CN1254702C - Colored light sensitive resin composition - Google Patents
Colored light sensitive resin composition Download PDFInfo
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- CN1254702C CN1254702C CNB021560218A CN02156021A CN1254702C CN 1254702 C CN1254702 C CN 1254702C CN B021560218 A CNB021560218 A CN B021560218A CN 02156021 A CN02156021 A CN 02156021A CN 1254702 C CN1254702 C CN 1254702C
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- pigment
- acid
- aqueous solution
- photosensitive composition
- film
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-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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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
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
-
- 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
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- 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
-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- 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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Abstract
A colored photosensitive resin composition comprises (A) a pigment, (B) a binder polymer, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a pigment dispersant and (F) a solvent. When the surface of a glass substrate is coated with the colored photosensitive resin composition by a spin coating method, the volatile components of the composition are volatilized by drying the composition at 100 DEG C for 3 min to form a film (whose thickness is 1.6 mu m), this film is immersed: (1) in an alkaline aqueous solution used in an amount 2,500 times (by mass) the amount of the film, the aqueous solution is stirred with a stirrer at 300 rpm for 80 sec and the particle size distribution of particles contained in the aqueous solution is measured by a light scattering method, (2) in an aqueous solution used in an amount 2,500 times (by mass) the amount of the film, the aqueous solution is stirred with a stirrer at 300 rpm for 80 sec and the particle size distribution of particles contained in the aqueous solution is measured by a light scattering method,the cumulative 90% particle diameter of the particles is <=0.5 mu m and the maximum particle diameter is <=1.0 mu m. Providing a colored pattern forming method using the colored photosensitive resin composition, especially a method for manufacturing a color filter using the forming method.
Description
Technical field
The present invention relates to photosensitive composition.
Background technology
Photosensitive composition (colour resist) is, the photosensitive polymer combination that is colored (resist) that contains colorant, known to have and contain (A) colorant, (B) binder polymer, (C) optical polymerism compound and (D) material of Photoepolymerizationinitiater initiater, for example be used to form the material of the painted figure that constitutes color filter.At this, color filter 1 refers to, as is loaded on color liquid crystal display arrangement to be used for the colorize of presentation video, is loaded on the colour solid imaging apparatus to be used to obtain the optical element of coloured image.
Painted figure 2 is that as red pixel, green pixel, blue picture element isochrome pixel, this type of painted figure 2 is formed on the substrate 3 usually, constitutes color filter (Fig. 1).The look pixel is the hyaline layer that is colored, by its light color of colour generation pixel separately.
As using this type of photosensitive composition to form the method for painted figure 2, have by be formed at the layer that photosensitive composition on the substrate 3 forms [below, be called the photosensitive composition layer] 4 (Fig. 2 (a)), after irradiation light 6 is exposed (Fig. 2 (b)), the method for development (Fig. 2 (c)).Through overexposure, photosensitive composition layer 4 generates not field of not shining 41 that is shone by light 6 and the irradiation field of being arrived by irradiate light 42 (Fig. 2 (b)).Do not shine field 41 and in developing next time, be eliminated (Fig. 2 (c)).On the other hand, irradiation field 42 still remains in developing next time and forms painted figure 2.Especially painted figure 2 is with the width (W of its section configuration substrate-side
0) than upside width (W
1) wide suitable cone-shaped (Fig. 5 (a)) or the width (W of substrate 3 sides
0) be same as upside width (W
1) rectangular-shaped (Fig. 5 (b)) for well.
In the formation method of this type of painted figure, shine irradiation light quantity in the light in irradiation field less for well, this be because can be in short irradiation time the painted figure of formation.Therefore, use the highly sensitive photosensitive composition that also is enough to form painted figure with a small amount of irradiation light quantity.This type of highly sensitive photosensitive composition preferably shines light quantity too much also can form the painted figure of target.
But highly sensitive photosensitive composition in the past exists, if the section configuration of the irradiation formed at most painted figure of light quantity (2) easily becomes the width (W of substrate (3) side
0) than upside width (W
1) narrow contrary cone-shaped (Fig. 5 (c)), or even film coated surface is stone when developing, and is insoluble to developer solution so film, and can peel off, and then, because of coarse phenomenon takes place the poor adherence section, make behind the color filter because of section coarse and seem rough problem.
Summary of the invention
The objective of the invention is to, provide a kind of high sensitivity and, forming section configuration during development be the photosensitive composition of suitable cone-shaped and even rectangular-shaped, not coarse painted figure, adopts its painted pattern forming method and color filter manufacture method.
The present inventor is found that of discussing meticulously, to film under given conditions and impregnated in alkaline aqueous solution or solvent, when measuring the size-grade distribution of the particle in this alkaline aqueous solution or the solvent, accumulate 90% particle diameter and the maximum particle diameter photosensitive composition in particular range and can solve above-mentioned problem, to such an extent as to finish the present invention.
That is, the present invention relates to following invention.
The present invention's 1 contains (A) pigment, (B) binder polymer, (C) optical polymerism compound, (D) Photoepolymerizationinitiater initiater, (E) pigment dispersing agent and (F) photosensitive composition of solvent, this photosensitive composition is, after being coated with this photosensitive composition with method of spin coating on the glass baseplate surface, made the volatile component volatilization down in dry 3 minutes at 100 ℃, form film (thickness is 1.6 μ m), with the gained film immersion in the alkaline aqueous solution of these film 2500 times of weight (with percentage by weight, contain potassium hydroxide 0.05% respectively, the aqueous solution of sodium butylnaphthalenesulfonate 0.2%), with stirring machine this aqueous solution was stirred for 80 seconds with 300rpm, when measuring the size-grade distribution of the particle that is contained in this aqueous solution by light scattering method, accumulate 90% particle diameter below 0.5 μ m, the photosensitive composition of maximum particle diameter below 1.0 μ m, wherein for the solid constituent of photosensitive composition, with percentage by weight, (A) content of pigment is more than 15% below 50%, (B) content of binder polymer is more than 20% below 55%, (C) content of optical polymerism compound is more than 10% below 45%, (D) content of Photoepolymerizationinitiater initiater is more than 3% below 20%, (A) pigment 1 weight portion (E) pigment dispersing agent is 0.01～1 weight portion relatively, and (E) pigment dispersing agent is that polyethyleneimine is spreading agent or polyurethane series spreading agent.
