the heteroarylalkyl of many rings, and each ring has 3 to 8 annular atomses.And in certain embodiments, hydrogen on each annular atoms can be replaced by halogen, alkyl, sulfane base (sulfane), alkoxy, alkane thiazolinyl, alkane alkynyl, alkene oxygen base, alkynyloxy group or aromatic radical as required, wherein, alkyl, sulfane base, alkoxy, alkane thiazolinyl, alkane alkynyl, alkene oxygen base or alkynyloxy group contain 1-12 carbon atom, for straight chain or have the group of Zhi Jian.
In one embodiment, A can be
Wherein Z be oxygen ,-CH
2-,-C (CH
3)
2-,-Ar-O-Ar-, Ar-CH
2-Ar-,-Ar-C (CH
3)
2-Ar-or-Ar-SO
2-Ar-, and Ar represents phenyl ring, and the hydrogen among the A on each annular atoms can be replaced by halogen, alkyl, sulfane base, alkoxy, alkane thiazolinyl, alkane alkynyl, alkene oxygen base, alkynyloxy group or aromatic radical as required.
In another embodiment, A can be
And X and Y are-H ,-CH
3,-R ,-CF
3,-OH ,-OR ,-Br ,-Cl or-I, and R represents the alkyl of 1-18 carbon number, in addition, Z is-O-,-S-,-CH
2-,-C (CH
3)
2-,-SO
2-,-Ar-O-Ar-,-Ar-CH
2-Ar-,-O-Ar-Ar-O-,-O-Ar-C (CF
3)
2-Ar-O-,-O-Ar-C (CH
3)
2-Ar-O-,-O-Ar-SO
2-Ar-O-, and Ar represents phenyl ring.
In addition, the B of formula (I) is naphthenic base, heterocyclic radical, the naphthenic base with one or more unsaturated links and heterocyclic radical, aryl, heteroaryl, fatty group, ring grease dialkylene, aralkyl or the heteroarylalkyl of one or more many rings, and each ring has 3 to 8 annular atomses.In certain embodiments, hydrogen on each annular atoms can be replaced by halogen, alkyl, sulfane base, alkoxy, alkane thiazolinyl, alkane alkynyl, alkene oxygen base, alkynyloxy group or aromatic radical as required, wherein, alkyl, sulfane base, alkoxy, alkane thiazolinyl, alkane alkynyl, alkene oxygen base or alkynyloxy group contain 1-12 carbon atom, for straight chain or have the group of Zhi Jian.
In one embodiment, B can be
And Z be oxygen ,-CH
2-,-C (CH
3)
2-,-Ar-O-Ar-, Ar-CH
2-Ar-,-Ar-C (CH
3)
2-Ar-or-Ar-SO
2-Ar-, and Ar represents phenyl ring, and the hydrogen among the B on each annular atoms can be replaced by halogen, alkyl, sulfane base, alkoxy, alkane thiazolinyl, alkane alkynyl, alkene oxygen base, alkynyloxy group or aromatic radical as required.
In another embodiment, B is
And X and Y are-H ,-CH
3, ,-R ,-CF
3,-OH ,-OR ,-Br ,-Cl or-I, and R represents the alkyl of 1-18 carbon number, in addition, Z is-O-,-S-,-CH
2-,-C (CH
3)
2-,-SO
2-,-Ar-O-Ar-,-Ar-CH
2-Ar-,-O-Ar-Ar-O-,-O-Ar-C (CF
3)
2-Ar-O-,-O-Ar-C (CH
3)
2-Ar-O-,-O-Ar-SO
2-Ar-O-, and Ar represents phenyl ring.
With silicon dioxide with after polyimide evenly mixes, add silicone surfactant again and participate in reaction to form silicon dioxide and composite polyimide material with polar functional group.Then silicon dioxide and composite polyimide material are solidified to form bendable transparency carrier.
In thermally-stabilised chromatic photoresist material, can comprise: alkali soluble resin system, about 30-90wt%; Photosensitive system, about 5-60wt%; And the pigment that coats with inorganic alkoxide, about 10-50wt%.
