CN101105630A - Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device - Google Patents
Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device Download PDFInfo
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- CN101105630A CN101105630A CNA2007101360146A CN200710136014A CN101105630A CN 101105630 A CN101105630 A CN 101105630A CN A2007101360146 A CNA2007101360146 A CN A2007101360146A CN 200710136014 A CN200710136014 A CN 200710136014A CN 101105630 A CN101105630 A CN 101105630A
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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
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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
-
- 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
- C09B19/00—Oxazine dyes
- C09B19/02—Bisoxazines prepared from aminoquinones
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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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
- G03F7/0005—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
- G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Optical Filters (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention relates to a radiation sensitive composition formed on the dyed layer which contains the following components: (A) a colorant, (B) an alkaline soluble resin, (C) a polyfunctional monomer and (D) a photopolymerization evocating agent, wherein the (B) alkaline soluble resin is the polyester which is provided with a alicyclic ring hydrocarbon skeleton at the backbone chain and a polymerized unsaturated bond at the side chain. The invention provides the radiation sensitive composition for forming the dyed layer which will not generate residue of the non-solute material or the scum of the pattern margin when it is developed, and will not generate the defect of the patter margin or the side-corroded dyed layer when the amount of the exposure is low.
Description
Technical field
The present invention relates to be used to form radiation-ray sensitive composition, color filter and the color liquid crystal display device of dyed layer.In more detail, relate to the radiation-ray sensitive composition that uses in the formation of dyed layer, this dyed layer is used for preparing the color filter that color liquid crystal display arrangement in transmission-type or reflection-type, colour pick-up tube element etc. use; Color filter with the dyed layer that forms by this radiation-ray sensitive composition; And the color liquid crystal display device that possesses this color filter.
Background technology
In the past, when known use colored radiation-sensitive composition is made color filter, on the substrate or be pre-formed the painted radiation-ray sensitive composition of coating on the substrate of light shield layer of desired pattern, dry, then dry coating is shone radioactive ray (hereinafter referred to as " exposure ") by desired pattern form, develop, thereby obtain the method (referring to Japanese kokai publication hei 2-144502 communique and Japanese kokai publication hei 3-53201 communique) of versicolor pixel.
In addition, in recent years, in the technical field of color filter, main flow is to reduce exposure, shortening productive temp time, and in addition, also tight demand liquid crystal display cells high-fineness shows, can form finer pattern.But for colored radiation-sensitive composition in the past, damaged or the lateral erosion of pattern edge takes place during development easily, so be difficult in the shortening productive temp in the time of the time, and obtain the pixel and the black matrix" of good pattern form, we can say to also have deficiency aspect the high meticulous pattern of formation.
Summary of the invention
Purpose of the present invention relates to the radiation-ray sensitive composition that is used to form dyed layer that shows excellent development, more particularly, its purpose does not have when being to be provided at and developing that dissolved matter is not residual, pattern edge scum silica frost can not occur, and under low exposure, also can obtain not have the damaged and lateral erosion of pattern edge pixel and black matrix", can form the novel radiation-ray sensitive composition that is used to form dyed layer of fine pattern.
Another object of the present invention is to provide color filter with dyed layer and the color liquid crystal display device that possesses color filter.
Other purpose of the present invention and advantage such as following illustrated.
According to the present invention, above-mentioned purpose of the present invention and advantage first aspect realize by radiation-ray sensitive composition, this radiation-ray sensitive composition contains (A) colorant, (B) alkali soluble resins, (C) multi-functional monomer and (D) optical free radical propellant, and be used to form dyed layer, wherein (B) alkali soluble resins contains polyester, and have the ester ring type hydrocarbon skeleton on the main chain of described polyester, and have the polymerism unsaturated link on the side chain.
Above-mentioned " dyed layer " of the present invention is meant the layer that contains pixel and/or black matrix" that uses in color filter.
According to the present invention, above-mentioned purpose of the present invention and advantage second aspect realize that by color filter this color filter has the dyed layer that is formed by above-mentioned radiation-ray sensitive composition.
According to the present invention, the above-mentioned purpose of the present invention and the advantage third aspect realize that by color liquid crystal display device this color liquid crystal display device possesses above-mentioned color filter.
Below the present invention is described in detail.
The best mode that carries out an invention
Radiation-ray sensitive composition
-(A) composition-
There is no particular limitation as the tone of the colorant of (A) composition, can be suitably selected according to the purposes of gained color filter.For example pigment, dyestuff or natural colouring matter all can.
Color filter requires high meticulous colour developing and thermotolerance, therefore as colorant of the present invention, and preferred colour rendering height and the high colorant of thermotolerance, the high colorant of preferred especially heat-resisting decomposability.Preferred organic pigment or the inorganic pigment of using especially preferably uses organic pigment, carbon black.
As above-mentioned organic pigment, can enumerate at Colour Index (C.I.; The distribution of The Society ofDyers and Colourists society) is categorized as the compound of pigment in, specifically can enumerates the compound of following Colour Index (C.I.) numbering.
C.I. 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 55, C.I. pigment yellow 60, C.I. pigment yellow 61, C.I. pigment yellow 65, C.I. pigment yellow 71, C.I. pigment yellow 73, C.I. pigment yellow 74, C.I. pigment yellow 81, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 95, C.I. pigment yellow 97, C.I. pigment yellow 98, C.I. pigment yellow 100, C.I. pigment yellow 101, C.I. pigment yellow 104, C.I. pigment yellow 106, C.I. pigment yellow 108, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 113, C.I. pigment yellow 114, C.I. pigment yellow 116, C.I. pigment yellow 1 17, C.I. pigment yellow 119, C.I. pigment Yellow 12 0, C.I. pigment Yellow 12 6, C.I. pigment Yellow 12 7, C.I. pigment Yellow 12 8, C.I. pigment Yellow 12 9, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 151, C.I. pigment yellow 152, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 156, C.I. pigment yellow 166, C.I. pigment yellow 168, C.I. pigment yellow 17 5, C.I. pigment yellow 180, C.I. pigment yellow 185;
C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. pigment orange 17, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. pigment orange 73;
C.I. pigment violet 1, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29, C.I. pigment violet 32, C.I. pigment violet 36, C.I. pigment violet 38;
C.I. paratonere 1, C.I. paratonere 2, C.I. pigment red 3, C.I. pigment red 4, C.I. paratonere 5, C.I. paratonere 6, C.I. paratonere 7, C.I. pigment Red 8, C.I. Pigment Red 9, C.I. paratonere 10, C.I. paratonere 11, C.I. paratonere 12, C.I. paratonere 14, C.I. paratonere 15, C.I. paratonere 16, C.I. paratonere 17, C.I. paratonere 18, C.I. paratonere 19, C.I. pigment red 21, C.I. paratonere 22, C.I. paratonere 23, C.I. pigment red 30, C.I. pigment red 31, C.I. pigment red 32, C.I. pigment red 37, C.I. pigment red 38, C.I. pigment red 40, C.I. pigment red 41, C.I. pigment red 42, C.I. pigment red 4 8:1, C.I. pigment red 4 8:2, C.I. pigment red 4 8:3, C.I. pigment red 4 8:4, C.I. pigment red 4 9:1, C.I. pigment red 4 9:2, C.I. paratonere 50:1, C.I. paratonere 52:1, C.I. paratonere 53:1, C.I. paratonere 57, C.I. paratonere 57:1, C.I. paratonere 57:2, C.I. paratonere 58:2, C.I. paratonere 58:4, C.I. paratonere 60:1, C.I. paratonere 63:1, C.I. paratonere 63:2, C.I. paratonere 64:1, C.I. pigment red 81: 1, C.I. pigment Red 83, C.I. pigment Red 88, C.I. Pigment Red 9 0:1, C.I. Pigment Red 97, C.I. paratonere 101, C.I. paratonere 102, C.I. paratonere 104, C.I. paratonere 105, C.I. paratonere 106, C.I. paratonere 108, C.I. pigment red 112, C.I. paratonere 113, C.I. paratonere 114, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 146, C.I. pigment red 149, C.I. paratonere 150, C.I. paratonere 151, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 170, C.I. paratonere 171, C.I. paratonere 172, C.I. paratonere 174, C.I. paratonere 175, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 178, C.I. paratonere 179, C.I. paratonere 180, C.I. paratonere 185, C.I. paratonere 187, C.I. paratonere 188, C.I. paratonere 190, C.I. paratonere 193, C.I. paratonere 194, C.I. paratonere 202, C.I. paratonere 206, C.I. Pigment Red 207, C.I. paratonere 208, C.I. paratonere 209, C.I. pigment red 21 5, C.I. pigment red 21 6, C.I. paratonere 220, C.I. paratonere 224, C.I. paratonere 226, C.I. paratonere 242, C.I. paratonere 243, C.I. paratonere 245, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 264, C.I. paratonere 265;
C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. pigment blue 60;
C.I. pigment Green 7, C.I. pigment green 36;
C.I. pigment brown 23, C.I. pigment brown 25;
C.I. pigment black 1, C.I. pigment black 7.
These organic pigments can be by using behind the suitable method purifying such as for example sulfuric acid recrystallization method, solvent wash method or their combination etc.
As inorganic pigment for example can enumerate that titanium dioxide, barium sulphate, lime carbonate, zinc white, lead sulfate, lead and yellow-collation, zinc yellow, colcother (red iron oxide (III)), cadmium red, ultramarine, Prussian blue, chrome oxide green, cobalt green, umber, titanium are black, synthetic magmetite, carbon black etc.
In the present invention, above-mentioned pigment can be distinguished use separately, and perhaps 2 kinds or above mixing use also can be used organic pigment and inorganic pigment together.When forming pixel, preferably use a kind or above organic pigment, when forming black matrix", preferably use 2 kinds or above organic pigment and/or carbon black.
In the present invention, as required, can carry out modification to the particle surface of above-mentioned pigment with polymkeric substance and use.As the polymkeric substance that the particle surface of pigment is carried out modification, for example can enumerate the special polymkeric substance of opening record in the flat 8-259876 communique etc., polymkeric substance that commercially available various dispersed colors are used or oligomer etc.
In addition, in the present invention, as required, colorant can use together with spreading agent.
As above-mentioned spreading agent, can enumerate surfactants such as kation system, negative ion system, nonionic system, both sexes, type siloxane, fluorine class.
As above-mentioned surfactant, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether are for example arranged; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether; Polyethylene glycol di such as polyethylene glycol dilaurate, polyglycol distearate; Sorbitan fatty acid esters; Fatty acid modified polyester; The tertiary amine modified polyurethane; Polyethyleneimines etc. are discussed the KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing) that the name of an article is represented face to face below also having in addition, Port リ Off ロ one (common prosperity society chemistry (strain) system), ェ Off ト Star プ (ト one Network system プ ロ ダ Network Star society system), メ ガ Off ア Star Network (big Japanese ink chemical industry (strain) system), Off ロ ラ one De (Sumitomo ス リ-ェ system (strain) system), ア サ ヒ ガ one De, サ one Off ロ Application (above is Asahi Glass (strain) system), BYK, Disperbyk (above is PVC Star Network Network ミ one ジ ヤ パ Application (strain) system), Application Le ス パ one ス (セ ネ カ (strain) system), EFKA (ェ Off カ one Network ミ カ Le ズ PVC one Block イ society system) etc.
These surfactants can be used singly or two or more kinds mixed.
The use amount of surfactant is preferably below 50 weight portions, more preferably the 0-30 weight portion with respect to 100 weight portion colorants.
Among the present invention, radiation-ray sensitive composition can utilize suitable method preparation.When using pigment as colorant, for example be preferably as follows preparation: in solvent, spreading agent in the presence of, for example use ball mill, roller mill etc., with this pigment and according to circumstances pulverize and mix, disperse with (B) described later alkali soluble resins, make dispersible pigment dispersion, it is become to grade to mix with (B)-(D) described later prepares.
When preparing above-mentioned dispersible pigment dispersion, the consumption of above-mentioned spreading agent is with respect to 100 weight portion pigment, preferred 100 weight portions or following, more preferably 0.5-100 weight portion, further preferred 1-70 weight portion, preferred especially 10-50 weight portion.When the consumption of spreading agent surpasses 100 weight portions, have the possibility that diminishes development etc.
In addition, the above-mentioned solvent that uses during above-mentioned dispersible pigment dispersion as preparation for example can be identical with cited solvent in the fluid composition of radiation-ray sensitive composition described later.
The consumption of above-mentioned solvent is with respect to 100 weight portion pigment, preferred 500-1,000 weight portion, more preferably 700-900 weight portion.