The present invention's 2 contains (A) pigment, (B) binder polymer, (C) optical polymerism compound, (D) Photoepolymerizationinitiater initiater, (E) pigment dispersing agent and (F) photosensitive composition of solvent, this photosensitive composition is, after being coated with this photosensitive composition with method of spin coating on the glass baseplate surface, made the volatile component volatilization down in dry 3 minutes at 100 ℃, form film (thickness is 1.6 μ m), with gained film immersion this solvent in these film 2500 times of weight, with stirring machine this solvent was stirred for 80 seconds with 300rpm, by light scattering method measure be contained in this solvent be coated with the size-grade distribution of film component the time, accumulate 90% particle diameter below 0.5 μ m, the photosensitive composition of maximum particle diameter below 1.0 μ m.
The present invention's 3 is that (D) Photoepolymerizationinitiater initiater is that acetophenone is 1～2 any photosensitive composition of being put down in writing of the present invention of Photoepolymerizationinitiater initiater.
The present invention's 4 is formation methods of a kind of painted figure, coats on the substrate with any photosensitive composition that the present invention's 1～3 is put down in writing, and drying, formation is filmed, and develop and be feature in this back of filming of exposing.
The present invention's 5 is manufacture methods of a kind of color filter, is feature with the formation method of required color being carried out repeatedly the present invention's the 4 painted figures of being put down in writing.
The present invention's 6 is that required color is the manufacture method of red, green and blue the present invention's 5 color filters of being put down in writing.
Description of drawings
Fig. 1 is the mode chart of an example of expression color filter.
Fig. 2 is the mode chart of the formation technological process of the painted figure of expression.
Fig. 3 is the mode chart of the formation technological process of the painted figure of expression.
Fig. 4 is the mode chart of the formation technological process of the painted figure of expression.
Fig. 5 is the mode chart of the section configuration of the painted figure of expression.
Among the figure,
1: color filter
2: painted figure 2R: red pixel
2 ': painted figure 2G: green pixel
2 ": painted figure 2B: blue picture element
3: substrate
4: the coloring phototonus layer
4 ': the coloring phototonus layer
4 ": the coloring phototonus layer
5: photomask 51: glass plate
52: light shield layer
53: the transmittance section
6: light
Embodiment
Photosensitive composition of the present invention (below be designated as in line with the color sensation photosensitive resin composition) contains, (A) pigment, (B) binder polymer, (C) optical polymerism compound, (D) Photoepolymerizationinitiater initiater, (E) pigment dispersing agent and (F) solvent.
(A) pigment can be organic organic pigment, also can be the inorganic pigment of inorganics.Inorganic pigment can be enumerated the inorganic salts (body pigment) of metal oxide, metal complex salt, barium sulphate etc.In this type of pigment, use organic pigment to be advisable.
Organic pigment can specifically be enumerated, and is categorized as the pigment of Pigment among the coulour index (The Society of Dyers andColourists publication).Specifically can enumerate C.I. pigment yellow (pigment yellow)-1, C.I. pigment yellow-3, C.I. pigment yellow-12, C.I. pigment yellow-13, C.I. pigment yellow-14, C.I. pigment yellow-15, C.I. pigment yellow-16, C.I. pigment yellow-17, C.I. pigment yellow-20, C.I. pigment yellow-24, C.I. pigment yellow-31, C.I. pigment yellow-53, C.I. pigment yellow-83, C.I. pigment yellow-86, C.I. pigment yellow-93, C.I. pigment yellow-94, C.I. pigment yellow-109, C.I. pigment yellow-110, C.I. pigment yellow-117, C.I. pigment yellow-125, C.I. pigment yellow-128, C.I. pigment yellow-137, C.I. pigment yellow-138, C.I. pigment yellow-139, C.I. pigment yellow-147, C.I. pigment yellow-148, C.I. pigment yellow-150, C.I. pigment yellow-153, C.I. pigment yellow-154, C.I. pigment yellow-166, yellow uitramarine such as C.I. pigment yellow-173 grade; C.I. orange (the Pigment orange) 13 of pigment, C.I. pigment is orange 31, C.I. pigment orange 36, C.I. pigment is orange 38, and C.I. pigment is orange 40, C.I. pigment orange 42, C.I. pigment is orange 43, and C.I. pigment is orange 51, C.I. pigment orange 55, C.I. pigment orange 59, C.I. pigment is orange 61, and C.I. pigment is orange 64, C.I. pigment orange 65, C.I. pigment is orange 71, orange 73 orange pigments such as grade of C.I. pigment; C.I. paratonere (Pigmentred) 9, C.I. Pigment Red 97, C.I. paratonere 105, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 149, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 180, C.I. paratonere 192, C.I. pigment red 21 5, C.I. pigment red 21 6, C.I. paratonere 224, C.I. pigment 242, C.I. paratonere 254, C.I. pigment 264, red pigments such as C.I. paratonere 265; C.I. alizarol saphirol (Pigmentblue) 15, the C.I. pigment blue 15: 3, the C.I. pigment blue 15: 4, the C.I. pigment blue 15: 6, blue pigments such as C.I. pigment blue 60; C.I. pigment violet rowland (Pigmentviolet) 1, C.I. pigment violet rowland 19, C.I. pigment violet rowland 23, C.I. pigment violet rowland 29, C.I. pigment violet rowland 32, C.I. pigment violet rowland 36, pansy (purple) pigment such as C.I. pigment violet rowland 38; C.I. naphthol green (Pigmentgreen) 7, viridine greens such as C.I. pigment green 36; C.I. brown (Pigmentbrown) 23 of pigment, brown 25 browns such as grade of C.I. pigment; Deng.This type of organic pigment can use separately separately, also can mix more than 2 kinds and use.
This type of organic pigment can carry out surface treatment that rosin (rosin) handled, adopted the pigment derivative that imports acidic groups or basic group etc., utilize the skill (graft) that connects of the surface of pigments of macromolecular compound etc. to handle, utilize the micronize of sulfuric acid micronize method to handle or remove the cleaning treatment by organic solvent or water etc. of impurity for purpose as required.The particle diameter of this type of organic pigment is probably about below the above 150nm of 10nm.
The content of pigment, be contained in relatively in line with the solid constituent after the volatilization of the volatile component (solvent) of color sensation photosensitive resin composition (below be designated as this solid constituent), with percentage by weight usually more than 5%, if will form fully painted painted figure more than 15%, better more than 20%, be preferably in more than 30%,, be preferably in 45% following scope usually below 60%.And, when using organic pigment, the use amount of this organic pigment, the pigment total amount, is preferably in more than 55% usually more than 50% with percentage by weight relatively, and pigment all (100%) all is that organic pigment is also passable.
(B) binder polymer uses as the multipolymer of (methyl) acrylic acid and (methyl) benzyl acrylate, and more than 25% below 40%, acid number is more than 90 below 160 with molar percentage for the content of (methyl) acrylic acid structure unit, weight average molecular weight (M
W) be advisable about below 40000 more than 20000.The acid number of binder polymer can be used, the water-soluble 10cm of binder polymer 1g
3With acetone 40cm
3Mixed solvent, titration potassium hydroxide aqueous solution limit, limit is measured the method for its pH and is obtained.Weight average molecular weight (M
W) be to be the value that benchmark is measured by permeation chromatography (GPC) with the polystyrene.