The alkali soluble resin system can comprise alkali soluble resin.Alkali soluble resin comprises the homopolymer or the multipolymer of vinylation unsaturated monomer.The vinylation insatiable hunger is closed monomer and is comprised methyl acrylic ester such as methyl methacrylate (methyl (meth) acrylate), phenyl methacrylate (benzyl (meth) acrylate), Jia Jibingxisuanyizhi (ethyl (meth) acrylate), methacrylic acid 2-hydroxyl ethyl ester (2-hydroxyethyl (meth) acrylate), hydroxy propyl methacrylate (hydroxylpropyl (meth) acrylate), isobutyl methacrylate (isobutyl (methy) acrylate) etc., or esters of acrylic acid such as methyl acrylate (methylacrylate), phenyl acrylate (benzyl acrylate), ethyl acrylate (ethyl acrylate), acrylic acid 2-hydroxyl ethyl ester (2-hydroxyethyl acrylate), hydroxypropyl acrylate (hydroxylpropyl acrylate), isobutyl acrylate (isobutyl acrylate), methacrylic acid 3-(trimethoxysilyl) propyl ester (3-(Trimethoxysilyl) propyl methacrylate) etc.
In one embodiment, alkali soluble resin comprises vinylation unsaturated monomer that contains silane structure and the multipolymer that does not contain the vinylation unsaturated monomer of silane structure, wherein, this vinylation unsaturated monomer that contains silane structure in this multipolymer shared content less than 20mol%.
In another embodiment, alkali soluble resin comprises the acryl macromolecule that contains acid group, and wherein, acid group is for example methacrylic acid or acrylic acid etc.
In addition, in another embodiment, alkali soluble resin serve as reasons contain that monomer copolymerization is closed in vinylation insatiable hunger that acid group such as methacrylic acid or acrylic acid monomer and other vinylation insatiable hunger close monomer or contain silane structure and macromolecule, wherein, contain the acid group monomer mole ratio to can be about 10-50%, preferred about 20-40%, the about 1000-100 of multipolymer weight-average molecular weight (g/mol), 000, preferred about 6,000-20,000.
Photosensitive system can comprise polyfunctional monomer and the light trigger with two keys more than two.
Plural polyfunctional monomer can carry out cross-linking reaction and form reticulate texture.Polyfunctional monomer can comprise ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), 1,4-butanediol diacrylate (1,4-butanediol diacrylate), diethylene glycol diacrylate (diethyleneglycol diacrylate, DEGDA), pentaerythritol triacrylate (pentaerythritol triacrylate), ethoxylated trimethylolpropane triacrylate (ethoxylated trimethylolpropanetriacrylate), dipentaerythritol five acrylate (dipentaerythritol pentaacrylate), ethoxylation tetramethylol methane tetraacrylate (ethoxylated pentaerythritol tetraacrylate), tetramethylol methane tetraacrylate (pentaerythritol tetraacrylate) and dipentaerythritol acrylate (dipentaerythritol hexaacrylate) etc.
The UV exposure of the optional comfortable broad band wavelength of light trigger can discharge free radical to carry out the organism of cross-linking reaction down, and the light trigger of relative greater efficiency is preferably arranged below the 400nm wavelength, as:
(1) acetophenone (Acetophenone) class: 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholinyl-1-acetone (2-Methyl-1-(4-(methylthio) phenyl)-2-morpholino-propane-1), 1-hydroxy-cyclohexyl phenyl ketone (1-Hydroxy cyclohexyl phenyl ketone), diethoxy acetophenone (Diethoxyacetophenone), 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone (2-Hydroxy-2-methyl-1-phenyl-propane-1-one), 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone (2-Benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl) phenyl]-1-butanone) etc.; (2) styrax (Benzoin) class: styrax (Benzoin), benzoin methyl ether (Benzoin methyl ether), two methyl ethers (Benzyl dimethyl ketal) of resting in peace; (3) diphenylketone (Benzophenone) class: diphenylketone (Benzophenone), 4-phenyl benzophenone (4-Phenyl benzophenone), hydroxy benzophenone (Hydroxyl benzophenone) etc.; (4) plug ton ketone (Thioxanthone) class: isopropyl thioxanthone (Isopropylthioxanthone), 2-clopenthixal ketone (2-Chlorothioxanthone etc.); And (5) anthraquinone (anthraquinone) class: 2-EAQ (2-ethylanthraquinone).