When using ball mill to prepare above-mentioned dispersible pigment dispersion, for example can use beaded glass about diameter 0.5-10mm or titanium dioxide pearl etc., the pigment mixed liquor that will contain pigment, solvent and spreading agent mixes simultaneously, disperses and implement preferably with coolings such as chilled waters.
At this moment, the 50-80vol% of the preferred grinding machine capacity of the filling rate of pearl.About the 20-50vol% of the preferred grinding machine capacity of the injection rate IR of pigment mixed liquor.Preferred 2-50 of processing time hour, more preferably 2-25 hour.
When using roller mill to be prepared, for example can use triple-roller mill, two roller mills etc., the pigment mixed liquor preferably with coolings such as chilled waters, is handled simultaneously and implemented.
At this moment, roller is preferred 10 μ m or following at interval, shearing force for example 10
8Dyn/ is about second.Preferred 2-50 of processing time hour, more preferably 2-25 hour.
-(B) composition-
(B) composition among the present invention is the alkali soluble resins (hereinafter referred to as " (B) alkali soluble resins ") that contains polyester (hereinafter referred to as " the unsaturated alicyclic polyester of side chain "), wherein said polyester has the ester ring type hydrocarbon skeleton on main chain, and on side chain, has the polymerism unsaturated link, be somebody's turn to do of the effect of (B) composition to (A) colorant performance bonding agent, and be in preparation during color filter, the resin that has solubility for the alkaline developer that in its development treatment step, uses.
Ester ring type hydrocarbon skeleton in the unsaturated alicyclic polyester of side chain for example has cyclopentane, methyl cyclopentane, ethyl cyclopentane, the n-pro-pyl cyclopentane, the isopropyl cyclopentane, 1-methyl-3-isopropyl cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, ethyl cyclohexane, the n-pro-pyl cyclohexane, isopropyl cyclohexane, 1-methyl-3-isopropyl cyclohexane, 1-methyl-4-isopropyl cyclohexane, cyclohexene, cycloheptane, the methyl cycloheptane, ethyl cycloheptane, the n-pro-pyl cycloheptane, the isopropyl cycloheptane, 1-methyl-3-isopropyl cycloheptane, 1-methyl-4-isopropyl cycloheptane, cycloheptene, cyclooctane, cyclooctene etc. are from the skeleton of the hydrocarbon with 4-8 unit carbocyclic ring.
In these ester ring type hydrocarbon skeletons, preferably has the skeleton of cyclohexane ring, preferred especially skeleton from 1-methyl-3-isopropyl cyclohexane, 1-methyl-4-isopropyl cyclohexane etc.
In the unsaturated alicyclic polyester of side chain, the ester ring type hydrocarbon skeleton can be directly or via the binding groups of divalence, forms the main chain ester structure that the formation unit that makes polyester connects.
It is straight chain or the branching alkylene of 1-6 that the binding groups of above-mentioned divalence for example has methylene such as methylene, ethylidene, propylidene, trimethylene, four butylidenes or backbone c atoms number; Inferior cyclobutyl, cyclopentylene, cyclohexylidene etc. have the cycloalkanes support of 4-8 unit ring carbocyclic ring; Cyclopentylene methylene, cyclopentylene ethylidene, cyclopentylene propylidene, cyclohexylidene methylene, cyclohexylidene ethylidene, cyclohexylidene propylidene etc. connect the bivalent hydrocarbon chain gained group that backbone c atoms such as methylene, ethylidene, propylidene are counted 1-6 in the cycloalkanes support with 4-8 unit ring carbocyclic ring; 1,3-phenylene, 1,4-phenylene, 1, the arlydene of carbon number 6-10 such as 4-naphthylene; Connect backbone c atoms such as methylene, ethylidene, propylidene on the arlydene of above-mentioned carbon number 6-10 and count the bivalent hydrocarbon chain gained group of 1-6; Between inferior phenoxy group (m-C
6H
4-O-), to inferior phenoxy group (p-C
6H
4-O-) wait the inferior aryloxy group of carbon number 6-10; Connect backbone c atoms such as methylene, ethylidene, propylidene on the oxygen base in the above-mentioned inferior aryloxy group and count bivalent hydrocarbon chain gained group of 1-6 etc.
In the binding groups of these divalence, the inferior aryloxy group of preferred carbon number 6-10 is especially preferably to inferior phenoxy group.
In the unsaturated alicyclic polyester of side chain, the polymerism unsaturated link of side chain is so long as can get final product with (C) described later multi-functional monomer or the simple function monomer copolymerization that according to circumstances uses when making the radiation-ray sensitive composition that is used to form dyed layer, be not particularly limited, consider from the angle of the synthetic easiness of the unsaturated alicyclic polyester of side chain, for example preferably from the unsaturated link of polymerizable unsaturated carboxylic acids such as (methyl) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, especially preferably from (methyl) acrylic acid unsaturated link.
Among the present invention, polyester (hereinafter referred to as " polyester (1) ") shown in the preferred especially following formula (1) of the unsaturated alicyclic polyester of side chain.
[in the formula (1), each X is separate, the divalent group shown in expression following formula (2) or the formula (3), and each Y is separate, and the residue of four carboxyl gained, each R are removed in expression from organic tetrabasic carboxylic acid
1Separate, expression hydrogen atom or methyl, each R
2Separate, expression hydrogen atom or carboxyl sealer residue, n is the integer of 1-40].
The unsaturated alicyclic polyester of side chain for example can be prepared as follows: have the diol compound that has the polymerism unsaturated link on ester ring type hydrocarbon skeleton and the side chain on the synthetic main chain, make this diol compound and divalent or above, preferred 2-4 valency, especially preferably and tetracarboxylic anhydride carry out esterification.
Polyester (1) can be preferably by diol compound that contains two (methyl) acryloyl group shown in following formula (6) or the formula (7) and the tetracarboxylic dianhydride's shown in the following formula (8) (hereinafter referred to as " tetracarboxylic dianhydride (8) ") esterification preparation.
[in the formula (6), R
1With the R in the formula (1)
1Implication is identical].
[in the formula (7), R
1With the R in the formula (1)
1Implication is identical].
[in the formula (8), Y is identical with Y implication in the formula (1)].
Below, for the preparation method of the unsaturated alicyclic polyester of side chain, be that representative describes with the situation of polyester (1).
At first; the diol compound that contains two (methyl) acryloyl group for example can be prepared as follows: the biphenol (hereinafter referred to as " biphenol (10) ") shown in biphenol shown in the following formula (9) (hereinafter referred to as " biphenol (9) ") and/or the formula (10) is carried out the 2-glycidyl etherificate; diglycidyl ether thing shown in synthetic following formula (11) or the formula (12), addition acrylic acid and/or methacrylic acid on the epoxy radicals of two ends of this diglycidyl ether thing then.
Above-mentioned gained contains the diol compound of two (methyl) acryloyl group, and preferably its acid number is lower than 10mgKOH/g, and epoxide equivalent is 10,000-20,000.
Synthetic when containing the diol compound of two (methyl) acryloyl group, biphenol can be separately or with 2 kinds or above mixing use, preferably biphenol (9) and biphenol (10) used together according to the weight ratio of 80-60: 20-40.
Synthesize when containing the diol compound of two (methyl) acryloyl group, the diglycidyl ether reaction of biphenol can be implemented according to the synthetic method of conventional epoxy resin.For example, can be by in the presence of base catalyst, it is synthetic that the reaction of chloropropylene oxide and biphenol is come.
The epoxide equivalent of the above-mentioned diglycidyl ether thing that obtains is preferably 260-300.
Tetracarboxylic dianhydride (8) is not particularly limited, and preferably enumerates the compound shown in the compound shown in the compound shown in the following formula (8-1), the formula (8-2), the formula (8-3) etc.
The implementation method of diol compound that contains two (methyl) acryloyl group during preparation polyester (1) and tetracarboxylic dianhydride's (8) esterification is not particularly limited; the diol compound that for example can will contain two (methyl) acryloyl group under heating is dissolved in the organic solvent; to wherein adding tetracarboxylic dianhydride (8); reaction while stirring, preparation polyester (1).
In the polyester (1) that obtains by above-mentioned esterification, the R in the formula (1)
2All be hydrogen atom, each residue of tetracarboxylic dianhydride (8) partly has 2 to 3 carboxyls, shows the dissolubility to the excellence of aqueous alkali thus.
Among the present invention, at least a portion of the free carboxy in the polyester (1) that can obtain esterification with the carboxyl sealer is sealed and is used.In this case,, can regulate the acid number of polyester (1), the control alkali dissolution by changing the sealing ratio of carboxyl.
Above-mentioned carboxyl sealer is not particularly limited, and can be known materials such as glycidyl ethers, carbodiimide class.For example preferred phenylglycidyl ether, 4-n-butylphenyl glycidyl ether, resorcinol glycidyl ether etc.
Among the present invention, the preferred 20-80mgKOH/g of acid number of polyester (1), further preferred 30-70mgKOH/g.R in the polyester (1)
2According to tetracarboxylic dianhydride's (8) kind and difference, preferred 50mol% or above, more preferably 70mol% or above be hydrogen atom, this considers preferably from guaranteeing good alkali-developable angle.
The epoxide equivalent of the polyester (1) after sealing with the carboxyl sealer be preferably 60,000 or more than.
Polyester (1) has the acryloyl group or the methacryl of a plurality of tool polymerisms; because of exposure is solidified; the difficulty that becomes is dissolved in the aqueous alkali; and under its uncured state, be dissolvable in water in the aqueous alkali, therefore, as the resist tunicle; can pass through partial exposure; keep cured portion, and uncured portion is removed by the aqueous alkali dissolving, express alkali-developable.In addition, polyester (1) is good with various substrate attachment, and cure shrinkage is little, glass transition temperature (Tg) height, and excellent heat resistance, the while can form the resist tunicle of high rigidity.And the ester ring type hydrocarbon skeleton that contains in the molecular backbone partly forms soft structure, has good flexibility.
Among the present invention, by gel permeation chromatography (GPC) (eluting solvent: tetrahydrofuran) side chain unsaturated link alicyclic polyester is measured, through the weight-average molecular weight (hereinafter referred to as " Mw ") preferred 3 of polystyrene conversion, 000-100,000, further preferred 5,000-25,000.Mw is littler than above-mentioned scope, and then flexibility and tack may reduce, and bigger than above-mentioned scope, and then alkali dissolution under photo-curable, its uncured state etc. may reduce.When being polyester (1), Mw can regulate by the amount that changes organic solvent in the above-mentioned esterification or reaction raw materials.
By gel permeation chromatography (GPC) (eluting solvent: tetrahydrofuran) side chain unsaturated lipid ring type polyester is measured, preferred 1 through the number-average molecular weight (hereinafter referred to as " Mn ") of polystyrene conversion, 000-60,000, more preferably 2,000-25,000.
Consider that from the angle of guaranteeing the good alkali dissolution under its uncured state preferred its acid number of the unsaturated alicyclic polyester of side chain is 60-70mgKOH/g.
Among the present invention, the unsaturated alicyclic polyester of side chain can be separately or two kinds or above mixing is used.
Among the present invention,, can use other alkali soluble resins with the unsaturated alicyclic polyester of side chain as alkali soluble resins.
But the multipolymer of the polymerism unsaturated monomer that above-mentioned other alkali soluble resins for example can be enumerated acidic functionalities such as having carboxyl, phenolic hydroxyl, sulfonic group and the unsaturated monomer (hereinafter referred to as " copolymerization unsaturated monomer ") of other copolymerization different with them.
Polymerism unsaturated monomer (hereinafter referred to as " unsaturated monomer that contains carboxyl ") with carboxyl can exemplify:
Unsaturated monocarboxylic acids such as (methyl) acrylic acid, crotonic acid, α-Lv Bingxisuan, cinnamic acid;
Unsaturated dicarboxylic acid or its acid anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid;
Ternary or above unsaturated polybasic carboxylic acid or its acid anhydrides;
List [(methyl) acryloxyalkyl] ester of binary such as mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester or above polybasic carboxylic acid;
ω-two ends such as carboxyl polycaprolactone list (methyl) acrylate have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl etc.
The above-mentioned unsaturated monomer that contains carboxyl can be separately or two kinds or above mixing is used.
Polymerism unsaturated monomer with phenolic hydroxyl for example has: o-hydroxy ethene, a hydroxy styrenes, para hydroxybenzene ethene, adjacent hydroxyl-α-Jia Jibenyixi, hydroxyl-α-Jia Jibenyixi, to hydroxy phenyl maleimide, N-p-hydroxybenzene maleimide etc. between hydroxyl-α-Jia Jibenyixi, N-o-hydroxy-phenyl maleimide, N-.