In line with the binder polymer content of color sensation photosensitive resin composition, this solid constituent, is preferably in more than 20% usually more than 5% with percentage by weight relatively, below 90%, is preferably in below 55% usually.
(C) the optical polymerism compound is, carries out polymeric compounds according to the living radical that is produced from Photoepolymerizationinitiater initiater by rayed, acid etc., can enumerate the compound as the carbon-carbon unsaturated link with polymerism.
This type of optical polymerism compound with 4 polyfunctional group optical polymerism compounds more than the functional group for well.As 4 polyfunctional group optical polymerism compounds more than the functional group, can enumerate tetramethylol methane tetraacrylate, pentaerythrite tetra methylacrylate, dipentaerythritol five acrylate, dipentaerythritol tetra methylacrylate, dipentaerythritol acrylate, dipentaerythritol six methacrylates etc.
In line with the optical polymerism compounds content of color sensation photosensitive resin composition, this solid constituent relatively,, is preferably in more than 10% below 45% better more than 3% below 50% usually more than 1% below 60% with percentage by weight.
(D) Photoepolymerizationinitiater initiater can be enumerated by rayed and produce the living radical propellant of living radical, acidic acid-producing agent etc.As the living radical propellant, for example can enumerating, acetophenone is that Photoepolymerizationinitiater initiater, benzoin are that Photoepolymerizationinitiater initiater, triazine are Photoepolymerizationinitiater initiater, benzoyl benzene series Photoepolymerizationinitiater initiater etc.Wherein acetophenone is that Photoepolymerizationinitiater initiater is for well, preferably so that 2-methyl-2-morpholino-1-(4-methyl thio phenyl) propane-1-ketone is the initiating agent of major component.
As acetophenone is Photoepolymerizationinitiater initiater, can enumerate 2-methyl-2-morpholino-1-(4-methyl thio phenyl) propane-1-ketone, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, 1-hydroxyl cyclohexyl benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] oligomer etc. of propane-1-ketone.
As benzoin is Photoepolymerizationinitiater initiater, for example can enumerate benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether etc.
As triazine is Photoepolymerizationinitiater initiater, for example can enumerate 2,4-two (trichloromethyl)-6-(4-methoxyphenyl)-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-(4-methoxyl naphthyl)-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-piperonyl-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-(4-methoxyl-styrene)-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl]-1,3,5-triazines, 2,4-two (trichloromethyl)-6-[2-(furans-2-yl) vinyl]-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-1,3, the 5-triazine, 2,4-two (trichloromethyl)-6-[2-(3, the 4-Dimethoxyphenyl) vinyl]-1,3,5-triazine etc.
As benzoyl benzene series Photoepolymerizationinitiater initiater, for example can enumerate benzophenone, o-benzoylbenzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide, 3,3 ', 4,4 '-tetra-tert peroxide carbonyl benzophenone, 2,4,6-tri-methyl benzophenone etc.
As the living radical propellant, for example, can use 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, 2,2 '-two (o-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 10-butyl-2-chloro-acridine ketone, 2-EAQ, dibenzoyl, 9,10-phenanthrenequione, camphorquinone, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc.
As acid-producing agent, for example can enumerate salts such as 4-hydroxy benzenes dimethyl sulfonium p-toluene sulfonate, 4-hydroxy benzenes dimethyl sulfonium hexafluoro antimonate, 4-acetyloxy phenyl dimethyl sulfonium p-toluene sulfonate, 4-acetyloxy phenyl methylbenzene sulfonium hexafluoro antimonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoro antimonate, diphenyl iodonium p-toluene sulfonate, diphenyl iodonium hexafluoro antimonate, nitrobiphenyl acyl tosylate class, benzoin tosylate class etc.
And, in the above-claimed cpd as the living radical propellant, the compound that produces living radical and acid is simultaneously arranged, be that Photoepolymerizationinitiater initiater isoreactivity free radical generating agent also can use and is acid-producing agent as triazine.
This type of Photoepolymerizationinitiater initiater can use separately separately, use more than 2 kinds also capable of being combined.
In line with the Photoepolymerizationinitiater initiater content of color sensation photosensitive resin composition, this solid constituent relatively, is preferably in more than 3% below 20% usually more than 1% below 25% with percentage by weight.
Also can contain photopolymerization in line with the color sensation photosensitive resin composition and cause auxiliary agent.It is to be used in combination with Photoepolymerizationinitiater initiater and to be used to promote the polymeric compounds of optical polymerism compound that photopolymerization causes auxiliary agent.Cause auxiliary agent as photopolymerization, for example, can enumerate thioxanthones is that photopolymerization causes auxiliary agent, amine is that photopolymerization causes auxiliary agent, alkoxy anthracene is that photopolymerization causes auxiliary agent etc.
As thioxanthones is that photopolymerization causes auxiliary agent, for example, can enumerate 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.
As amine is that photopolymerization causes auxiliary agent, for example, can enumerate triethanolamine, the methyl diglycollic amide, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylamino isoamyl benzoate, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, N, the N-dimethyl-p-toluidine, 4,4 '-two (dimethylamino) benzophenone (common name Michler's keton), 4,4 '-two (diethylamino) benzophenone is [as (EAB-F), (protect native chemical industry (strain) system, commercially available), 4,4 '-two (ethylmethylamino) benzophenone etc.
As alkoxy anthracene is that photopolymerization causes auxiliary agent, can enumerate 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.
When using this type of photopolymerization to cause auxiliary agent, its use amount is with respect to every mole of Photoepolymerizationinitiater initiater normally below 10 moles, preferably more than 0.01 mole below 5 moles.
Among the present invention, it is Photoepolymerizationinitiater initiater that Photoepolymerizationinitiater initiater uses acetophenone, and photopolymerization causes auxiliary agent to use thioxanthones be Photoepolymerizationinitiater initiater to well.
Contain (E) pigment dispersing agent in line with the color sensation photosensitive resin composition.By containing pigment dispersing agent, can contain pigment with homogeneously dispersed state, can obtain evenly painted painted figure.This type of pigment dispersing agent is that spreading agent, ester are spreading agent, polyurethane series spreading agent for well with polyethyleneimine.Be used alone or in combination of two or more kinds separately.
The content of this pigment dispersing agent is more than 0.01 weight portion with respect to per 1 weight portion pigment usually, is preferably in more than 0.05 weight portion, below 1 weight portion, is preferably in below 0.5 weight portion usually.