In addition, above-mentioned light trigger can also mix use except can independently using, as isopropyl thioxanthone (Isopropylthioxanthone) mix 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone (2-Benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl) phenyl]-1-butanone) can get high film speed.
And the pigment manufacture method that inorganic alkoxide coats is to use sol-gel process, makes to have reactive inorganic alkyl oxide generation polycondensation reaction and be coated on the pigment particles skin.
Structural formula with reactive inorganic alkyl oxide is suc as formula shown in (II):
R---M---(OR ')
nX
3-nFormula (II)
Wherein, M is a metal, titanium for example, or be silicon; R is hydrogen, C
1-18Alkyl (alkyl group), aryl (aryl group), alkyl vinyl (alkyl vinyl group), alkyl amine group (alkyl aminegroup), alkyl nitrile (alkyl nitrile), alkyl isocyanate (alkyl isocyanate), alkyl epoxy base (alkyl epoxide group) or OR '; R ' is C
1-6Alkyl; X be halogen ,-OH ,-NCO or C
1-6Alkyl, and n is the positive integer of 1-3.
Can be before inorganic alkyl oxide coats pigment particles, earlier pigment particles is disperseed, its method is: at normal temperatures pigment was soaked into about 30 minutes with organic solvent, for example tetrahydrofuran (THF), disperse by grinding, reduce the particle diameter of pigment particles by this.In addition, also can add catalyzer in above-mentioned method and carry out polycondensation reaction, behind solvent evaporates and high-temperature maturing, can make to react completely, the temperature of above-mentioned polycondensation reaction is 30-150 ℃, is preferably 70-120 ℃.The thermotolerance and the water wettability of the pigment that inorganic alkoxide coats significantly improve, and help its stability in manufacturing process and improve application.
Above-mentioned catalyzer can be mineral acid, organic acid acidic catalyst, or the base catalyst of inorganic base, organic base.Acidic catalyst for example is HNO
3 (aq), H
2SO
4 (aq), HCl
(aq), HBr
(aq), HI
(aq), HClO
4 (aq), acetic acid or glacial acetic acid etc.; Base catalyst for example is NaOH
(aq), NH
3 (aq), NaNH
2, CH
3OK, KOH, uncle's ammonia, parahelium or uncle's ammonia etc.Wherein acidic catalyst is preferably HCI
(aq), HI
(aq)Or acetic acid, base catalyst is preferably NaOH
(aq)Or NH
3 (aq)
Thermally-stabilised chromatic photoresist material then is to mix and get with above-mentioned alkali soluble resin system, photosensitive system and with the pigment that inorganic alkoxide coats.
The solid content of thermally-stabilised chromatic photoresist material can be 10-40%, and the coating method therefore is different with the coating thickness that will form and control its solid content, basically if with rotary coating mode control coating thickness at the 1-1.5 micron, solid content preferably is adjusted at 18-28%.And the better ratio of each composition is shown in table 1 in the thermally-stabilised chromatic photoresist material.
The composition of the thermally-stabilised chromatic photoresist material of table 1.
| Composition | Weight ratio wt% |
| Alkali soluble resin | 6-20 |
| Polyfunctional monomer | 4-7 |
| Light trigger | 1-5 |
| Pigment with inorganic alkoxide coating | 2-10 |
| Spreading agent | 0.8-10 |
| Solvent | 85-60 |
In one embodiment, the generation type of thermally-stabilised chromatic photoresist material can be: will disperse with spreading agent with the pigment that inorganic alkoxide coats earlier, add polyfunctional monomer again and light trigger mixes, other composition is added with high-speed stirred evenly use the back at last.
At last, above-mentioned thermally-stabilised chromatic photoresist material is coated on the above-mentioned bendable transparency carrier, coating method can comprise rotary coating, slit extrusion coated, ink-jet application etc.Afterwards substrate is carried out prebake conditions, the photomask with specific pattern exposes to the thermally-stabilised chromatic photoresist material of coating on the substrate again, is then developed with alkaline aqueous solution, and unexposed portion is then by the alkali lye flush away, and the pattern of exposed portion will keep.Pattern dries by the fire firmly through washing and after drying up, and the photoresistance that can finish once applies step.Repeat the making that this step respectively imposes other photoresistance and corresponding optical mask patterns such as redness, green, blueness respectively and can finish colored filter afterwards.Heat-resisting flexible colored filter of the present invention is made except using existing developing technique, also have the effect of high degree of dimensional stability, low aberration, low thermal coefficient of expansion, and its thermal expansivity is about 8-30.High thermal stability chromatic photoresist material of the present invention is except can be applicable to silica/polyimides blendes together on the substrate, can also be applied to other polymer base material such as polyethylene terephthalate (polyethylene terephthalate, PET), polyethersulfone (polyether sulfone, PES) etc., be not limited to above-mentioned polyimide.