These polymerism unsaturated monomers with phenolic hydroxyl can be separately or two kinds or above mixing are used.
Have sulfonic polymerism unsaturated monomer isoprene sulfonic acid, p styrene sulfonic acid etc. are for example arranged.
These have sulfonic polymerism unsaturated monomer can be separately or two kinds or above mixing used.
The copolymerization unsaturated monomer for example has:
The end of polymer molecular chains such as polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane has the macromonomer (being designated hereinafter simply as " macromonomer ") of list (methyl) acryloyl group;
N-phenylmaleimide, N-o-hydroxy-phenyl maleimide, hydroxy phenyl maleimide between N-, N-p-hydroxybenzene maleimide, N-o-methyl-phenyl-maleimide, aminomethyl phenyl maleimide between N-, N-p-methylphenyl maleimide, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, N position-substituted maleimide the amine of N-aryl maleimides such as N-p-methoxyphenyl maleimide or N-cyclohexyl maleimide etc.;
Styrene, α-Jia Jibenyixi, adjacent vinyltoluene, a vinyltoluene, to vinyltoluene, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to aromatic vinyl compounds such as vinyl benzyl glycidyl ethers; Indenes classes such as indenes, 1-methyl indenes;
(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) acrylic acid 3-hydroxyl butyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, (methyl) allyl acrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-phenoxy ethyl, (methyl) acrylic acid methoxyl diglycol ester, (methyl) acrylic acid methoxyl triethyleneglycol ester, (methyl) acrylic acid MPEG ester, (methyl) acrylic acid methoxyl dipropylene glycol ester, (methyl) isobornyl acrylate, (methyl) acrylic acid bicyclopentadiene ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, esters of unsaturated carboxylic acids such as single (methyl) acrylic acid glyceride;
Unsaturated carboxylic acid aminoalkyl esters such as (methyl) acrylic acid 2-amino ethyl ester, (methyl) acrylic acid 2-dimethylamino ethyl ester, the amino propyl ester of (methyl) acrylic acid 2-, (methyl) acrylic acid 2-dimethylamino propyl ester, the amino propyl ester of (methyl) acrylic acid 3-, (methyl) acrylic acid 3-dimethylamino propyl ester;
Unsaturated carboxylic acid glycidyl esters classes such as (methyl) acrylic acid glycidyl esters;
Vinyl carboxylates such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, EVE, allyl glycidyl ether;
Vinyl cyanide compounds such as (methyl) vinyl cyanide, α-Lv Bingxijing, vinylidene dinitrile;
Unsaturated amides such as (methyl) acrylamide, α-chloropropene acid amides, N-2-hydroxyethyl (methyl) acrylamide;
Aliphatic conjugated diene such as 1,3-butadiene, isoprene, chlorbutadiene etc.
Among the present invention, above-mentioned other alkali soluble resins for example preferably contains the unsaturated monomer of carboxyl and the multipolymer of copolymerization unsaturated monomer (being designated hereinafter simply as " multipolymer that contains carboxyl "), further preferably contain (a) and contain (methyl) acrylic acid carboxyl unsaturated monomer that contains, (b) be selected from the polystyrene macromolecular monomer, poly-(methyl) methyl acrylate macromonomer, N-phenylmaleimide, N-cyclohexyl maleimide, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) benzyl acrylate and (methyl) acrylic acid glyceride at least a (c) according to circumstances also contains and is selected from styrene, α-Jia Jibenyixi, (methyl) methyl acrylate, the multipolymer of at least a monomer mixture of (methyl) allyl acrylate and (methyl) phenyl acrylate.
The Mw of other alkali soluble resins is preferred 2,000-300,000, more preferably 3,000-100,000.Mn is preferred 1,000-60,000, more preferably 2,000-25,000.
Among the present invention, other alkali soluble resins can be separately or two kinds or above mixing is used.
Among the present invention, with respect to 100 weight portions (A) colorant, the preferred 10-1 of total consumption of alkali soluble resins, 000 weight portion, more preferably 20-500 weight portion.Total consumption of alkali soluble resins is lower than 10 weight portions, and then for example alkali-developable reduces, and scum or residual film take place on the substrate of unexposed portion or on the light shield layer; And surpass 1000 weight portions, then colorant concentration reduces relatively, is difficult to realize the aim colour density of film.
The preferred 10-100 weight of the usage ratio % of the unsaturated alicyclic polyester of side chain in the alkali soluble resins, preferred especially 20-100 weight %.The usage ratio of the unsaturated alicyclic polyester of side chain is lower than 10 weight %, and the effect that then the present invention expected can be impaired.
-(C) composition-
(C) of the present invention composition is the multi-functional monomer that has 2 or above polymerism unsaturated link in the molecule.
As above-mentioned multi-functional monomer, for example can enumerate:
Two (methyl) acrylate of aklylene glycol such as ethylene glycol, propylene glycol;
Two (methyl) acrylate of poly alkylene glycol such as polyglycol, polypropylene glycol;
Many (methyl) acrylate of ternarys such as glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol or above polyvalent alcohol and their dicarboxylic acids modifier;
Oligomeric (methyl) acrylate of polyester, epoxy resin, urethane resin, alkyd resin, organic siliconresin, spirane resin etc.;
Two terminal hydroxyls are poly--two (methyl) acrylate and three [2-(methyl) acryloxy ethyl] phosphate of two terminal hydroxyl fluidized polymers such as 1,3-butadiene, two terminal hydroxyl polyisoprene, two terminal hydroxyl polycaprolactones etc.
In these multi-functional monomers, many (methyl) acrylate of preferred ternary or above polyvalent alcohol and their dicarboxylic acids modifier, specifically, preferred trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, compound shown in the following formula (13), compound shown in the following formula (14) etc.
Good and be difficult to produce considerations such as scum, residual film on the substrate of unexposed portion and on the light shield layer, preferred especially trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol acrylate for the flatness on dyed layer intensity height, dyed layer surface.
Above-mentioned multi-functional monomer can use separately or 2 kinds or above mixing are used.
With respect to 100 weight portions (B) alkali soluble resins, the consumption of multi-functional monomer of the present invention is preferably the 5-500 weight portion, more preferably the 20-300 weight portion.At this moment, multi-functional monomer consumption is lower than 5 weight portions, and the intensity of dyed layer, surface smoothing have the tendency of reduction, and if surpass 500 weight portions, for example have alkali-developable and reduce, perhaps easily on the substrate of unexposed portion or produce the tendency of scum, residual film etc. on the light shield layer.
Among the present invention, multi-functional monomer can with molecule in have a polymerism unsaturated link the simple function combination of monomers use.
As above-mentioned simple function monomer; can enumerate with above-mentioned other alkali soluble resins in the unsaturated monomer that contains carboxyl or the copolymerization unsaturated monomer in the same compound of compound that exemplified; N-(methyl) acryloyl morpholine; the N-vinyl pyrrolidone; N-vinyl-epsilon-caprolactams; in addition, also has M-5600 (trade name, East Asia synthetic (strain) system) as commercially available product etc.
These simple function monomers can use separately or 2 kinds or above mixing use.
The usage ratio of simple function monomer is preferably 90 weight % or following with respect to the total amount of multi-functional monomer and simple function monomer, more preferably 50 weight % or following.If the usage ratio of simple function monomer surpasses 90 weight %, the intensity of gained dyed layer and surface smoothing may be not enough.
With respect to 100 weight portions (B) alkali soluble resins, total consumption of multi-functional monomer of the present invention and simple function monomer is preferably the 5-500 weight portion, more preferably the 20-300 weight portion.If above-mentioned total consumption is lower than 5 weight portions, the tendency that reduces of the intensity of dyed layer and surface smoothing existence then, if and surpass 500 weight portions, for example have then that alkali-developable reduces, perhaps on the substrate of unexposed portion or be easy to produce the tendency of scum, residual film etc. on the light shield layer.
-(D) the optical free radical propellant-
(D) of the present invention optical free radical propellant is by visible light, ultraviolet ray, far ultraviolet, charged particle ray, the exposure of X ray isoradial, and generation can cause (C) multi-functional monomer and the free radical of the simple function monomer polymerization that according to circumstances is used in combination.
Among the present invention, the compound (hereinafter referred to as " carbazole based compound (D1) ") shown in for example preferred following formula (4) of optical free radical propellant or the formula (5).
[in formula (4) and the formula (5), each R
3Separate, straight chain, branching or cyclic alkyl or the phenyl of expression carbon number 1-12, each R
4Separate, straight chain, branching or cyclic alkyl or the phenyl of expression hydrogen atom, carbon number 1-12, each R
5Separate, straight chain, branching or the cyclic alkyl of expression hydrogen atom or carbon number 1-12, each R
6, each R
7With each R
8Separate, straight chain, branching or the cyclic alkyl of expression hydrogen atom or carbon number 1-6; R
3, R
4, R
5, R
6, R
7And R
8The alkyl substituting group of alkoxy, phenyl and halogen atom that can be selected from straight chain, branching or the ring-type of carbon number 1-6 separately replace; R
3And R
4Phenyl can be selected from straight chain, branching or the cyclic alkyl of carbon number 1-6 separately, the straight chain of carbon number 1-6, branching or cyclic alkoxy, the substituting group of phenyl and halogen atom replaces].
In formula (4) and the formula (5), R
3, R
4And R
5The alkyl of straight chain, branching or ring-type of carbon number 1-12 methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, cyclopentyl, cyclohexyl etc. are for example arranged.
R
6, R
7And R
8Straight chain, branching or the cyclic alkyl of carbon number 1-6 methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl etc. are for example arranged.
R
3, R
4, R
5, R
6, R
7And R
8The substituting group and the R of each alkyl
3And R
4The substituting group of each phenyl in, the straight chain of carbon number 1-6, branching or cyclic alkoxy for example have methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy etc., halogen atom for example has fluorine atom, chlorine atom etc.
R
3And R
4The substituting group of each phenyl in, the straight chain of carbon number 1-6, branching or cyclic alkyl for example have methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group etc.
In each alkyl and each phenyl, above-mentioned substituting group can exist one or above or one or more.
In formula (4) and the formula (5), R
3Preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, phenyl etc., R
4Preferred hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl etc., R
5Preferred hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl etc., further preferred R
6, R
7And R
8Be hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl etc.
The object lesson of the preferred carbazole based compound of the present invention (D1) for example has: 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-nonane-1; 2-nonane-2-oxime-O-benzoic ether; 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-nonane-1; 2-nonane-2-oxime-O-acetic acid esters; 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-pentane-1; 2-pentane-2-oxime-O-acetic acid esters; 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-octane-1-ketoxime-O-acetic acid esters; 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-acetic acid esters; 1-[9-ethyl-6-(1; 3, the 5-trimethylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; 1-[9-normal-butyl-6-(2-ethylamino benzonitrile acyl group)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether etc.
In these carbazole based compounds (D1), preferred especially 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-acetic acid esters.
Among the present invention, carbazole based compound (D1) can be separately or two kinds or above mixing is used.
Among the present invention, can use carbazole based compound (D1) optical free radical propellant (hereinafter referred to as " other optical free radical propellant ") in addition. its object lesson for example has: have shown in a kind of following formula (15-1), formula (15-2) or the formula (15-3) the bisglyoxaline based compound, benzoin based compound, acetophenone based compound, benzophenone based compound, α-diketone based compound, multinuclear quinone based compound, xanthone based compound, phosphine based compound, triazine based compound of main skeleton etc. at least.
Above-mentioned bisglyoxaline based compound for example has:
2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline,
2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline,
2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,
2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,
2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,
2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,
2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline,
2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.
In these bisglyoxaline based compounds, preferred 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline and 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, preferred especially 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
-hydrogen donor-
Among the present invention, when using the bisglyoxaline based compound, consider, preferably with following hydrogen donor and usefulness from can further improving sensitivity as the optical free radical propellant.
Here alleged " hydrogen donor " is meant the compound that hydrogen atom can be provided to the free radical that is produced from the bisglyoxaline based compound by exposure.
As above-mentioned hydrogen donor, the mercaptan based compound of preferred following definitions, the amine compound of following definitions etc.
Above-mentioned mercaptan based compound contain with phenyl ring or heterocycle as parent nucleus, have 1 or above, preferred 1-3, further preferred 1-2 compound (hereinafter referred to as " mercaptan is hydrogen donor ") that is bonded directly to the sulfydryl on this parent nucleus.
Above-mentioned amine compound contain with phenyl ring or heterocycle as parent nucleus, have 1 or above, preferred 1-3, further preferred 1-2 compound (hereinafter referred to as " amine is hydrogen donor ") that is bonded directly to the amino on this parent nucleus.