In line with the color sensation photosensitive resin composition, with state manufacturing, the preservation of (F) solvent dilution.As (F) solvent, can enumerate the identical solvent that is used in photosensitive composition usually, for example, ethylene glycol monoalkyl ether classes such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ether classes such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and dibutyl ethylene glycol ether;
Ethylene glycol alkyl ether acetate (ester) classes such as methyl acetic acid ester cellosolve, ethylhexoate cellosolve;
Propylene glycol monomethylether acetate (ester), dihydroxypropane single-ether acetate (ester), propylene glycol monopropyl ether acetate (ester), propylene glycol monobutyl ether acetate (ester) and methoxyl amyl group acetate aklylene glycol alkyl ether acetate (ester) classes such as (esters);
Benzene,toluene,xylenes etc. are aromatic hydrocarbon based;
Methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone;
Alcohols such as ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine;
Ester classes such as 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters;
Cyclic ester classes such as gamma-butyrolacton.
This kind solvent can use separately or be used in combination more than 2 kinds separately, its use amount is to represent with the content in line with in the color sensation photosensitive resin composition under the state of solvent dilution,, be preferably in more than 60% below 85% usually more than 50% below 90% with percentage by weight.
Be diluted in solvent in line with in the color sensation photosensitive resin composition, (A) pigment is scattered in the composition usually.
(B) binder polymer, (C) optical polymerism compound, (D) Photoepolymerizationinitiater initiater, (E) dye dispersant are dissolved in (F) solvent.
In line with the color sensation photosensitive resin composition be, after being coated with this photosensitive composition with the rotary plating method on the glass baseplate surface, made the volatile component volatilization down in dry 3 minutes at 100 ℃, form film (thickness is 1.6 μ m), with the gained film immersion in the alkaline aqueous solution of 2500 times of weight of this film (with percentage by weight, contain potassium hydroxide 0.05% respectively, the aqueous solution of sodium butylnaphthalenesulfonate 0.2%), with stirring machine this aqueous solution was stirred for 80 seconds with 300 rev/mins, when measuring the size-grade distribution of the particle that is contained in this aqueous solution by light method at random, accumulate 90% particle diameter below 0.5 μ m, the photosensitive composition of maximum particle diameter below 1.0 μ m.
And, photosensitive composition of the present invention is, after being coated with this photosensitive composition with the rotary plating method on the glass baseplate surface, made the volatile component volatilization down in dry 3 minutes at 100 ℃, form film (thickness is 1.6 μ m), with the gained film immersion in this solvent of 2500 times of weight of this film, with stirring machine this solvent was stirred for 80 seconds with 300 rev/mins, by light method at random measure be contained in this solvent be coated with the size-grade distribution of film component the time, accumulate 90% particle diameter below 0.5 μ m, the photosensitive composition of maximum particle diameter below 1.0 μ m.
Glass substrate should use Corning Incorporated's system, [#7059] glass substrate.
In order to form the film that thickness is 1.6 μ m, want the use amount of suitable selective solvent, the rotational speed during with rotary plating method coating photosensitive composition, temperature etc., for example should take to reduce the use amount or the measures such as attenuating rotating speed or reduction temperature of solvent, should take to strengthen the use amount of solvent or increase measures such as rotation number, raising temperature in order to reduce thickness in order to strengthen thickness.
In order to make above-mentioned accumulation 90% particle diameter below 0.5 μ m, maximum particle diameter is (alkaline aqueous solution dipping and (F) solvent impregnated situation) below 1.0 μ m, and should use polyethyleneimine as pigment dispersing agent is that spreading agent, ester are spreading agent or polyurethane dispersant.
Also can add adjuvants such as the macromolecular compound beyond filling agent, (B) binder polymer, adhesion promoter, antioxidant, ultraviolet light absorber, coagulation-prevention agent, organic acid, organic aminated compound, rigidizer in line with the color sensation photosensitive resin composition.
As filling agent, for example can enumerate the particulate of glass, aluminium oxide etc.
(B) binder polymer can be enumerated as polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, polyacrylic acid fluoroalkyl ester etc. with macromolecular compound.
As adhesion promoter, can enumerate for example ethene trimethoxy silane, vinyl triethoxysilane, vinyl three (tris) (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, 3-metacryloxy propyl trimethoxy silicane, 3-sulfydryl propyl trimethoxy silicane etc.
As antioxidant, for example can enumerate 2,2-sulfo-two (4-methyl-6-tert butyl phenol), 2,6-two-tert-butyl phenol etc.
As ultraviolet light absorber, can enumerate 2-(3-tert-butyl-5-methyl-2-hydroxy benzenes)-5-chlorobenzene triazole, alkoxy benzophenone etc.
Prevent agent as condensing, can enumerate sodium polyacrylate etc.
As organic acid, can enumerate formic acid, acetate, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethacetic acid, enanthic acid, aliphatic monocarboxylic acid class such as sad,
Aliphatic dicarboxylic acid classes such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, tridecandioic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, cyclohexyl dicarboxylic acid, methylene-succinic acid, citraconic acid, cis-1 (maleic acid), fumaroyl, mesaconic acid
Aliphatic tricarboxylic acids classes such as tricarballylic acid, aconitic acid's (aconitic acid), camphoronic acid,
Benzoic acid, toluic acid, cumfrey (cumfrey), mesitylenic acid, 3, aromatic monocarboxylate's classes such as 5-mesitylenic acid,
Aromatic dicarboxylic acid classes such as phthalic acid, isophthalic acid, terephthalic acids,
Aromatic series polycarboxylic acids such as trimellitic acid, trimesic acid, mellophanic acid, Pyromellitic Acid.