[embodiment]
1. polyimide is synthetic
(1) polyimide B1317 (dicyclo [2.2.2] suffering-7-alkene-2,3,5,6-tetracarboxylic dianhydride-BAPPm (2,2 '-two [4-(4-amino-benzene oxygen phenyl)] propane), (BB) synthetic
At room temperature, in the nitrogen, the BAPPm diphenylamine of 0.0147mole is dissolved in the metacresol (m-cresol) of 32.94g, treat again the B1317 dicarboxylic anhydride of 0.015mole to be added after BAPPm dissolves fully, after B1317 dissolves fully, continue to stir 1 hour, and form thick polyamic acid solution.Be heated to 220 ℃ then, 3 hours, in course of reaction, with de-watering apparatus water got rid of simultaneously.Afterwards reactant liquor is splashed into and make the polyimide precipitation in the methyl alcohol, oven dry is 12 hours in vacuum drying oven.Utilize gel permeation chromatograph (Gel Permeation Chromatography, GPC) result who carries out molecular weight determination shows, the Mn of product is 39381, Mw is 1011539, Mw/Mn is 25.69.
2. the preparation of bendable transparency carrier
(1) substrate 1: silica/polyimides B1317-BAPPm (SiO
2/ BB=3/7) blend together synthesizing of substrate
At room temperature, 3g is dissolved in silicon dioxide (SiO among the DMAc with solid content 20%
2) put into the 20g sample bottle with 7g with the B1317-BAPPm (BB) that solid content 20% is dissolved among the DMAc, add the 0.3g aminopropyl trimethoxysilane, at room temperature stirred 30 minutes, coat on glass in the scraper mode it, putting into baking oven respectively toasted under 80 ℃ and 150 ℃ 1 hour, and take off from glass, can obtain silica/polyimides B 1317-BAPPm (SiO
2/ BB=3/7) blend together substrate.
(2) substrate 2: silica/polyimides B 1317-BAPPm (SiO
2/ BB=5/5) blend together synthesizing of substrate
At room temperature, 5g is dissolved in silicon dioxide (SiO among the DMAc with solid content 20%
2) put into the 20g sample bottle with 5g with the B1317-BAPPm (BB) that solid content 20% is dissolved among the DMAc, add the 0.2g aminopropyl trimethoxysilane, at room temperature stirred 30 minutes, coat on glass in the scraper mode it, putting into baking oven respectively toasted under 80 ℃ and 150 ℃ 1 hour, and take off from glass, can obtain silica/polyimides B1317-BAPPm (SiO
2/ BB=5/5) blend together substrate.
(3) substrate 3: silica/polyimides B 1317-BAPPm (SiO
2/ BB=7/3) blend together synthesizing of substrate
At room temperature, 7g is dissolved in silicon dioxide (SiO among the DMAc with solid content 20%
2) put into the 20g sample bottle with 3g with the B1317-BAPPm (BB) that solid content 20% is dissolved among the DMAc, add the 0.12g aminopropyl trimethoxysilane, at room temperature stirred 30 minutes, coat on glass in the scraper mode it, putting into baking oven respectively toasted under 80 ℃ and 150 ℃ 1 hour, and take off from glass, can obtain silicon dioxide (SiO
2)/polyimide B1317-BAPPm (SiO
2/ BB=7/3) blend together substrate.
Substrate 1,2 and 3 characteristic are shown in table 2.