In addition, these hydrogen donors can have sulfydryl and amino simultaneously.
Below be described more specifically hydrogen donor.
Mercaptan is that hydrogen donor can have 1 or above phenyl ring or heterocycle respectively, can also have phenyl ring and heterocycle the two.Have 2 or above these whens ring, can form fused rings.
Mercaptan is hydrogen donor when having 2 or above sulfydryl, as long as residual at least 1 free sulfydryl, 1 or above remaining sulfydryl can be replaced by alkyl, aralkyl or aryl.And then, promptly can have structural unit by 2 sulphur atoms of divalent organic group bondings such as alkylidene or 2 sulphur atoms structural unit with the form bonding of disulfide as long as residual have at least 1 free sulfhydryl groups.
And then mercaptan is that the position of hydrogen donor beyond sulfydryl can be by carboxyl, replacement or unsubstituted alkoxy carbonyl, replacement or replacements such as unsubstituted phenoxy carbonyl, itrile group.
As such mercaptan is the object lesson of hydrogen donor, can enumerate 2-mercaptobenzothiazole, 2-sulfydryl benzoxazol, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazoles, 2-sulfydryl-2,5-dimethyl aminopyridine etc.
These mercaptan are in the hydrogen donor, preferred 2-mercaptobenzothiazole, 2-sulfydryl benzoxazol, preferred especially 2-mercaptobenzothiazole.
Amine is that hydrogen donor can have 1 or above phenyl ring or heterocycle respectively, can also have phenyl ring and heterocycle the two.Have 2 or above these whens ring, can form fused rings.
And amine is in the hydrogen donor, and 1 or above amino can be replaced by alkyl or substituted alkyl, and the position beyond amino also can be by carboxyl, replacement or unsubstituted alkoxy carbonyl, replacement or replacements such as unsubstituted phenoxy carbonyl, itrile group.
As such amine is the object lesson of hydrogen donor, can enumerate 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4-two-ethylamino acetophenone, 4-dimethylamino propiophenone, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid, 4-dimethylamino benzonitrile etc.
At these amine is in the hydrogen donor, preferred 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, preferred especially 4,4 '-two (diethylamino) benzophenone.When not having the bisglyoxaline based compound, 4,4 '-two (dimethylamino) benzophenone or 4,4 '-two (diethylaminos) but the separately effect of performance optical free radical propellant of benzophenone self.
In the present invention, hydrogen donor can use separately or 2 kinds or above mixing are used.Because the dyed layer that forms is difficult to come off from substrate when developing, and dyed layer intensity and sensitivity are also high, preferably are that hydrogen donor and a kind or above amine are that hydrogen donor is used in combination with a kind or above mercaptan.
Preferred mercaptan is that hydrogen donor and amine are that the object lesson that hydrogen donor makes up can be enumerated 2-mercaptobenzothiazole/4,4 '-two (dimethylamino) benzophenone, 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone, 2-sulfydryl benzoxazol/4,4 '-two (dimethylamino) benzophenone, 2-sulfydryl benzoxazol/4,4 '-two (diethylamino) benzophenone etc.Preferred combination has 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone, 2-sulfydryl benzoxazol/4,4 '-two (diethylamino) benzophenone, particularly preferred 2-mercaptobenzothiazole/4 that are combined as, 4 '-two (diethylamino) benzophenone.
At mercaptan is that hydrogen donor and amine are in the combination of hydrogen donor, and mercaptan is that hydrogen donor and amine are that the weight ratio of hydrogen donor is preferably 1: 1-1: 4, more preferably 1: 1-1: 3.
Above-mentioned benzoin based compound as the optical free radical propellant for example has: benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether, 2-benzoyl methyl benzoate etc.
Above-mentioned acetophenone based compound for example has: 2, the 2-dimethoxy-acetophenone, 2, the 2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 2-methyl-(4-methyl mercapto phenyl)-2-morpholino-1-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, the 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone etc.
Above-mentioned benzophenone based compound for example has: 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone etc.
Above-mentioned α-diketone based compound for example has: diacetyl, dibenzoyl, toluyl carbamate etc.
Above-mentioned multinuclear quinone based compound for example has: anthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1,4-naphthoquinones etc.
Above-mentioned xanthone based compound for example has: xanthone, thioxanthones, 2-clopenthixal ketone etc.
Above-mentioned phosphine based compound for example has: two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.
Above-mentioned triazine based compound for example has: 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(furans-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(5-methylfuran-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-ethoxybenzene vinyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-n-butoxy phenyl)-4, two (the trichloromethyl)-s-triazines of 6-, compound shown in the following formula (16);
Compound shown in the following formula (17)
Deng compound with halogenated methyl etc.
Among the present invention, the optical free radical propellant can be separately or 2 kinds or above mixing is used.
Among the present invention, can also be as required, be used in combination one or more of sensitizer, curing accelerator or the crosslinked sensitizer of high-molecular optical with above-mentioned optical free radical propellant.
In the present invention, with respect to (C) multi-functional monomers of 100 weight portions or with the total amount of the simple function monomer that according to circumstances uses, the consumption of optical free radical propellant of the present invention is preferably the 0.01-200 weight portion, and more preferably the 1-120 weight portion is preferably the 1-100 weight portion especially.At this moment, if the consumption of optical free radical propellant is lower than 0.01 weight portion, then because the curing that exposure causes becomes not enough, be difficult to obtain the pattern array of pattern of pixels or black matrix pattern alignment arrangements according to the rules, if and surpass 200 weight portions, then the dyed layer of Xing Chenging when developing, come off from substrate easily, generation scum, residual film etc. easily on the substrate of unexposed portion or on the light shield layer.
Among the present invention, when being used in combination with other optical free radical propellant as the carbazole based compound (D1) of optical free radical propellant, the usage ratio of other optical free radical propellant is with respect to the preferred 50 weight % or following of the total of carbazole based compound (D1) and other optical free radical propellant, further preferred 30 weight % or following.
-adjuvant-
The radiation-ray sensitive composition that is used to form dyed layer of the present invention also can contain various adjuvants as required.
As above-mentioned adjuvant, can enumerate demonstration more improve radiation-ray sensitive composition in alkaline developer dissolution characteristics and more suppress to develop after the not organic acid of the residual effect etc. of dissolved matter or organic amino compounds (except the above-mentioned hydrogen donor) etc.
As above-mentioned organic acid, preferably in molecule, have the aliphatic carboxylic acid of 1 or above carboxyl or contain the carboxylic acid of phenyl.
As above-mentioned aliphatic carboxylic acid, for example have:
Formic acid, acetate, propionic acid, butyric acid, valeric acid, neopentanoic acid, caproic acid, diethacetic acid, enanthic acid, monocarboxylic acid such as sad;
Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, brassylic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoronic acid etc.
In addition, as the above-mentioned carboxylic acid that contains phenyl, can enumerate carboxyl directly and the compound of phenyl bonding, the carboxyl carboxylic acid by carbochain and phenyl bonding etc.
Carboxylic acid as containing phenyl for example has:
Benzoic acid, toluic acid, cumic acid, 2,3-mesitylenic acid, 3, aromatic series monocarboxylic acids such as 5-mesitylenic acid;
Aromatic dicarboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid (TPA);
Ternary or above aromatic series polybasic carboxylic acids such as trimellitic acid, trimesic acid, mellophanic acid, pyromellitic acid, and
Phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, the acid of シ Application Na ミ リ デ Application, coumaric acid, the acid of Umbrella shape etc.
In these organic acids, from alkali dissolution, to the dissolubility of aftermentioned solvent, prevent on the substrate of unexposed portion or viewpoint such as the scum on the light shield layer and residual film, as aliphatic carboxylic acid, the preferred aliphat dicarboxylic acid, preferred especially malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid etc.As the carboxylic acid that contains phenyl, optimization aromatic dicarboxylic acid, preferred especially phthalic acid.
Above-mentioned organic acid can use separately or 2 kinds or above mixing use.
The organic acid use amount is overall with respect to radiation-ray sensitive composition, preferred 15 weight % or following, more preferably 10 weight % or following.At this moment, if the organic acid use amount surpasses 15 weight %, the tendency that the dyed layer that existence forms and the tack of substrate reduce.
In addition, as above-mentioned organic amino compounds, preferably in molecule, have the fatty amine of 1 or above amino or contain the amine of phenyl.
As above-mentioned fatty amine, for example have:
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 amine, n-dodecane amine, cyclo-hexylamine, 2-methylcyclohexyl amine, 3-methylcyclohexyl amine, 4-methylcyclohexyl amine, 2-ethyl cyclo-hexylamine, 3-ethyl cyclo-hexylamine, 4-ethyl cyclo-hexylamine;
Two (ring) alkyl amines such as Methylethyl amine, diethylamide, methyl n-pro-pyl amine, ethyl n-pro-pyl amine, di-n-propyl amine, diisopropylamine, di-n-butyl amine, diisobutyl amine, two sec-butylamine, di-t-butyl amine, two n-pentyl amine, di-n-hexyl amine, methylcyclohexyl amine, ethyl cyclo-hexylamine, dicyclohexyl amine;
Three (ring) alkyl amines such as dimethylethyl amine, methyl diethylamide, triethylamine, dimethyl n propyl group amine, diethyl n-pro-pyl amine, methyl di-n-propyl amine, ethyl di-n-propyl amine, three n-pro-pyl amine, triisopropylamine, tri-n-butyl amine, triisobutyl amine, three sec-butylamine, tri-tert amine, three n-pentyl amine, three n-hexyl amine, dimethylcyclohexylam,ne, diethyl cyclo-hexylamine, methyl bicyclic hexyl amine, ethyl dicyclohexyl amine, thricyclohexyl 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) alkanolamines 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) alkanolamines 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) alkane glycol such as ammediol;
1-Aminocyclopentane methyl alcohol, 4-Aminocyclopentane methyl alcohol, 1-aminocyclohexane methyl alcohol, 4-aminocyclohexane methyl alcohol, 4-dimethylamino cyclopentane methyl alcohol, 4-diethylamino cyclopentane methyl alcohol, 4-dimethylamino cyclohexane methanol, 4-diethylamino cyclohexane methanol etc. contain amino cycloalkanes methyl alcohol;
Amino carboxylic 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, 1-1-aminocyclopropane-1-carboxylic acid, 1-aminocyclohexane carboxylic acid, 4-aminocyclohexane carboxylic acid etc.
In addition, as the above-mentioned amine that contains phenyl, can enumerate amino directly with the compound of phenyl bonding, the amino compound by carbochain and phenyl bonding etc.
Amine as containing phenyl for example has:
Aniline, 2-aminotoluene, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-pro-pyl aniline, 4-isopropyl aniline, 4-n-butyl aniline, 4-tert-butyl group aniline, naphthalidine, 2-naphthylamines, N, accelerine, N, N-diethylaniline, 4-methyl-N, aromatic amines such as accelerine;
Aminobenzyl alcohols such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylamino benzylalcohol, 4-diethylamino benzylalcohol;
Amino phenol such as 2-amino-phenol, 3-amino-phenol, 4-amino-phenol, 4-dimethylamino phenol, 4-diethylamino phenol etc.
In these organic amino compounds, from to the dissolubility of aftermentioned solvent, prevent on the substrate of unexposed portion or viewpoint such as the scum on the light shield layer and residual film, as fatty amine, preferred single (ring) alkanolamine, amino (ring) alkane glycol, preferred especially 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1,2-propylene glycol, 2-amino-1, ammediol, 4-amino-1,2-butylene glycol etc.In addition, as the amine that contains phenyl, preferred amino-phenol, preferred especially 2-amino-phenol, 3-amino-phenol, 4-amino-phenol etc.
Above-mentioned organic amino compounds can be separately or 2 kinds or above mixing is used.
Overall with respect to radiation-ray sensitive composition, the preferred 15 weight % or following of the consumption of organic amino compounds, more preferably 10 weight % or following.At this moment, if the consumption of organic amino compounds surpasses 15 weight %, the tack of then formed dyed layer and substrate has the tendency of reduction.
Adjuvant beyond above-mentioned organic acid and the organic amino compounds for example has:
The dispersing aid of blue pigment derivants such as copper phthalocyanine derivative thing, yellow uitramarine derivant etc.;
Filling agent such as glass, aluminium oxide;
Macromolecular compounds such as polyvinyl alcohol (PVA), polyalkylene glycol monoalkyl ethers, poly-(fluoroalkyl acrylate) class;
Surfactants such as nonionic system, kation system, negative ion system;
Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (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 propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, adhesion promoters such as 3-sulfydryl propyl trimethoxy silicane;
2, antioxidants such as 2 '-thiobis (4-methyl-6-tert butyl phenol), 2,6 di t butyl phenol;
Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone class;
Anti-coagulants such as sodium polyacrylate;
1,1 '-azo two (cyclohexane-1-nitrile), 2-phenylazos-4-methoxyl-2, hot radical propellants such as 4-methyl pentane nitrile etc.