As organic aminated compound, can enumerate single (ring) alkyl amines such as n-propylamine, isopropylamine, n-butylamine, isobutyl amine, sec-butylamine, tert-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane base amine, dodecyl amine, cyclohexylamine, 2-methyl cyclohexylamine, 3-methyl cyclohexylamine, 4-methyl cyclohexylamine
Two (ring) alkyl amines such as Methylethyl amine, diethylamide, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-iso-butylmanice, di-sec-butylamine, two tert-butylamines, di-n-propylamine, two n-hexylamines, methyl cyclohexylamine, the own cyclohexylamine of second, dicyclohexyl amine
Three (ring) alkyl amines such as dimethylethyl amine, methyl diethylamide, triethylamine, dimethyl n propylamine, methyl di-n-propylamine, ethyl di-n-propylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, triisobutylamine, tri sec-butylamine, three tert-butylamines, tri-n-amyl amine, three n-hexylamines, dimethyl cyclohexyl amine, diethyl cyclohexylamine, methyl bicyclic hexylamine, ethyl dicyclohexyl amine, tricyclohexyltin amine
The 2-ethylaminoethanol, single (ring) alkanolamine such as 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, 4-amino-1-butanols, 5-amino-1-amylalcohol, 6-amino-1-hexanol, 4-amino-1-cyclohexanol,
Two (ring) alkanolamine such as diethanolamine, two n-propanol amine, diisopropanolamine, two normal butyl alcohol amine, two isobutyl hydramine, two n-amyl alcohol amine, two n-hexyl alcohol amine, two (4-cyclohexanol) amine,
Three (ring) alkanolamine such as triethanolamine, three n-propanol amine, triisopropanolamine, three normal butyl alcohol amine, three isobutyl hydramine, three n-amyl alcohol amine, three n-hexyl alcohol amine, three (4-cyclohexanol) amine,
3-amino-1,2-propylene glycol, 2-amino-1, ammediol, 4-amino-1,2-butylene glycol, 4-amino-1,3-butylene glycol, 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propylene glycol, 3-diethylamino-1,2-propylene glycol, 2-dimethylamino-1, ammediol, 2-diethylamino-1, amino (ring) alkanediol class such as ammediol
1-amino cyclopentyl ketone methyl alcohol, 4-amino cyclopentyl ketone methyl alcohol, the amino cyclohexanone methyl alcohol of 1-, the amino cyclohexanone methyl alcohol of 4-, 4-dimethylamino cyclopentane methyl alcohol, 4-diethylamino cyclopentane methyl alcohol, 4-dimethylamino cyclohexane methanol, 4-diethylamino cyclohexane methanol etc. contain amino cyclanone methyl alcohol class
Aminocarboxylic acids such as Beta-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaprolc acid, the amino cyclopropyl carboxylic acid of 1-, the amino cyclohexane carboxylic of 1-, the amino cyclohexane carboxylic of 4-
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, p-n-pro-pyl aniline, p-isopropyl aniline, p-n-butyl aniline, p-tert-butyl group aniline, 1-naphthyl aniline, 2-naphthyl aniline, N, accelerine, N, N-diethylaniline, p-methyl-N, aromatic amines such as accelerine
Aminobenzyl alcohol classes such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylamino benzylalcohol, p-diethylamino benzylalcohol,
Amino phenols such as o-amino-phenol, m-amino-phenol, p-amino-phenol, p-dimethylamino phenol, p-diethylamino phenol,
Aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, p-diethyl amino yl benzoic acid.
As rigidizer, for example can enumerate by the heating with binder polymer (B) in carboxyl reaction can binder polymer is crosslinked compound.In addition, also can enumerate the compound that carries out homopolymerization and painted figure is solidified.As this compound, can enumerate epoxy compound, oxetane compound etc.
As epoxy compound, can enumerate bisphenol-A is epoxy resin, hydrogenated bisphenol A is an epoxy resin, Bisphenol F is an epoxy resin, A Hydrogenated Bisphenol A F is an epoxy resin, phenolic resin varnish type epoxy resin, other fragrant family epoxy resin, alicyclic ring family epoxy resin, hetero ring type epoxy resin, ethylene oxidic ester is a resin, glycidyl amine is a resin, epoxidation wet goods epoxy resin, and the brominated derivative of this based epoxy resin, aliphatics beyond epoxy resin and the brominated derivative thereof, alicyclic or aromatic epoxy compound, the epoxide of butadiene (being total to) polymkeric substance, the epoxide of isoprene (being total to) polymkeric substance, (being total to) polymkeric substance of (different) glycidyl acrylate, isocyanuric acid three-glycidyl ester etc.
As oxetane compound, can enumerate carbonic ester dioxetane, xylylene dioxetane, adipate dioxetane, terephthalate dioxetane, cyclohexane dicarboxylic acid dioxetane etc.
Photosensitive composition of the present invention also can contain, when containing the epoxy compound of making rigidizer, oxetane compound, also can contain the compound of the oxetanes skeleton ring-opening polymerization of the epoxy radicals that can make epoxy compound, oxetane compound.This compounds for example can be enumerated, polybasic carboxylic acid class, polybasic acid anhydride class, acid-producing agent etc.
The polybasic carboxylic acid class for example can be enumerated, phthalic acid, 3,4-dimethyl phthalic acid, isophthalic acid, terephthalic acid (TPA), Pyromellitic Acid, trimesic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 3,3 ', 4, aromatic series polybasic carboxylic acid classes such as 4 '-benzophenone tetrabasic carboxylic acid
Succinic acid, glutaric acid, hexane diacid, 1,2,3, aliphatics polybasic carboxylic acid classes such as 4-butyl tetrabasic carboxylic acid, maleic acid, fumaroyl, methylene-succinic acid,
Hexahydro-phthalic acid, 3,4-dimethyl tetrahydro phthalic acid, hexahydro isophthalic acid, hexahydroterephthalic acid, 1,2,4-encircles penta tricarboxylic acids, 1,2,4-hexamethylene tricarboxylic acids, ring penta tetrabasic carboxylic acid, 1,2,4, alicyclic polybasic carboxylic acid classes such as 5-hexamethylene tetrabasic carboxylic acid etc.
As polybasic acid anhydride, can enumerate phthalate anhydride, pyromellitic dianhydride, trimesic acid acid anhydride, 3,3 ', 4, aromatic series polybasic acid anhydride classes such as 4 '-benzophenone tetracarboxylic dianhydride,
Itaconic anhydride, succinic anhydride, citraconic acid acid anhydride, dodecenyl succinic anhydride, tricarballylic acid acid anhydride, maleic anhydride, 1,2,3, aliphatics polybasic acid anhydride classes such as 4-butyl tetracarboxylic dianhydride,
Hexahydro phthalic anhydride, 3,4-dimethyl tetrahydro phthalate anhydride, 1,2,4-encircles penta tricarboxylic acid anhydride, 1,2,4-hexamethylene tricarboxylic acid anhydride, ring penta tetracarboxylic dianhydride, 1,2,4, alicyclic polybasic acid anhydride classes such as 5-hexamethylene tetracarboxylic dianhydride, Ha イ ミ Star Network acid anhydrides, Na ヅ Application acid anhydrides
Ethylene glycol bis trimellitic acid, glycerine three trimellitate acid anhydrides etc. contain the carboxyanhydrides of ester group etc.
Carboxyanhydrides can use, on the market the epoxy resin hardener of Xiao Shouing.This type of epoxy resin hardener can be enumerated trade name [adeka hardner-EH-700] (rising sun electrochemical industry (strain)), trade name [rikasit HH] (new Japanese physics and chemistry (strain)), trade name [MH-700] (new Japanese physics and chemistry (strain)) etc.