Table 2. substrate 1,2 and 3 characteristic
| Thickness (μ m) | CTE (ppm/℃) | TT (％) | b | ||
| BB | 57 | 75.4 | 89.3 | 1.95 | |
| Substrate 1 | SiO 2/BB＝3/7 | 53 | 56.6 | 89.5 | 2.01 |
| Substrate 2 | SiO 2/BB＝5/5 | 52 | 48.6 | 89.6 | 2.13 |
| Substrate 3 | SiO 2/BB＝7/3 | 51 | 28.3 | 90.1 | 2.25 |
*CTE (thermal expansivity Coefficient of Thermal Expansion): record according to ASSTM E831
*TT (total transmittance): record according to ASTM D1003-07
(CIE L
*a
*b
*International Commission on Illumination's three degree color spaces: its tridimensional L=luminance brightness, the red-green axle in a=space, the blue-yellow colour axis in b=space)
3. coat the preparation of pigment with inorganic alkyl oxide
(1) pigment 1 (coating) with inorganic alkyl oxide
Tygon (Polyethylene at 250ml, PE) add 1/2 in the mill jar and grind the 1mm diameter zirconium ball of tank volume, add 100g THF solvent, add 40g red pigment (Pigment Red 254 again, Ciba) with 5g 3-aminopropyl triethoxysilane (3-Aminopropyltriethoxysilane) (surface modifier), this mixed solution disperseed 2 hours with sand mill, took out to be placed in the 250g round bottom reaction bulb, add 1.7g aqueous hydrochloric acid solution (pH 2.1) again, continue to stir; Add 5g triethoxy methyl silicane (Triethoxymethyl silane again, TEOS), this 5g TEOS carries out hydrolysis reaction earlier in the aqueous solution (pH 2.1) of 1.7g, whole solution at room temperature stirred 24 hours, and treat that THF volatilizees, high temperature (110 ℃) slaking 8 hours makes condensation reaction complete, clean 4 times with pure water after finishing after drying for standby.
(2) pigment 2 (coating) with inorganic alkyl oxide
With pigment 1, wherein pigment changes into and uses carbo black MA7 (from Mistsubishi).
(3) pigment 3 (coating) with inorganic alkyl oxide
With pigment 1, wherein pigment changes into and uses Pigment Green 36 (from BASF).
(4) pigment 4 (coating) with inorganic alkyl oxide
With pigment 1, wherein pigment changes into and uses Pigment Blue 15: 6 (from BASF).
4. the preparation of heat-resisting flexible colored filter
(1) embodiment 1
Get the tygon mill jar of 250ml, the 1mm diameter zirconium ball that adds 1/2 mill tank volume, add the above-mentioned pigment 1 of 10g, (SOLSPERSE produces for 80g PGMEA and 5.5g spreading agent, model 22000,0.5g and model 24000,5g), disperseed 4 hours with muller, filter the mill pearl and take out dispersion liquid, in nitrogen environment, add solvent PGMEA 96.7g, acryl resin solution 20g, reactive monomer dipentaerythritol acrylate (dipentaerythritol hexaacrylate) 6g, initiating agent isopropyl thioxanthone (Isopropylthioxanthone, ITX) 0.5g, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone (2-Benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl) phenyl]-1-butanone, I369) 4.5g, stirring and dissolving becomes photosensitive resin.
Again above-mentioned dispersion liquid is added in the photosensitive resin gradually under stirring, add lasting the stirring and finished the preparation of photonasty chromatic photoresist in 2 hours; With the photonasty chromatic photoresist for preparing with rotating speed 600rpm, 15 seconds, 900rpm, 20 seconds rotary coating on aforesaid substrate 1 through 90 ℃ of prebake conditions 2 minutes, again through energy 150mj/cm
2Ultraviolet source be equipped with photomask and expose, then develop with 0.5%KOH alkali lye, unexposed portion is then by the alkali lye flush away, the pattern of reservation through washing with dry up after, with the hard baking of 230 ℃ of high temperature 1 hour, promptly finish colored filter again.
(2) embodiment 2
With embodiment 1, wherein, pigment changes the cladded type black pigment of above-mentioned pigment 2 into.
(3) embodiment 3
With embodiment 1, wherein, pigment changes the cladded type viridine green of above-mentioned pigment 3 into.
(4) embodiment 4
With embodiment 1, wherein, pigment changes the cladded type blue pigment of above-mentioned pigment 4 into.
(5) comparative example 1
With embodiment 1, wherein, pigment is not for coating Pigment Red 254 (Ciba of manufacturer).
(6) comparative example 2
With embodiment 1, wherein, pigment is not for coating Pigment MA7 (Mitsubish of manufacturer).