Solvent
The radiation-ray sensitive composition that is used to form dyed layer of the present invention be with above-mentioned (A)-(D) composition as must composition, can contain above-mentioned additive component as required, cooperate solvent to make fluid composition usually.
As long as above-mentioned solvent can disperse or dissolve (A)-(D) composition and the additive component that constitutes radiation-ray sensitive composition, and do not react with these compositions, the volatility with appropriateness gets final product, and can suitably select to use.
Above-mentioned solvent for example has: the glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl n-propyl ether, the glycol monomethyl n-butyl ether, the diglycol monotertiary methyl ether, carbiphene, the diglycol monotertiary n-propyl ether, the diglycol monotertiary n-butyl ether, the triethylene glycol monomethyl ether, triethylene glycol list ethylether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether, the dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, dipropylene glycol list n-propyl ether, dipropylene glycol list n-butyl ether, the tripropylene glycol monomethyl ether, (many) alkylene glycol monoalkyl ethers such as tripropylene glycol list ethylether;
(many) alkylene glycol monoalkyl ethers acetic acid esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, diglycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters;
Other ethers such as diethylene glycol dimethyl ether, diglycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketone such as MEK, cyclohexanone, 2-heptanone, 3-heptanone;
Lactic acid alkyl ester such as methyl lactate, ethyl lactate;
2-hydroxy-2-methyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, acetate 3-methyl-3-methoxyl butyl ester, propionic acid 3-methyl-3-methoxyl butyl ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, other esters such as 2-ketobutyric acid ethyl ester;
Aromatic hydrocarbon such as toluene, dimethylbenzene;
N, acid amides such as dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone or lactams etc.
In these solvents, from dissolubility, pigment-dispersing, the coating equal angles is considered, preferred propylene glycol monomethyl ether, the ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, diethylene glycol dimethyl ether, the diglycol methyl ethyl ether, cyclohexanone, the 2-heptanone, the 3-heptanone, ethyl lactate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, propionic acid 3-methyl-3-methoxyl butyl ester, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, ethyl pyruvate etc.
Above-mentioned solvent can use separately or two kinds or above mixing are used.
Can also be used in combination high boiling solvents such as benzylisoeugenol, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzylalcohol, acetate benzyl ester, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, glycol monomethyl phenyl ether acetic acid esters with above-mentioned solvent.
These high boiling solvents can use separately or two kinds or above mixing are used.
The consumption of solvent is not particularly limited, and considers from viewpoints such as the coating of the radiation-ray sensitive composition that obtains, stability, preferably makes each composition total concentration of removing the said composition solvent reach 5-50 weight %, especially preferably reaches the amount of 10-40 weight %.
Color filter
Color filter of the present invention has the dyed layer that is formed by the radiation-ray sensitive composition that is used to form dyed layer of the present invention.
Below describe for the method for the dyed layer that forms color filter of the present invention.
At first, as required, on the surface of substrate, form light shield layer, the part that forms pixel is distinguished, and coating for example is dispersed with the fluid composition of the radiation-ray sensitive composition of red pigment on this substrate, carries out prebake conditions then, make solvent evaporation, formation is filmed.Then, to this exposure of filming, use alkaline-based developer to develop via photomask then, the unexposed portion of filming is removed in dissolving, by the back baking, forms pel array then, and this pel array is that red pattern of pixels alignment arrangements according to the rules obtains.
Use each fluid composition of the radiation-ray sensitive composition that is dispersed with green or blue pigment then, with above-mentioned coating, prebake conditions, exposure, development and the back baking of similarly carrying out fluid composition, on same substrate, form green pixel array and blue pixel array successively, redness, green and blue trichromatic pixel array configuration can obtain color filter on substrate.Among the present invention, the order that forms each color pixel is not limited to above-mentioned.
In addition, black matrix" can use the radiation-ray sensitive composition that is used to form dyed layer that for example is dispersed with black pigment, similarly forms with the situation of above-mentioned pixel.
The substrate that uses during as formation pixel and/or black matrix" for example has glass, silicon, polycarbonate, polyester, aromatic poly amide, polyamidoimide, polyimide etc.
According to expectation, can also implement to utilize the suitable pre-treatments such as chemical reagent processing, Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, vacuum evaporation of silane coupling agent etc. to these substrates.
When coating the fluid composition of radiation-ray sensitive composition on the substrate, can adopt spraying process, rolling method, method of spin coating (spin-coating method), slit die rubbing method, rod to be coated with suitable coating processes such as method, ink-jet method.Preferred especially spin-coating method, slit die rubbing method.
The thickness of coating calculates according to dried thickness, preferred 0.1-10 μ m, more preferably 0.2-8.0 μ m, especially preferably 0.2-6.0 μ m.
The radioactive ray that use during as formation pixel and/or black matrix" can use for example visible light, ultraviolet ray, far ultraviolet, electron ray, X ray etc.Optimal wavelength is at the radioactive ray of 190-450nm scope.
The exposure of radioactive ray is preferably 10-10,000J/m
2
As above-mentioned alkaline-based developer, preference such as sodium carbonate, NaOH, potassium hydroxide, tetramethyl ammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecylene, 1, the aqueous solution of 5-diazabicyclo-[4.3.0]-5-nonene etc.
In above-mentioned alkaline-based developer, can also add for example water-miscible organic solvent such as methyl alcohol, ethanol or surfactant etc. in right amount.Usually after alkaline development, wash.
As developing method, for example can adopt spray development method, spray development method, immersion development method, soak and put (liquid is contained り) development method etc.Development conditions is preferably carried out 5-300 second at normal temperatures.
The color filter of the present invention that obtains like this is for example extremely useful for transmission-type or reflection-type color liquid crystal display element, colour pick-up tube element, color sensor etc.
Color liquid crystal display device
Color liquid crystal display device of the present invention possesses color filter of the present invention.
A scheme of color liquid crystal display device of the present invention is to use the radiation-ray sensitive composition that is used to form dyed layer of the present invention, as mentioned above, on the thin film transistor base plate array, form pixel and/or black matrix", thereby can prepare color liquid crystal display device with excellent especially characteristic.
The radiation-ray sensitive composition that is used to form dyed layer of the present invention contains above-mentioned (A)-(D) composition as must composition, below specifically provides particularly preferred composition, as following (i)-(iv).
(i) be used to form the radiation-ray sensitive composition of dyed layer, wherein, (B) alkali soluble resins contains polyester (1); this polyester (1) is obtained by diol compound that contains two (methyl) acryloyl group and tetracarboxylic dianhydride's (8) esterification; Mw is 3,000-100,000.
The radiation-ray sensitive composition that is used to form dyed layer of (ii) above-mentioned (i), wherein, (C) multi-functional monomer contains and is selected from least a of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol acrylate.
(iii) above-mentioned (i) or the radiation-ray sensitive composition that is used to form dyed layer (ii); wherein, (D) the optical free radical propellant contains 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-acetic acid esters is as carbazole based compound (D1).
(iv) above-mentioned (i), (ii) or the radiation-ray sensitive composition that is used to form dyed layer (iii), wherein, (A) colorant contains organic pigment and/or carbon black.
Preferred color filter of the present invention has:
(v) pixel and/or the black matrix" that forms by above-mentioned (i), (ii), (iii) or (iv) the radiation-ray sensitive composition that is used to form dyed layer.
Preferred color liquid crystal display device of the present invention possesses:
(vi) above-mentioned (color filter v),
The color liquid crystal display device of present invention further optimization:
(vii) on the thin film transistor base plate array, possesses above-mentioned (color filter v).
As above, even the radiation-ray sensitive composition of dyed layer that is used to form of the present invention is when high concentration contains pigment, in the time of can not developing on the substrate of unexposed portion and on the light shield layer edge of residual not dissolved matter or pattern of pixels and black matrix pattern produce scum silica frost, and under low exposure, also can form the good pattern of pixels and the black matrix pattern of the damaged and lateral erosion that does not have pattern edge.
Use the pixel that the radiation-ray sensitive composition that is used to form dyed layer of the present invention forms and the surface smoothing height of black matrix", good with the tack of substrate.
Therefore, the radiation-ray sensitive composition that is used to form dyed layer of the present invention can be applied in the manufacturing of various color filters that the color liquid crystal display device color filter with electronics industry is representative admirably.
Embodiment
Below provide embodiment, further specify the present invention.The present invention is not limited by following embodiment.Here, part is a weight basis.
The preparation of＜alkali soluble resins 〉
Synthesis example 1 (synthesizing of the diglycidyl ether thing of biphenol)
In the flask that possesses condenser pipe and stirring machine, add 1,070g biphenol (9): the potpourri of biphenol (10)=70: 30 (weight ratio) (trade name YP-90, ヤ ス Ha ラ Network ミ カ Le (strain) system), 1520g chloropropylene oxide, 1, the 700g dimethyl sulfoxide (DMSO), being heated to 50 ℃ while stirring dissolves, add 290g sodium hydroxide then, reacted 10 hours down at 65-90 ℃.Measure epoxide equivalent to confirm the carrying out and the terminal point of reaction, after epoxide equivalent reached desired value, decompression was heated up in a steamer and is desolvated under 90-100 ℃.Then reaction product is dissolved in 50-70 ℃ the toluene again, adds the distilled water washing again, standing separation, decompression obtains the 1260g reaction product down with the organic layer desolventizing then.The epoxide equivalent of gained reaction product is 260.
This reaction product is measured
1H-NMR composes (solvent: CDCl
3, the tetramethylsilane benchmark, below identical), visible chemical shift δ (ppm) 6.8-7.3 (from the phenyl ring of cyclohexane skeleton bonding; 8H), 3.3 and 3.9-4.2 (from epoxy radicals; 6H), 0.7-0.9 (from the isopropyl of cyclohexane skeleton bonding in two methyl; The peak of 6H) locating.
Measure infrared absorption spectrum (IR), visible 1241cm
-1(from aromatic oxide structure and epoxy radicals), 1036cm
-1And 828cm
-1The absorption of (from the aromatic oxide structure).
Can be confirmed by above result: this reaction product is the potpourri of diglycidyl ether thing shown in diglycidyl ether thing shown in the following formula (11) and the following formula (12).
Synthesis example 2 (diol compound synthetic that contains the dimethyl propylene enoyl-)
The potpourri, 350g methacrylic acid, the 1.0g Hydroquinone monomethylether that in the flask that possesses condenser pipe and stirring machine, add the diglycidyl ether thing of 1000g synthesis example 1 gained, be heated to 60 ℃ while stirring and make its dissolving, add the 8g tetraethylammonium bromide then, under 70-90 ℃, continue reaction while stirring, acid number until reaction product is 8mgKOH/g, epoxide equivalent is 17,000.Confirm terminal point by acid number and epoxide equivalent after 15 hours, be cooled to room temperature then, obtain 1, the 300g reaction product.Acid number=the 8mgKOH/g of gained reaction product, hydroxyl value=165mgKOH/g, epoxide equivalent=17,000.
For this reaction product, measure
1H-NMR spectrum, visible chemical shift δ (ppm) 5.6 and 6.1 (from two keys of methacrylic acid; 4H), 3.9-4.4 is (from the peak of the potpourri of diglycidyl ether thing " 3.3 and 3.9-4.2 " because the open loop of epoxy radicals and displacement; Peak 10H).
Measure infrared absorption spectrum (IR), visible 1720cm
-1The absorption of (from the aliphatic (acid) ester structure).
Shown by above result: this reaction product is to contain the diol compound of dimethyl propylene enoyl-and the potpourri of the diol compound that contains the dimethyl propylene enoyl-shown in the following formula (7-1) shown in the following formula (6-1).
Synthesis example 3 (diol compound synthetic that contains two acryloyl groups)
In the synthesis example 2; use 293g acrylic acid to replace methacrylic acid, in addition similarly obtain the potpourri of the diol compound that contains two acryloyl groups shown in diol compound that contains two acryloyl groups shown in the 1200g following formula (6-2) and the following formula (7-2) with synthesis example 2.Acid number=the 6mgKOH/g of gained potpourri, hydroxyl value=171mgKOH/g, epoxide equivalent=16,500.