This type of rigidizer can use separately or be used in combination more than 2 kinds separately.
Go up coating in line with the color sensation photosensitive resin composition at substrate (3), remove (F) solvent, just can form the layer 4 that forms by this solid constituent at substrate 3.Coating can be used in line with the color sensation photosensitive resin composition, coats method, method of spin coating of substrate etc. with homogeneous thickness.After the coating, the method for available heating is removed (F) solvent.Heating-up temperature is for example, the scope more than 60 ℃ below 120 ℃.The formed layer 4 of this solid constituent is, by the formed layer of the solid constituent of removing volatile components such as (F) solvent in line with the color sensation photosensitive resin composition.
The formed layer 4 of this type of this solid constituent, its thickness is generally below 2.5 μ m more than the 0.8 μ m, but, suitably select use amount, the rotational speed with method of spin coating coating during, temperature etc. in line with the color sensation photosensitive resin composition in line with the contained solvent of color sensation photosensitive resin composition in order to guarantee this thickness.For example, can reduce use amount, minimizing rotation number, the temperature that reduces of solvent in order to strengthen thickness; In order to reduce thickness, can increase use amount, increase rotation number, the temperature that improves of solvent.
For well, this i line is that wavelength is the light of 365nm to irradiates light with the i line.I line parallel light can be shone by the exposure machine that is used to make color filter.By the slit irradiation of wire spoke 100 μ m, can irradiate wire spoke (W) is the wire i line parallel light of 100 μ m.
Behind the irradiation i line parallel light, the available method that impregnated in alkaline aqueous solution is developed.Alkaline aqueous solution can be enumerated the aqueous solution that contains potassium hydroxide and sodium butylnaphthalenesulfonate.Specifically, this aqueous solution of relative 100 weight portions, potassium hydroxide content is 0.05 weight portion, the content of sodium butylnaphthalenesulfonate is 0.05 weight portion.Normally about 23 ℃, dip time is about normally 40 seconds～120 seconds for the temperature of alkaline aqueous solution.Behind the dipping, the mode that washes with water is usually removed developer solution.
After the development, formed painted figure in about 20 minutes by heating under about 180 ℃～240 ℃ the heating-up temperature, but this figure is a wire.
In line with the color sensation photosensitive resin composition, relative solid constituent, with percentage by weight, (A) content of colorant is more than 15% below 50%, (B) content of binder polymer is more than 20% below 55%, (C) content of optical polymerism compound is more than 10% below 45%, and (D) content of Photoepolymerizationinitiater initiater is more than 3% below 20%, and (A) pigment 1 weight portion (E) pigment dispersing agent is 0.01～1 weight portion for well relatively.
The formation method of painted figure of the present invention is characterized in that using forming on substrate 2 in line with the color sensation photosensitive resin composition and films, and behind this layer that exposes, developing is.The manufacture method of color filter of the present invention is characterised in that, adopts the formation method of above-mentioned painted figure, and the formation method of this painted figure is fit to be used in the technology of manufacture method of color filter.
Specifically, form layer 4 (Fig. 2 (a)) that formed by this solid constituent at substrate 2, exposure is developed (Fig. 2 (c)) by layer 4 back (Fig. 2 (b)) that this solid constituent forms.
On substrate 3, be coated be diluted in (F) solvent in line with the color sensation photosensitive resin composition, form the layer 4 that forms by this solid constituent.Coating process can adopt and can photosensitive composition be coated method on the substrate, for example method of spin coating etc. with homogeneous thickness.After the coating, remove and desolvate.The mode of available heating is removed and is desolvated.The formed layer 4 of this solid constituent is that by the formed layer of the solid constituent of removing volatile components such as (F) solvent in line with the color sensation photosensitive resin composition, its thickness is generally below 2.5 μ m more than the 0.8 μ m.
Then, the formed layer of this solid constituent 4 (Fig. 2 (b)) that expose.For example by photomask 5 irradiation light 6.Light 6 uses the ultraviolet ray that is called i line (wavelength 365nm) usually.Light is by photomask irradiation, and this photomask 5 is that the light shield layer 52 that glass plate 5 surfaces are provided with shield lights forms.The part that shadow shield is not set in the glass plate is exactly the transmittance section 53 that light sees through, the formed layer of this solid constituent 4 is figures that the figure according to this transmittance section exposes and forms, and forms field of not shining 41 that light do not shine and the irradiation field of being arrived by irradiate light 42.The exposure basis of the light in irradiation field 42, kind, the content of the kind of the weight average molecular weight of kind of employed (A) colorant and content, (B) binder polymer, content, list amount body unit composition, (C) optical polymerism compound, content, (D) Photoepolymerizationinitiater initiater wait suitably and select.
After the exposure, develop (Fig. 2 (c)).The formed layer of this solid constituent after the exposure 4 contact with developer solution, develop, specifically formation on the surface be impregnated in developer solution by the substrate 3 of formed layer 4 of this solid constituent.Developer solution uses alkaline aqueous solution usually.Alkaline aqueous solution can be enumerated, the aqueous solution of alkali compounds such as sodium carbonate, sal tartari, NaOH, potassium hydroxide, tetramethyl ammonia oxyhydroxide.By developing, eliminate the not irradiation field 41 that light does not shine in the formed layer 4 of this solid constituent.On the other hand, irradiate light field 42 continues to keep, and forms painted figure 2.
After the development, wash with water usually, dry method obtains painted figure 2.After the drying, also can heat.By the temper tiniting figure, can increase hardness, physical strength also has and improves tendency, contains the situation of rigidizer in line with the color sensation photosensitive resin composition, can improve physical strength more.Heating-up temperature is generally more than 180 ℃, preferably more than 200 ℃, is generally below 250 ℃.
The painted figure 2 that forms like this, its section configuration are along cone-shaped and even rectangular-shaped.
So forming on the substrate 3 of painted figure 2, form again and contain the formed layer of this solid constituent different colours colorant, painted different colours 4 ' (Fig. 3 (a)), this layer 4 ' back (Fig. 3 (b)) of exposing by developing (Fig. 3 (c)), forms painted figure 2 ' again.Repeat aforesaid operations by what use painted different colours in line with the color sensation photosensitive resin composition, can form the color-patch map 2 of Red Green Blue in turn " (Fig. 4), can make the color filter 1 (Fig. 1) that contains painted figure 2.
Embodiment
Below, by embodiment the present invention is described in further detail, but the present invention is not limited to these
Embodiment.
The assay method of particle diameter: adopt light scattering method.Employed device is LEED ﹠amp; NORTHRUPCOMPANY society system, MICROTRAC particle size determination device UPA 150, form 9230 UPA.