(7) comparative example 3
With embodiment 1, wherein, pigment is not for coating Pigment Green 36 (BASF of manufacturer).
(8) comparative example 4
With embodiment 1, wherein, pigment is not for coating Pigment Blue 15: 6 (BASF of manufacturer).
And the various characteristics of the foregoing description and comparative example is shown in table 3.
The various characteristics of table 3. embodiment and comparative example
| Pigment (g) | The 3-aminopropyl triethoxysilane | Triethoxy methyl silicane | Thermogravimetric analysis (temperature of 5% loss in weight ℃) | Thermal expansivity (ppm/ ℃ of out of plane) (100-250 ℃) | ΔEab | |
| Embodiment 1 | PR254 (40g) | 5 | 5 | 257 | 14.33 | 0.48 |
| Embodiment 2 | Black (40g) | 5 | 5 | 267 | 13.39 | 0.78 |
| Embodiment 3 | Green (40g) | 5 | 5 | 223 | 28.55 | 1.43 |
| Embodiment 4 | Blue (40g) | 5 | 5 | 261 | 9.1 | 2.60 |
| Comparative example 1 | PR254 | NA | NA | 202 | 19.85 | 3j3 |
| Comparative example 2 | Black | NA | NA | 220 | 18.75 | |
| Comparative example 3 | Green | NA | NA | 211 | 47.34 | 2.28 |
| Comparative example 4 | Blue | NA | NA | 218 | 14.11 | 3.20 |
*Δ Eab (calculated color difference): value of chromatism records according to ASTM E831
*Thermal expansivity (out of plane): be defined as the Coefficient of Thermal Expansion value that vertical direction records
In order to estimate the development quality that silicon dioxide and polyimide is blended together substrate with the pigment of embodiment and comparative example, the residue (scum) of metacoxal plate of promptly developing is analyzed, the pixel penetrability of developing fully and removing is decided to be 100%, develop the back if there is residue to adhere on the pixel, then penetrability is with less than 100%, so define the residue degree with the penetrability of the back pixel of developing.The residual residue of the high more representative of penetrability is few more.
As shown in Table 3, silicon dioxide and polyimide blend together between substrate and the photoresist-Gao heat resistant paint cladded type photoresistance, have advantages such as good interface compatibility, development, the swollen account coefficient of low-heat and low aberration.
In addition, Figure 1A and Figure 1B show embodiment 2 and the optical microscope photograph of comparative example 2 after developing respectively.And by Figure 1A and Figure 1B as can be known, the bottom noresidue of embodiment 2, and the bottom of comparative example 2 is residual serious.
Though the present invention discloses as above with embodiment more preferably; but these embodiment are not in order to limit the present invention; any those skilled in the art without departing from the spirit and scope of the present invention; can do a little change and retouching, so protection scope of the present invention should be as the criterion with the scope that appending claims was defined.
Claims (15)
1. heat-resisting flexible colored filter comprises:
Bendable transparency carrier, it forms material and comprises silicon dioxide and polyimide, and wherein, the ratio of this formation material of this silica comprises is about 20-70wt%; And
Coat the thermally-stabilised chromatic photoresist material on this bendable transparency carrier, wherein, this thermally-stabilised chromatic photoresist material comprises
The alkali soluble resin system of about 30-90wt%,
The photosensitive system of about 5-60wt%, and
The pigment of about 10-50wt% with inorganic alkoxide coating.
The percent by weight of each component is based on this thermally-stabilised chromatic photoresist material in this thermally-stabilised chromatic photoresist material, and the summation of each component weight percentage is 100%.
2. heat-resisting flexible colored filter as claimed in claim 1, wherein, the material of this bendable transparency carrier further comprises silicone surfactant.
3. heat-resisting flexible colored filter as claimed in claim 1, wherein, the molecular formula of this polyimide is suc as formula shown in (I):
Wherein, n is the integer of about 15-10000;
A is naphthenic base, heterocyclic radical, the naphthenic base with one or more unsaturated links and heterocyclic radical, aryl, heteroaryl, fatty group, ring grease dialkylene, aralkyl or the heteroarylalkyl of many rings, and each ring has 3 to 8 annular atomses;
B is naphthenic base, heterocyclic radical, the naphthenic base with one or more unsaturated links and heterocyclic radical, aryl, heteroaryl, fatty group, ring grease dialkylene, aralkyl or the heteroarylalkyl of one or more many rings, and each ring has 3 to 8 annular atomses.