Synthesis example 4 (preparation of polyester (1))
The potpourri that in the flask that possesses condenser pipe and stirring machine, adds the diol compound that contains the dimethyl propylene enoyl-of 670g synthesis example 2 gained; 1; the 300g methyl isobutyl ketone; be heated to 60 ℃ while stirring and make its dissolving; add the pyromellitic dianhydride shown in the 220g following formula (8-1) (ダ イ セ Le chemical industry (strain) preparation) then; sustained response while stirring under 80 ℃; make the acid number average out to 67.9mgKOH/g of reaction product; the amplitude of fluctuation of acid number is at 2mgKOH/g or following. after reaction finishes; in reaction solution, add distilled water; washing; standing separation, then under reduced pressure with organic layer; heat up in a steamer under 50-70 ℃ and desolvate, obtain the 860g resin.The Mw=18 of gained resin, 000, acid number=61.2mgKOH/g.
This resin is measured
1The H-NMR spectrum, as seen chemical shift δ (ppm) 6.9-7.6 (from the phenyl ring of cyclohexane skeleton bonding and the phenyl ring of Pyromellitic Acid), 5.8 and 6.2 (from two keys positions of methacrylic acid), 1.1-2.2 (from the cyclohexane skeleton), 0.7-0.9 (from 2 of cyclohexane skeleton bonding, two methyl in the 2-propylidene; Peak 6H).
Measure infrared absorption spectrum (IR), visible 1735cm
-1(from the aliphatic (acid) ester structure), 1735cm
-1, 1241cm
-1And 1102cm
-1The absorption of (from the aromatic ester structure).
Shown by above result: this resin is a polyester (1) shown in the following formula (I-1).
This polyester (1) is called " alkali soluble resins (B-1) ".
[in the formula (I-1), X is identical with X implication in the formula (1)].
Synthesis example 5 (preparation of polyester (1))
In the synthesis example 4; the potpourri of the diol compound that contains the dimethyl propylene enoyl-that obtains in the potpourri replacement synthesis example 2 of the diol compound that contains two acryloyl groups of use 660g synthesis example 3 gained; in addition same with synthesis example 4, obtain polyester (1) shown in the 840g following formula (I-2).The Mw=15 of gained polyester (1), 000, acid number=60.9mgKOH/g.
This polyester (1) is called " alkali soluble resins (B-2) ".
[in the formula (I-2), X is identical with X implication in the formula (1)].
Synthesis example 6 (preparation of carboxyl sealing polyester (1))
The polyester (1), the 275g propyleneglycol monomethyl acetates that in the flask that possesses condenser pipe and stirring machine, add 275g synthesis example 4 gained, be heated to 60 ℃ while stirring and make its dissolving, add the 1.5g tetraethylammonium bromide then, add the phenylglycidyl ether (trade name ェ ピ オ one Le P, Japanese grease (strain) preparation) of 30g as the carboxyl sealer, sustained response while stirring under 80-90 ℃, make the amplitude of fluctuation of acid number reach 2mgKOH/g or following. behind the reaction terminating, be cooled to room temperature, obtain the 300g resin.The Mw=21 of gained resin, 000, acid number=52.1mgKOH/g.
This resin is measured
1H-NMR spectrum among the chemical shift δ (ppm), except the peak of the polyester (1) of synthesis example 4 gained, is also shown in the peak of 6.9-7.6 (from the phenyl ring in the phenylglycidyl ether base).
Measure infrared absorption spectrum (IR), visible 1047cm
-1The absorption of (from the aromatic oxide structure), this absorbs because carboxyl seals stronger than the polyester (1) of synthesis example 4 gained.
Shown by above result: this resin is to have 78% of the hydrogen atom in the carboxyl in the following formula (I-1) to be closed agent residue (CH
2CH (OH) CH
2OC
6H
5) polyester (1) of the structure that replaces.
This polyester (1) is called " alkali soluble resins (B-3) ".
Synthesis example 7 (preparation of the polyester (1) of carboxyl sealing)
In the synthesis example 6, use the polyester (1) of polyester (1) replacement synthesis example 4 gained of 300g synthesis example 5 gained, in addition similarly obtain the 340g resin with synthesis example 6.The Mw=25 of gained resin, 000, acid number=50.0mgKOH/g.
This polyester (1) is called " alkali soluble resins (B-4) ".
Synthesis example 8 (preparation of polyester (1))
The potpourri, the 1470g methyl isobutyl ketone that in the flask that possesses condenser pipe and stirring machine, add the diol compound that contains the dimethyl propylene enoyl-of 670g synthesis example 2 gained; be heated to 60 ℃ while stirring; make its dissolving; add the diphenyl ether tetracarboxylic dianhydride shown in the 313g following formula (8-2) (マ Na Star Network (strain) preparation) then; reaction while stirring under 80 ℃, sustained response to acid number is 53.3mgKOH/g.After reaction finishes, in reaction solution, add distilled water, washing, standing separation, then with organic layer under reduced pressure, heat up in a steamer under the 50-70 ℃ and desolvate, obtain the 800g resin.The Mw=18 of gained resin, 000, acid number=61.2mgKOH/g.
This polyester (1) is called " alkali soluble resins (B-5) ".
[in the formula (I-3), X is identical with X implication in the formula (1), Y
1For from the diphenyl ether tetrabasic carboxylic acid, removing the residue of four carboxyl gained].
Synthesis example 9 (preparation of polyester (1))
The potpourri, the 1660g methyl isobutyl ketone that in the flask that possesses condenser pipe and stirring machine, add the diol compound that contains the dimethyl propylene enoyl-of 670g synthesis example 2 gained; be heated to 60 ℃ while stirring and make its dissolving; add ethylene glycol bis (trimellitate) dianhydride shown in the 434g following formula (8-3) (new Japanese physics and chemistry (strain) preparation) then; reaction while stirring under 80 ℃, sustained response to acid number is 46.2mgKOH/g.Behind the reaction terminating, in reaction solution, add distilled water, washing, standing separation, then with organic layer under reduced pressure, heat up in a steamer under the 50-70 ℃ and desolvate, obtain the 900g resin.The Mw=13 of gained resin, 000, be the polyester (1) shown in the following formula (1-4).
This polyester (1) is called " alkali soluble resins (B-6) ".
[in the formula (I-4), X is identical with X implication in the formula (1), Y
2For from ethylene glycol bis (trimellitate), removing the residue of four carboxyl gained].
Synthesis example 10 (being used for the preparation of the alkali soluble resins of comparison)
In the flask that possesses condenser pipe, stirring machine, add 4 part 2,2 '-azo two (2, the 4-methyl pentane nitrile), 200 parts of propylene glycol monomethyl ether, then add 12 parts of methacrylic acids, 18 parts of styrene, 24 parts of benzyl methacrylates, 30 parts of N-phenylmaleimides, 16 parts of 2-hydroxyethyl methacrylates, 6.5 parts of α-Jia Jibenyixierjuwus as chain-transferring agent, the nitrogen displacement, slowly stir then, reaction solution is heated to 80 ℃, keep this temperature, carry out polymerization in 3 hours.Polymerization is heated to 100 ℃ with reaction solution after stopping, and adds 0.5 part 2,2 '-azo two (2, the 4-methyl pentane nitrile), and polymerization is 1 hour again, obtains alkali soluble resins solution (solid concentration=33.2 weight %).
The Mw=8 of gained alkali soluble resins, 500, Mn=4,500.
This alkali soluble resins is called " alkali soluble resins (B-7) ".
Synthesis example 11 (being used for the preparation of the alkali soluble resins of comparison)
In the flask that possesses condenser pipe, stirring machine, add 2 part 2,2 '-azo two (2, the 4-methyl pentane nitrile), 200 parts of propylene glycol monomethyl ether, then add 10 parts of methacrylic acids, 15 parts of styrene, 30 parts of benzyl methacrylates, 25 parts of N-phenylmaleimides, 20 parts of ω-carboxyl polycaprolactone list (methyl) acrylate, 2 parts of α-Jia Jibenyixierjuwus as chain-transferring agent, the nitrogen displacement, slowly stir then, reaction solution is heated to 80 ℃, keep this temperature, carry out polymerization in 3 hours.Polymerization is heated to 100 ℃ with reaction solution after stopping, and adds 0.5 part 2,2 '-azo two (2, the 4-methyl pentane nitrile), and polymerization is 1 hour again, obtains alkali soluble resins solution (solid concentration=33.1 weight %).
The Mw=20 of gained alkali soluble resins, 000, Mn=9,000.
This alkali soluble resins is called " alkali soluble resins (B-8) ".
Synthesis example 12 (being used for the preparation of the alkali soluble resins of comparison)
To possessing condenser pipe, add 4 part 2 in the flask of stirring machine, 2 '-azo two (2, the 4-methyl pentane nitrile), 200 parts of propylene glycol monomethyl ether, then add 10 parts of methacrylic acids, 15 parts of styrene, 40 parts of benzyl methacrylates, 25 parts of N-phenylmaleimides, 10 parts of 2-hydroxyethyl methacrylates, 6.5 part α-Jia Jibenyixierjuwu as chain-transferring agent, the nitrogen displacement, slowly stir then, reaction solution is heated to 80 ℃, keep this temperature, carry out polymerization in 3 hours. after polymerization stops, reaction solution is heated to 100 ℃, add 0.5 part 2,2 '-azo two (2, the 4-methyl pentane nitrile), polymerization is 1 hour again, obtains alkali soluble resins solution (solid concentration=33.3 weight %).
The Mw=7 of gained alkali soluble resins, 800, Mn=4,500.
This alkali soluble resins is called " alkali soluble resins (B-9) ".
Embodiment 1
The preparation of＜fluid composition 〉
8 parts of potpourri, 4 parts of EFKA-46 as spreading agent (being converted into solid content), 75 parts of propylene glycol monomethyl ether as solvent that obtain according to 80: 20 (weight ratio) as the C.I. paratonere 254 and the C.I. paratonere 177 of (A) colorant are handled the preparation dispersible pigment dispersion with ball mill.
Then with 87 parts of gained dispersible pigment dispersions; the alkali soluble resins (B-1) of 8 parts of conducts (B) alkali soluble resins; 2 part of six acrylic acid dipentaerythritol ester and 4 parts of pentaerythritol tetracrylates as (C) multi-functional monomer; 1-[9-ethyl-6-(2-the methyl benzoyl)-9.H.-carbazole-3-yl of 3 parts of conducts (D) optical free radical propellant]-ethane-1-ketoxime-O-acetic acid esters (trade name CGI-242; チ バ ス ペ チ ヤ リ テ イ one Network ミ カ Le ズ society system; as follows); 70 parts of methoxyl butylacetic acid esters and 96 parts of ethyl-3-ethoxy-c acid esters as solvent mix preparation fluid composition (R1).
The formation of＜dyed layer 〉
With spin coater fluid composition (R1) is coated on formation silicon dioxide (SiO
2) on the soda-lime glass substrate of film, prebake conditions 2 minutes on 90 ℃ hot plate then, what form thickness 1.2 μ m films wherein said silicon dioxide (SiO
2) film can prevent the sodion stripping to the surface.
After then substrate being cooled to room temperature, with high-pressure sodium lamp, via photomask (slit width 30 μ m), with containing the ultraviolet ray of 365nm, 405nm and each wavelength of 436nm to the exposure of filming. the exposure of this moment is 100J/m
2Then substrate was soaked 45 seconds in 23 ℃, 0.04 weight % potassium hydroxide aqueous solution, develop, with the ultrapure water washing, air-dry then. back baking 30 minutes in 230 ℃ cleaning oven then forms red striated pattern of pixels on substrate.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 μ m.
Above main contents are shown in table 1-1.
Embodiment 2-5
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent according to table 1-1 change, in addition similarly to Example 1, is prepared fluid composition (R2)-(R5) respectively.
Then, use fluid composition (R2)-(R5) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form red striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 8 or 6 μ m.
Above main contents are shown in table 1-1.
Embodiment 6
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-2), in addition similarly to Example 1, preparation fluid composition (R6).
Then, use fluid composition (R6) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form red striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6 μ m.
Above main contents are shown in table 1-1.
Embodiment 7-10
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent according to table 1-1 change, in addition similarly to Example 6, is prepared fluid composition (R7)-(R10) respectively.
Then, use fluid composition (R7)-(R10) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form red striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5,8 or 6 μ m.
Above main contents are shown in table 1-1.
Embodiment 11
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-3), in addition similarly to Example 1, preparation fluid composition (R11).
Then, use fluid composition (R11) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form red striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 μ m.
Above main contents are shown in table 1-2.
Embodiment 12-15
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent according to table 1-2 change, in addition similarly to Example 11, is prepared fluid composition (R12)-(R15) respectively.