[manufacturing of blue-colored photosensitive polymer combination]
With the multipolymer of (B) methacrylate and benzene methacrylate [ratio of methacrylate unit and benzene methacrylate unit is, with amount of substance than (mol ratio) 30: 70, acid number be 113, weight average molecular weight is 25000] 0.828 weight portion,
(C) two or five erythrites, six acrylate, 0.828 weight portion,
(D) Photoepolymerizationinitiater initiater [2-methyl-2-morpholino-1-(4-methyl thio phenyl) propane-1-ketone] 0.199 weight portion,
(D) photopolymerization initiation auxiliary agent [2,4-diethyl sulfenyl thioxanthones] 0.099 weight portion reaches
(F) mixing of propylene glycol methyl ether acetate 6.522 weight portions has obtained potpourri 1.
With (A) pigment [C.I. pigment blue 15: 6] 1.030 weight portions,
(A) pigment [C.I. pigment violet rowland 23] 0.016 weight portion,
(E) polyethyleneimine is that spreading agent 0.298 weight portion reaches
(F) propylene glycol methyl ether acetate 5.178 weight portions are mixed into 2 back mixing with potpourri 1 of potpourri and have obtained photosensitive composition (blueness).
[dissolubility of filming]
In glass substrate [Corning Incorporated's system, (#7059)] on (3) surface, after being coated with above-mentioned gained photosensitive composition with method of spin coating, 100 ℃ of down dry 3 minutes its volatile components that volatilize form photosensitive composition layer [thickness is 1.6 μ m] (4).It is filmed impregnated in alkaline aqueous solution [with percentage by weight, the aqueous solution that respectively contains potassium hydroxide 0.05%, sodium butylnaphthalenesulfonate 0.2%], after with stirring machine developer solution being stirred for 80 seconds with 300rpm, the sight glass substrate then can be seen the dissolving of filming, and the transmittance of glass substrate is 100%.And the result of the size-grade distribution of the particle that exists in the developer solution of investigation dissolving back accumulates 90% particle diameter: 0.085 μ m, mean grain size: 0.05 μ m, maximum particle diameter: 0.15 μ m.
And gained filmed impregnated in propylene glycol methyl ether acetate equally, with stirring machine propylene glycol methyl ether acetate was stirred for 80 seconds with 300rpm after, the sight glass substrate then can be seen the dissolving of filming, the transmittance of glass substrate is 100%.And the result of the size-grade distribution of the particle that exists in the propylene glycol methyl ether acetate of investigation dissolving back accumulates 90% particle diameter: 0.085 μ m, mean grain size: 0.05 μ m, maximum particle diameter: 0.15 μ m.
[formation of blue picture element]
In glass substrate [Corning Incorporated's system, (#7059)] on (3) surface, after being coated with above-mentioned gained photosensitive composition with method of spin coating, 100 ℃ of down dry 3 minutes its volatile components that volatilize form photosensitive composition layer [thickness is 1.6 μ m] (4).
After the cooling, shine this photosensitive composition layer (4) by photomask with i line [wavelength 365nm] and expose.The light source of i line uses ultrahigh pressure mercury lamp, shines after becoming directional light.The irradiation light quantity is 150mJ/cm
2Photomask uses the photomask of the formation wire look pixel of wire spoke 3 μ m, 4 μ m, 5 μ m, 6 μ m, 7 μ m, 8 μ m, 9 μ m, 10 μ m, 20 μ m, 30 μ m, 40 μ m, 50 μ m and 100 μ m.
Glass substrate after will exposing then [surface has formed the photosensitive composition layer] impregnated in developer solution [with percentage by weight, the aqueous solution that respectively contains potassium hydroxide 0.05%, sodium butylnaphthalenesulfonate 0.2%] develop for 80 seconds, after the pure water cleaning, with 220 ℃ of heating 20 minutes, form red pixel 2 (Fig. 2 (c)).The section configuration of formed blue picture element is along cone-shaped, does not have coarse phenomenon, and is good.
[manufacturing of blue-colored photosensitive polymer combination]
Polyethyleneimine among the embodiment 1 is that spreading agent changes into outside the polyurethane series spreading agent, mixes having obtained photosensitive composition (blueness) equally with embodiment.
[dissolubility of filming]
Replace outside the embodiment 1 gained photosensitive composition with above-mentioned gained photosensitive composition, operation similarly to Example 1, the result of the size-grade distribution of the particle that exists in the developer solution after the dissolving that inquiry agency must be filmed, accumulate 90% particle diameter: 0.085 μ m, mean grain size: 0.05 μ m, maximum particle diameter: 0.15 μ m.
The result of the size-grade distribution of the particle that exists in the investigation propylene glycol methyl ether acetate liquid accumulates 90% particle diameter: 0.085 μ m, mean grain size: 0.05 μ m, maximum particle diameter: 0.15 μ m.
[formation of blue picture element]
Replace outside the embodiment 1 gained photosensitive composition with above-mentioned gained photosensitive composition, operation similarly to Example 1, the section configuration of gained blue picture element is along cone-shaped, does not have coarse phenomenon, and is good.
Comparative example
[manufacturing of blue-colored photosensitive polymer combination]
With the interpolymer of (B) methacrylate and benzene methacrylate [ratio of methacrylate unit and benzene methacrylate unit is, with amount of substance than (mol ratio) 30: 70, acid number be 113, weight average molecular weight is 25000] 0.828 weight portion,
(C) two or five erythrites, six acrylate, 0.828 weight portion,
(D) Photoepolymerizationinitiater initiater [2-methyl-2-morpholine-1-(4-methylbenzene sulfenyl) propane-1-ketone] 0.199 weight portion,
(D) photopolymerization initiation auxiliary agent [2,4-diethyl sulfenyl thioxanthones] 0.099 weight portion reaches
(F) mixing of propylene glycol methyl ether acetate 6.522 weight portions has obtained potpourri 1.
With (A) pigment [C.I. pigment blue 15: 6] 1.030 weight portions,
(A) pigment [C.I. pigment violet rowland 23] 0.016 weight portion,
(E) modified acroleic acid is that spreading agent 0.298 weight portion reaches
(F) propylene glycol methyl ether acetate 5.178 weight portions are mixed into 2 back mixing with potpourri of potpourri and have obtained photosensitive composition (blueness).
[dissolubility of filming]
Replace outside the embodiment 1 gained photosensitive composition with above-mentioned gained photosensitive composition, operation similarly to Example 1, gained is filmed and is added on developer solution, reaches the propylene glycol methyl ether acetate stirring, then films into piece and peels off.Be the level that to distinguish affirmation with naked eyes, almost do not have painted in developer solution, and propylene glycol methyl ether acetate.