4. heat-resisting flexible colored filter as claimed in claim 3, wherein, hydrogen on each annular atoms of this A is replaced by halogen, alkyl, sulfane base, alkoxy, alkane thiazolinyl, alkane alkynyl, alkene oxygen base, alkynyloxy group or aromatic radical, hydrogen on each annular atoms of this B is replaced by halogen, alkyl, sulfane base, alkoxy, alkane thiazolinyl, alkane alkynyl, alkene oxygen base, alkynyloxy group or aromatic radical, wherein, alkyl, sulfane base, alkoxy, alkane thiazolinyl, alkane alkynyl, alkene oxygen base or alkynyloxy group contain the 1-12 carbon atom, for straight chain or have the group of Zhi Jian.
5. heat-resisting flexible colored filter as claimed in claim 3, wherein, A is
And Z be oxygen ,-CH
2-,-C (CH
3)
2-,-Ar-O-Ar-, Ar-CH
2-Ar-,-Ar-C (CH
3)
2-Ar-or-Ar-SO
2-Ar-, and Ar represents phenyl ring.
6. heat-resisting flexible colored filter as claimed in claim 3, wherein, A is
And X and Y are-H ,-CH
3,-R ,-CF3 ,-OH ,-OR ,-Br ,-Cl or-I, and R represents the alkyl of carbon number 1-18, and Z be-O-,-S-,-CH
2-,-C (CH
3)
2-,-SO
2-,-Ar-O-Ar-,-Ar-CH2-Ar-,-O-Ar-Ar-O-,-O-Ar-C (CF
3)
2-Ar-O-,-O-Ar-C (CH
3)
2-Ar-O-,-O-Ar-SO
2-Ar-O-, and Ar represents phenyl ring.
7. heat-resisting flexible colored filter as claimed in claim 3, wherein B is
And Z be oxygen ,-CH
2-,-C (CH
3)
2-,-Ar-O-Ar-, Ar-CH
2-Ar-,-Ar-C (CH
3)
2-Ar-or-Ar-SO
2-Ar-, and Ar represents phenyl ring.
8. heat-resisting flexible colored filter as claimed in claim 3, wherein, B is
And X and Y are-H ,-CH
3, ,-R ,-CF
3,-OH ,-OR ,-Br ,-Cl or-I, and R represents the alkyl of 1-18 carbon number, and Z be-O-,-S-,-CH
2-,-C (CH
3)
2-,-SO
2-,-Ar-O-Ar-,-Ar-CH
2-Ar-,-O-Ar-Ar-O-,-O-Ar-C (CF
3)
2-Ar-O-,-O-Ar-C (CH
3)
2-Ar-O-,-O-Ar-SO
2-Ar-O-, and Ar represents phenyl ring.
9. heat-resisting flexible colored filter as claimed in claim 1, wherein, this alkali soluble resin system comprises the acryl macromolecule that contains acid group, the homopolymer or the multipolymer of vinylation unsaturated monomer.
10. heat-resisting flexible colored filter as claimed in claim 9, wherein, this acid group comprises methacrylic acid or acrylic acid.
11. heat-resisting flexible colored filter as claimed in claim 9, wherein, the homopolymer of this vinylation unsaturated monomer or multipolymer comprise the vinylation unsaturated monomer that contains silane structure, this vinylation unsaturated monomer that contains silane structure in this multipolymer proportion less than 20mol%.
12. heat-resisting flexible colored filter as claimed in claim 9, wherein, the homopolymer of this vinylation unsaturated monomer or multipolymer comprise that the vinylation insatiable hunger that contains acid group closes the multipolymer that monomer is closed in monomer and the vinylation insatiable hunger that contains silane structure.
13. heat-resisting flexible colored filter as claimed in claim 9, wherein, the mol ratio that monomer is closed in the vinylation insatiable hunger that contains acid group can be about 10-50%, and multipolymer weight-average molecular weight (g/mol) is about 1000-100,000.
14. heat-resisting flexible colored filter as claimed in claim 1, wherein, this photosensitive system comprises polyfunctional monomer and the light trigger with two keys more than two.