Then, use fluid composition (R12)-(R15) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form red striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6 or 8 μ m.
Above main contents are shown in table 1-2.
Embodiment 16
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-4), in addition similarly to Example 1, preparation fluid composition (R16).
Then, use fluid composition (R16) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form red striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6 μ m.
Above main contents are shown in table 1-2.
Embodiment 17-20
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent according to table 1-2 change, in addition similarly to Example 16, is prepared fluid composition (R17)-(R20) respectively.
Then, use fluid composition (R17)-(R20) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form red striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5,8 or 6 μ m.
Above main contents are shown in table 1-2.
Embodiment 21
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-5), in addition similarly to Example 1, preparation fluid composition (R21).
Then, use fluid composition (R21) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form red striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 8 μ m.
Above main contents are shown in table 1-3.
Embodiment 22-25
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent according to table 1-3 change, in addition similarly to Example 21, is prepared fluid composition (R22)-(R25) respectively.
Then, use fluid composition (R22)-(R25) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form red striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5,8 or 6 μ m.
Above main contents are shown in table 1-3.
Embodiment 26
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-6), in addition similarly to Example 1, preparation fluid composition (R26).
Then, use fluid composition (R26) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form red striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6 μ m.
Above main contents are shown in table 1-3.
Embodiment 27-30
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent according to table 1-3 change, in addition similarly to Example 26, is prepared fluid composition (R27)-(R30) respectively.
Then, use fluid composition (R27)-(R30) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form red striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5,8 or 6 μ m.
Above main contents are shown in table 1-3.
Embodiment 31
The preparation of＜fluid composition 〉
11 parts of potpourri, 4 parts of EFKA-46 as spreading agent (being converted into solid content), 75 parts of propylene glycol monomethyl ether as solvent that obtain according to 60: 40 (weight ratio) as the C.I. pigment green 36 and the C.I. pigment yellow 150 of (A) colorant are handled the preparation dispersible pigment dispersion with ball mill.
Then with 90 parts of gained dispersible pigment dispersions, 8 parts of alkali soluble resinss (B-1) as (B) alkali soluble resins, as 2 part of six acrylic acid dipentaerythritol ester of (C) multi-functional monomer and 4 parts of pentaerythritol tetracrylates, 3 parts of 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl as (D) optical free radical propellant]-ethane-1-ketoxime-O-acetic acid esters, mix as 70 parts of methoxyl butylacetic acid esters and 96 parts of ethyl-3-ethoxy-c acid esters of solvent, prepare fluid composition (G1).
The formation of＜dyed layer 〉
Then, use fluid composition (G1) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form green striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6 μ m.
Above main contents are shown in table 2-1.
Embodiment 32-35
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 2-1 change, in addition same with embodiment 31, prepare fluid composition (G2)-(G5) respectively.
Then, use fluid composition (G2)-(G5) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form green striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 8 or 6 μ m.
Above main contents are shown in table 2-1.
Embodiment 36
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-2), in addition same with embodiment 31, preparation fluid composition (G6).
Then, use fluid composition (G6) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form green striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 μ m.
Above main contents are shown in table 2-1.
Embodiment 37-40
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 2-1 change, in addition same with embodiment 36, prepare fluid composition (G7)-(G10) respectively.
Then, use fluid composition (G7)-(G10) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form green striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6,8 or 5 μ m.
Above main contents are shown in table 2-1.
Embodiment 41
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-3), in addition same with embodiment 31, preparation fluid composition (G11).
Then, use fluid composition (G11) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form green striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 μ m.
Above main contents are shown in table 2-2.
Embodiment 42-45
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 2-2 change, in addition same with embodiment 41, prepare fluid composition (G12)-(G15) respectively.
Then, use fluid composition (G12)-(G15) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form green striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 or 6 μ m.
Above main contents are shown in table 2-2.
Embodiment 46
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-4), in addition same with embodiment 31, preparation fluid composition (G16).
Then, use fluid composition (G16) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form green striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6 μ m.
Above main contents are shown in table 2-2.
Embodiment 47-50
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 2-2 change, in addition same with embodiment 46, prepare fluid composition (G17)-(G20) respectively.
Then, use fluid composition (G17)-(G20) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form green striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6,5 or 8 μ m.
Above main contents are shown in table 2-2.
Embodiment 51
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-5), in addition same with embodiment 31, preparation fluid composition (G21).
Then, use fluid composition (G21) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form green striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6 μ m.
Above main contents are shown in table 2-3.
Embodiment 52-55
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 2-3 change, in addition same with embodiment 51, prepare fluid composition (G22)-(G25) respectively.
Then, use fluid composition (G22)-(G25) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form green striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6,8 or 5 μ m.
Above main contents are shown in table 2-3.
Embodiment 56
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-6), in addition same with embodiment 31, preparation fluid composition (G26).
Then, use fluid composition (G26) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form green striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 μ m.
Above main contents are shown in table 2-3.
Embodiment 57-60
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 2-3 change, in addition same with embodiment 56, prepare fluid composition (G27)-(G30) respectively.
Then, use fluid composition (G27)-(G30) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form green striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5,6 or 8 μ m.
Above main contents are shown in table 2-3.
Embodiment 61
The preparation of＜fluid composition 〉
With 9 parts of C.I. pigment blue 15s as (A) colorant: 6 and C.I. pigment Violet 23 potpourri, 4 parts of EFKA-46 (being converted into solid content), 75 parts of propylene glycol monomethyl ether of obtaining according to 95:5 (weight ratio) as solvent as spreading agent handle the preparation dispersible pigment dispersion with ball mill.
Then with 88 parts of gained dispersible pigment dispersions, 8 parts of alkali soluble resinss (B-1) as (B) alkali soluble resins, as 2 part of six acrylic acid dipentaerythritol ester of (C) multi-functional monomer and 4 parts of pentaerythritol tetracrylates, 3 parts of 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl as (D) optical free radical propellant]-ethane-1-ketoxime-O-acetic acid esters, mix as 70 parts of methoxyl butylacetic acid esters and 96 parts of ethyl-3-ethoxy-c acid esters of solvent, prepare fluid composition (B1).
The formation of＜dyed layer 〉
Then, use fluid composition (B1) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form blue striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 μ m.
Above main contents are shown in table 3-1.
Embodiment 62-65
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 3-1 change, in addition same with embodiment 61, prepare fluid composition (B2)-(B5) respectively.
Then, use fluid composition (B2)-(B5) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form blue striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 or 6 μ m.
Above main contents are shown in table 3-1.
Embodiment 66
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-2), in addition same with embodiment 61, preparation fluid composition (B6).
Then, use fluid composition (B6) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form blue striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6 μ m.
Above main contents are shown in table 3-1.
Embodiment 67-70
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 3-1 change, in addition same with embodiment 66, prepare fluid composition (B7)-(B10) respectively.
Then, use fluid composition (B7)-(B10) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form blue striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 8 or 5 μ m.
Above main contents are shown in table 3-1.
Embodiment 71
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-3), in addition same with embodiment 61, preparation fluid composition (B11).
Then, use fluid composition (B11) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form blue striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6 μ m.
Above main contents are shown in table 3-2.
Embodiment 72-75
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 3-2 change, in addition same with embodiment 71, prepare fluid composition (B12)-(B15) respectively.
Then, use fluid composition (B12)-(B15) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form blue striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5,6 or 8 μ m.
Above main contents are shown in table 3-2.
Embodiment 76
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-4), in addition same with embodiment 61, preparation fluid composition (B16).
Then, use fluid composition (B16) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form blue striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 μ m.
Above main contents are shown in table 3-2.
Embodiment 77-80
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 3-2 change, in addition same with embodiment 76, prepare fluid composition (B17)-(B20) respectively.
Then, use fluid composition (B17)-(B20) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form blue striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 or 8 μ m.
Above main contents are shown in table 3-2.
Embodiment 81
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-5), in addition same with embodiment 61, preparation fluid composition (B21).
Then, use fluid composition (B21) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form blue striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 μ m.
Above main contents are shown in table 3-3.
Embodiment 82-85
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 3-3 change, in addition same with embodiment 81, prepare fluid composition (B22)-(B25) respectively.
Then, use fluid composition (B22)-(B25) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form blue striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 or 8 μ m.
Above main contents are shown in table 3-3.
Embodiment 86
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-6), in addition same with embodiment 61, preparation fluid composition (B26).
Then, use fluid composition (B26) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form blue striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 8 μ m.
Above main contents are shown in table 3-3.
Embodiment 87-90
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 3-3 change, in addition same with embodiment 86, prepare fluid composition (B27)-(B30) respectively.
Then, use fluid composition (B27)-(B30) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form blue striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 8 or 5 μ m.
Above main contents are shown in table 3-3.
Embodiment 91
The preparation of＜fluid composition 〉
20 parts of carbon blacks as (A) colorant, 4 parts of EFKA-46 as spreading agent (being converted into solid content), 75 parts of propylene glycol monomethyl ether as solvent are handled the preparation dispersible pigment dispersion with ball mill.
Then with 99 parts of gained dispersible pigment dispersions, 8 parts of alkali soluble resinss (B-1) as (B) alkali soluble resins, as 2 part of six acrylic acid dipentaerythritol ester of (C) multi-functional monomer and 4 parts of pentaerythritol tetracrylates, 3 parts of 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl as (D) optical free radical propellant]-ethane-1-ketoxime-O-acetic acid esters, 150 parts of propylene glycol monomethyl ether as solvent mix, and prepares fluid composition (BK1).
The formation of＜dyed layer 〉
Then, use fluid composition (BK1) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form the striated pattern of pixels of black.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 8 μ m.
Above main contents are shown in table 4-1.
Embodiment 92-95
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 4-1 change, in addition same with embodiment 91, prepare fluid composition (BK2)-(BK5) respectively.
Then, use fluid composition (BK2)-(BK5) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form the striated pattern of pixels of black.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 or 6 μ m.
Above main contents are shown in table 4-1.
Embodiment 96
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-2), in addition same with embodiment 91, preparation fluid composition (BK6).
Then, use fluid composition (BK6) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form the striated pattern of pixels of black.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 μ m.
Above main contents are shown in table 4-1.
Embodiment 97-100
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 4-1 change, in addition same with embodiment 96, prepare fluid composition (BK7)-(BK10) respectively.
Then, use fluid composition (BK7)-(BK10) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form the striated pattern of pixels of black.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6 or 5 μ m.
Above main contents are shown in table 4-1.
Embodiment 101
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-3), in addition same with embodiment 91, preparation fluid composition (BK11).
Then, use fluid composition (BK11) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form the striated pattern of pixels of black.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6 μ m.
Above main contents are shown in table 4-2.
Embodiment 102-105
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 4-2 change, in addition same with embodiment 101, prepare fluid composition (BK12)-(BK15) respectively.
Then, use fluid composition (BK12)-(BK15) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form the striated pattern of pixels of black.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5,8 or 6 μ m.
Above main contents are shown in table 4-2.
Embodiment 106
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-4), in addition same with embodiment 91, preparation fluid composition (BK16).
Then, use fluid composition (BK16) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form the striated pattern of pixels of black.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 8 μ m.
Above main contents are shown in table 4-2.
Embodiment 107-110
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 4-2 change, in addition same with embodiment 106, prepare fluid composition (BK17)-(BK20) respectively.
Then, use fluid composition (BK17)-(BK20) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form the striated pattern of pixels of black.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6 or 5 μ m.
Above main contents are shown in table 4-2.
Embodiment 111
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-5), in addition same with embodiment 91, preparation fluid composition (BK21).
Then, use fluid composition (BK21) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form the striated pattern of pixels of black.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 6 μ m.
Above main contents are shown in table 4-3.
Embodiment 112-115
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 4-3 change, in addition same with embodiment 111, prepare fluid composition (BK22)-(BK25) respectively.
Then, use fluid composition (BK22)-(BK25) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form the striated pattern of pixels of black.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 8,6 or 5 μ m.
Above main contents are shown in table 4-3.
Embodiment 116
The preparation of＜fluid composition and the formation of dyed layer 〉
(B) alkali soluble resins is changed to alkali soluble resins (B-6), in addition same with embodiment 91, preparation fluid composition (BK26).
Then, use fluid composition (BK26) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form the striated pattern of pixels of black.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 5 μ m.
Above main contents are shown in table 4-3.
Embodiment 117-120
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is according to table 4-3 change, in addition same with embodiment 116, prepare fluid composition (BK27)-(BK30) respectively.