[formation of blue picture element]
Replace outside the embodiment 1 gained photosensitive composition with above-mentioned gained photosensitive composition, operation similarly to Example 1, the section configuration of gained blue picture element is contrary cone-shaped, the coarse phenomenon of sidewall is serious
Photosensitive composition of the present invention is the highly sensitive while, during development, can form section configuration and be suitable cone-shaped and even painted figure rectangular-shaped, that do not have coarse phenomenon.
Claims (5)
1. photosensitive composition, contain (A) pigment, (B) binder polymer, (C) optical polymerism compound, (D) Photoepolymerizationinitiater initiater, (E) pigment dispersing agent and (F) solvent, this photosensitive composition, after being coated with this photosensitive composition with method of spin coating on the glass baseplate surface, made the volatile component volatilization down in dry 3 minutes at 100 ℃, forming thickness is the film of 1.6 μ m, with the alkaline aqueous solution of gained film immersion in 2500 times of weight of this film, described alkaline aqueous solution is with percentage by weight, respectively contain potassium hydroxide 0.05%, the aqueous solution of sodium butylnaphthalenesulfonate 0.2%, with stirring machine this aqueous solution was stirred for 80 seconds with 300 rev/mins, when measuring the size-grade distribution of the particle that is contained in this aqueous solution by light scattering method, accumulate 90% particle diameter below 0.5 μ m, maximum particle diameter is below 1.0 μ m, solid constituent for photosensitive composition, with percentage by weight, (A) content of pigment is more than 15% below 50%, (B) content of binder polymer is more than 20% below 55%, (C) content of optical polymerism compound is more than 10% below 45%, (D) content of Photoepolymerizationinitiater initiater is more than 3% below 20%, (A) pigment 1 weight portion (E) pigment dispersing agent is 0.01～1 weight portion relatively, and (E) pigment dispersing agent is that polyethyleneimine is spreading agent or polyurethane series spreading agent.
2. photosensitive composition according to claim 1, wherein (D) Photoepolymerizationinitiater initiater is that acetophenone is a Photoepolymerizationinitiater initiater.
3. the formation method of a painted figure is characterized in that claim 1 or 2 described photosensitive compositions are coated on the substrate, forms by drying and films, and exposes and develops after this is filmed.
4. the manufacture method of a color filter is characterized in that required color is carried out repeatedly the formation method of the described painted figure of claim 3.
5. the manufacture method of color filter according to claim 4 is characterized in that required color is red, green and blue.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001-379808 | 2001-12-13 | ||
| JP2001379808A JP2003177525A (en) | 2001-12-13 | 2001-12-13 | Colored photosensitive resin composition |
| JP2001379808 | 2001-12-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005100763704A Division CN1696830A (en) | 2001-12-13 | 2002-12-11 | Colored photosensitive resin composition |
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| Publication Number | Publication Date |
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| CN1425928A CN1425928A (en) | 2003-06-25 |
| CN1254702C true CN1254702C (en) | 2006-05-03 |
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| CNB021560218A Expired - Fee Related CN1254702C (en) | 2001-12-13 | 2002-12-11 | Colored light sensitive resin composition |
| CNA2005100763704A Pending CN1696830A (en) | 2001-12-13 | 2002-12-11 | Colored photosensitive resin composition |
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| CNA2005100763704A Pending CN1696830A (en) | 2001-12-13 | 2002-12-11 | Colored photosensitive resin composition |
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| JP (1) | JP2003177525A (en) |
| KR (1) | KR20030076193A (en) |
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| JP4597638B2 (en) * | 2003-11-14 | 2010-12-15 | 富士フイルム株式会社 | Method for producing photocurable composition, color filter, and method for evaluating photocurable composition |
| CN100448377C (en) * | 2004-05-25 | 2009-01-07 | 卢立新 | Crystal glass ash tray, its adhesive composition and use of said adhesive composition |
| TWI401533B (en) * | 2004-06-28 | 2013-07-11 | Sumitomo Chemical Co | Colored photosensitive resin composition |
| CN100354663C (en) * | 2004-07-02 | 2007-12-12 | 华生科技股份有限公司 | Method for producing color filter |
| JP4449983B2 (en) * | 2004-08-11 | 2010-04-14 | 日立化成工業株式会社 | Photosensitive resin composition and photosensitive film using the same |
| WO2007007685A1 (en) * | 2005-07-08 | 2007-01-18 | Toyo Ink Manufacturing Co., Ltd. | Dispersing agent, method for producing same, and pigment dispersion and ink containing such dispersing agent |
| TWI406062B (en) * | 2005-07-29 | 2013-08-21 | Sumitomo Chemical Co | A photosensitive resin composition for optical spacers, an optical spacers, and a liquid crystal display device |
| EP2404940B1 (en) * | 2005-08-03 | 2014-12-24 | The Inctec Inc. | Method for producing polymer composition and polymer composition |
| CN101154043B (en) * | 2006-09-26 | 2011-04-20 | 新应材股份有限公司 | High-resolution negative-type photoresist |
| KR101422071B1 (en) * | 2007-09-21 | 2014-08-13 | 주식회사 동진쎄미켐 | A slurry for producing pdp electrode |
| CN101162364B (en) * | 2007-11-30 | 2011-04-20 | 京东方科技集团股份有限公司 | Photosensitive resin composition and method of making the same and film build method |
| CN102125306A (en) * | 2011-04-18 | 2011-07-20 | 卢立新 | Crystal glass ashtray |
| KR101769190B1 (en) * | 2011-12-09 | 2017-08-17 | 아사히 가세이 이-매터리얼즈 가부시키가이샤 | Photosensitive resin composition, method for producing hardened relief pattern, semiconductor device and display device |
| CN109100916A (en) * | 2018-07-19 | 2018-12-28 | 江苏博砚电子科技有限公司 | A kind of high-performance color photosensitive polymer combination and preparation method thereof |
| JPWO2021166879A1 (en) * | 2020-02-21 | 2021-08-26 |
-
2001
- 2001-12-13 JP JP2001379808A patent/JP2003177525A/en active Pending
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2002
- 2002-12-10 TW TW091135642A patent/TWI313789B/en not_active IP Right Cessation
- 2002-12-11 KR KR1020020078731A patent/KR20030076193A/en not_active Application Discontinuation
- 2002-12-11 CN CNB021560218A patent/CN1254702C/en not_active Expired - Fee Related
- 2002-12-11 CN CNA2005100763704A patent/CN1696830A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN1696830A (en) | 2005-11-16 |
| CN1425928A (en) | 2003-06-25 |
| KR20030076193A (en) | 2003-09-26 |
| TWI313789B (en) | 2009-08-21 |
| TW200301401A (en) | 2003-07-01 |
| JP2003177525A (en) | 2003-06-27 |
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