15. heat-resisting flexible colored filter as claimed in claim 1, wherein, the structural formula of this inorganic alkoxide is suc as formula shown in (II):
R-M-(OR ')
nX
3-nFormula (II)
Wherein R is hydrogen, C
1-18Alkyl (alkyl group), aryl (aryl group), alkyl vinyl (alkylvinyl group), alkyl amine group (alkyl amine group), alkyl nitrile (alkyl nitrile), alkyl isocyanate (alkyl isocyanate), alkyl epoxy base (alkyl epoxide group) or OR '
R ' is C
1-6Alkyl, X be halogen ,-OH ,-NCO or C
1-6Alkyl, and n is the positive integer of 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100021813A CN102129094A (en) | 2010-01-13 | 2010-01-13 | Heat resistant flexible color filter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100021813A CN102129094A (en) | 2010-01-13 | 2010-01-13 | Heat resistant flexible color filter |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102129094A true CN102129094A (en) | 2011-07-20 |
Family
ID=44267242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010100021813A Pending CN102129094A (en) | 2010-01-13 | 2010-01-13 | Heat resistant flexible color filter |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102129094A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080161473A1 (en) * | 2006-12-29 | 2008-07-03 | Industrial Technology Research Institute | Hybrid composition and films fabricated by the same |
| CN101241305A (en) * | 2007-02-09 | 2008-08-13 | 财团法人工业技术研究院 | Pigment -type photosensitive material |
-
2010
- 2010-01-13 CN CN2010100021813A patent/CN102129094A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080161473A1 (en) * | 2006-12-29 | 2008-07-03 | Industrial Technology Research Institute | Hybrid composition and films fabricated by the same |
| CN101241305A (en) * | 2007-02-09 | 2008-08-13 | 财团法人工业技术研究院 | Pigment -type photosensitive material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101128774B (en) | Photosensitive resin composition for forming light shielding layer, light shielding layer and color filter | |
| CN1279374C (en) | Colored composition, method of manufacturing color filter, and method of manufacturing black matrix substrate | |
| CN101923287B (en) | Photosensitive composition containing photoinitiator of diphenyl sulfide based ketoxime esters and application thereof | |
| CN103635541A (en) | Dye dispersion, photosensitive resin composition for color filter, color filter, liquid crystal display device, and organoluminescent display device | |
| CN1900172B (en) | Organic pigments for colour filters | |
| US20110111333A1 (en) | Heat-resistant flexible color filter | |
| JP2009175613A (en) | Pigment dispersion for color filter and pigment dispersion resist composition for color filter containing the same | |
| CN105159030A (en) | Photosensitive resin composition and base | |
| TWI298076B (en) | Precursor solution for polyimide/silica composite material, its manufacture method and polyimide/silica composite material having low volume shrinkage | |
| JP6113466B2 (en) | Black matrix pigment dispersion composition and black matrix pigment dispersion resist composition containing the same | |
| CN1782874A (en) | Photosensitive composition for forming light shading film, black bottom formed from said light shading film for photosensitive composition | |
| TWI720136B (en) | Surface treatment metal oxide sol | |
| CN101263424B (en) | Photosensitive composition, transfer material, light shielding film and production method thereof, color filter for display device, substrate for display device, and display device | |
| CN102129094A (en) | Heat resistant flexible color filter | |
| JP2008050589A (en) | Colored composition for forming pixels, method for producing color filter and color filter | |
| JPH09328618A (en) | Light-shielding material, black paste, color filter and liquid crystal display device | |
| CN101292196B (en) | Photosensitive resin composition and color filter | |
| CN101241305A (en) | Pigment -type photosensitive material | |
| CN105431777A (en) | Colored curable resin composition | |
| JP5108258B2 (en) | Method for producing pigment modifier | |
| JPH085829A (en) | Color filter for liquid crystal display element | |
| TWI330757B (en) | Pigmentary photosensitive material | |
| US11359093B2 (en) | Polyimide film and flexible display device cover substrate using the same | |
| JP2003255325A (en) | Color filter for liquid crystal display, the liquid crystal display and method for manufacturing color filter for the liquid crystal display | |
| JP3555322B2 (en) | Pigment-dispersed resin solution composition, method for producing the same, and 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 | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110720 |