Then, use fluid composition (BK27)-(BK30) to replace fluid composition (R1) respectively, in addition similarly to Example 1, on substrate, form the striated pattern of pixels of black.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, and the edge of pattern of pixels is not seen damaged.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), do not see lateral erosion, and can form the pattern of live width 8 or 5 μ m.
Above main contents are shown in table 4-3.
Comparative example 1
The preparation of＜fluid composition 〉
8 parts of potpourri, 4 parts of EFKA-46 as spreading agent (being converted into solid content), 75 parts of propylene glycol monomethyl ether as solvent that obtain according to 80: 20 (weight ratio) as the C.I. paratonere 254 and the C.I. paratonere 177 of (A) colorant are handled the preparation dispersible pigment dispersion with ball mill.
Then with 87 parts of gained dispersible pigment dispersions; as the 2 parts of alkali soluble resinss (B-7) of alkali soluble resins and the potpourri of 3 parts of alkali soluble resinss (B-8) and 4 parts of alkali soluble resinss (B-9); 2 part of six acrylic acid dipentaerythritol ester and 4 parts of pentaerythritol tetracrylates as (C) multi-functional monomer; 1-[9-ethyl-6-(2-the methyl benzoyl)-9.H.-carbazole-3-yl of 3 parts of conducts (D) optical free radical propellant]-ethane-1-ketoxime-O-acetic acid esters; 70 parts of methoxyl butylacetic acid esters and 96 parts of ethyl-3-ethoxy-c acid esters as solvent mix preparation fluid composition (CR1).
The formation of＜dyed layer 〉
Then, use fluid composition (CR1) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form red striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, visible development residue on the substrate of unexposed portion.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), visible lateral erosion, and only form the pattern of live width 35 μ m.
Above main contents are as shown in table 5.
Comparative example 2
The preparation of＜fluid composition 〉
11 parts of potpourri, 4 parts of BYK-2000 as spreading agent (being converted into solid content), 75 parts of propylene glycol monomethyl ether as solvent that obtain according to 60: 40 (weight ratio) as the C.I. pigment green 36 and the C.I. pigment yellow 150 of (A) colorant are handled the preparation dispersible pigment dispersion with ball mill.
Then with 90 parts of gained dispersible pigment dispersions; as the 2 parts of alkali soluble resinss (B-7) of alkali soluble resins and the potpourri of 3 parts of alkali soluble resinss (B-8) and 4 parts of alkali soluble resinss (B-9); 2 part of six acrylic acid dipentaerythritol ester and 4 parts of pentaerythritol tetracrylates as (C) multi-functional monomer; 1-[9-ethyl-6-(2-the methyl benzoyl)-9.H.-carbazole-3-yl of 3 parts of conducts (D) optical free radical propellant]-ethane-1-ketoxime-O-acetic acid esters; 70 parts of methoxyl butylacetic acid esters and 96 parts of ethyl-3-ethoxy-c acid esters as solvent mix preparation fluid composition (CG1).
The formation of＜dyed layer 〉
Then, use fluid composition (CG1) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form green striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, but observe the cross section of pattern of pixels by sweep electron microscope (SEM), visible lateral erosion, and only form the pattern of live width 45 μ m.
Above main contents are as shown in table 5.
Comparative example 3
The preparation of＜fluid composition 〉
With 9 parts of C.I. pigment blue 15s as (A) colorant: 6 and C.I. pigment Violet 23 potpourri, 4 parts of BYK-2001 (being converted into solid content), 75 parts of propylene glycol monomethyl ether of obtaining according to 95/5 (weight ratio) as solvent as spreading agent handle the preparation dispersible pigment dispersion with ball mill.
Then with 88 parts of gained dispersible pigment dispersions; as the 2 parts of alkali soluble resinss (B-7) of alkali soluble resins and the potpourri of 3 parts of alkali soluble resinss (B-8) and 4 parts of alkali soluble resinss (B-9); 2 part of six acrylic acid dipentaerythritol ester and 4 parts of pentaerythritol tetracrylates as (C) multi-functional monomer; 1-[9-ethyl-6-(2-the methyl benzoyl)-9.H.-carbazole-3-yl of 3 parts of conducts (D) optical free radical propellant]-ethane-1-ketoxime-O-acetic acid esters; 70 parts of methoxyl butylacetic acid esters and 96 parts of ethyl-3-ethoxy-c acid esters as solvent mix preparation fluid composition (CB1).
The formation of＜dyed layer 〉
Then, use fluid composition (CB1) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form blue striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, on the substrate of unexposed portion, do not see the development residue, but observe the cross section of pattern of pixels by sweep electron microscope (SEM), visible lateral erosion, and only form the pattern of live width 40 μ m.
Above main contents are as shown in table 5.
Comparative example 4
The preparation of＜fluid composition 〉
20 parts of carbon blacks as (A) colorant, 4 parts of BYK-164 as spreading agent (being converted into solid content), 75 parts of propylene glycol monomethyl ether as solvent are handled the preparation dispersible pigment dispersion with ball mill.
Then with 99 parts of gained dispersible pigment dispersions, as the potpourri of 2 parts of alkali soluble resinss (B-7) of alkali soluble resins and 3 parts of alkali soluble resinss (B-8) and 4 parts of alkali soluble resinss (B-9), as 2 part of six acrylic acid dipentaerythritol ester of (C) multi-functional monomer and 4 parts of pentaerythritol tetracrylates, 3 parts of 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl as (D) optical free radical propellant]-ethane-1-ketoxime-O-acetic acid esters, 150 parts of propylene glycol monomethyl ether mixing as solvent, prepare fluid composition (CBK1).
The formation of＜dyed layer 〉
Then, use fluid composition (CBK1) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form the striated pattern of pixels of black.
＜estimate
By the pel array on the observation by light microscope substrate, visible development residue on the substrate of unexposed portion.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), visible lateral erosion, and only form the pattern of live width 50 μ m.
Above main contents are as shown in table 5.
Comparative example 5
The preparation of＜fluid composition and the formation of dyed layer 〉
Spreading agent is changed to BYK-182, in addition same with comparative example 1, preparation fluid composition (CR2).
The formation of＜dyed layer 〉
Then, use fluid composition (CR2) to replace fluid composition (R1), in addition similarly to Example 1, on substrate, form red striated pattern of pixels.
＜estimate
By the pel array on the observation by light microscope substrate, visible development residue on the substrate of unexposed portion.
Observe the cross section of pattern of pixels by sweep electron microscope (SEM), visible lateral erosion, and only form the pattern of live width 45 μ m.
Above main contents are as shown in table 5.
Table 1-1
| Embodiment | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | |
| Red pigment (* 1) (part) spreading agent (part) EFKA-46 BYK-2000 BYK-2001 BYK-164 BYK-182 | 8 4 - - - - | 8 - 4 - - - | 8 - - 4 - - | 8 - - - 4 - | 8 - - - - 4 | 8 4 - - - - | 8 - 4 - - - | 8 - - 4 - - | 8 - - - 4 - | 8 - - - - 4 |
| (B) alkali soluble resins (part) B-1 B-2 B-3 B-4 B-5 B-6 | 8 - - - - - | 8 - - - - - | 8 - - - - - | 8 - - - - - | 8 - - - - - | - 8 - - - - | - 8 - - - - | - 8 - - - - | - 8 - - - - | - 8 - - - - |
| Estimate development residue lateral erosion live width (μ m) | Do not have 5 | Do not have 8 | Do not have 6 | Do not have 6 | Do not have 8 | Do not have 6 | Do not have 5 | Do not have 5 | Do not have 8 | Do not have 6 |
* 80/20 (weight ratio) potpourri of 1:C.I. paratonere 245 and C.I. paratonere 177
Table 1-2
| Embodiment | ||||||||||
| 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | |
| Red pigment (* 1) (part) spreading agent (part) EFKA-46 BYK-2000 BYK-2001 BYK-164 BYK-182 | 8 4 - - - - | 8 - 4 - - - | 8 - - 4 - - | 8 - - - 4 - | 8 - - - - 4 | 8 4 - - - - | 8 - 4 - - - | 8 - - 4 - - | 8 - - - 4 - | 8 - - - - 4 |
| (B) alkali soluble resins (part) B-1 B-2 B-3 B-4 B-5 B-6 | - - 8 - - - | - - 8 - - - | - - 8 - - - | - - 8 - - - | - - 8 - - - | - - - 8 - - | - - - 8 - - | - - - 8 - - | - - - 8 - - | - - - 8 - - |
| Estimate development residue lateral erosion live width (μ m) | Do not have 5 | Do not have 6 | Do not have 6 | Do not have 8 | Do not have 6 | Do not have 6 | Do not have 5 | Do not have 8 | Do not have 6 | Do not have 6 |
* 80/20 (weight ratio) potpourri of 1:C.I. paratonere 245 and C.I. paratonere 177
Table 1-3
| Embodiment | ||||||||||
| 21 | 22 | 23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 | |
| Red pigment (* 1) (part) spreading agent (part) EFKA-46 BYK-2000 BYK-2001 BYK-164 BYK-182 | 8 4 - - - - | 8 - 4 - - - | 8 - - 4 - - | 8 - - - 4 - | 8 - - - - 4 | 8 4 - - - - | 8 - 4 - - - | 8 - - 4 - - | 8 - - - 4 - | 8 - - - - 4 |
| (B) alkali soluble resins (part) B-1 B-2 B-3 B-4 B-5 B-6 | - - - - 8 - | - - - - 8 - | - - - - 8 - | - - - - 8 - | - - - - 8 - | - - - - - 8 | - - - - - 8 | - - - - - 8 | - - - - - 8 | - - - - - 8 |
| Estimate development residue lateral erosion live width (μ m) | Do not have 8 | Do not have 5 | Do not have 8 | Do not have 8 | Do not have 6 | Do not have 6 | Do not have 5 | Do not have 8 | Do not have 6 | Do not have 8 |
* 80/20 (weight ratio) potpourri of 1:C.I. paratonere 245 and C.I. paratonere 177
Table 2-1
| Embodiment | ||||||||||
| 31 | 32 | 33 | 34 | 35 | 36 | 37 | 38 | 39 | 40 | |
| Viridine green (* 2) (part) spreading agent (part) EFKA-46 BYK-2000 BYK-2001 BYK-164 BYK-182 | 11 4 - - - - | 11 - 4 - - - | 11 - - 4 - - | 11 - - - 4 - | 11 - - - - 4 | 11 4 - - - - | 11 - 4 - - - | 11 - - 4 - - | 11 - - - 4 - | 11 - - - - 4 |
| (B) alkali soluble resins (part) B-1 B-2 B-3 B-4 B-5 B-6 | 8 - - - - - | 8 - - - - - | 8 - - - - - | 8 - - - - - | 8 - - - - - | - 8 - - - - | - 8 - - - - | - 8 - - - - | - 8 - - - - | - 8 - - - - |
| Estimate development residue lateral erosion live width (μ m) | Do not have 6 | Do not have 8 | Do not have 6 | Do not have 6 | Do not have 6 | Do not have 5 | Do not have 6 | Do not have 8 | Do not have 8 | Do not have 5 |
* 60/40 (weight ratio) potpourri of 2:C.I. pigment green 36 and C.I. pigment yellow 150
Table 2-2
| Embodiment | ||||||||||
| 41 | 42 | 43 | 44 | 45 | 46 | 47 | 48 | 49 | 50 | |
| Viridine green (* 2) (part) spreading agent (part) EFKA-46 BYK-2000 BYK-2001 BYK-164 BYK-182 | 11 4 - - - - | 11 - 4 - - - | 11 - - 4 - - | 11 - - - 4 - | 11 - - - - 4 | 11 4 - - - - | 11 - 4 - - - | 11 - - 4 - - | 11 - - - 4 - | 11 - - - - 4 |
| (B) alkali soluble resins (part) B-1 B-2 B-3 B-4 B-5 B-6 | - - 8 - - - | - - 8 - - - | - - 8 - - - | - - 8 - - - | - - 8 - - - | - - - 8 - - | - - - 8 - - | - - - 8 - - | - - - 8 - - | - - - 8 - - |
| Estimate development residue lateral erosion live width (μ m) | Do not have 5 | Do not have 5 | Do not have 5 | Do not have 6 | Do not have 6 | Do not have 6 | Do not have 6 | Do not have 5 | Do not have 5 | Do not have 8 |
* 60/40 (weight ratio) potpourri of 2:C.I. pigment green 36 and C.I. pigment yellow 150
Table 2-3
| Embodiment | ||||||||||
| 51 | 52 | 53 | 54 | 55 | 56 | 57 | 58 | 59 | 60 | |
| Viridine green (* 2) (part) spreading agent (part) EFKA-46 BYK-2000 BYK-2001 BYK-164 BYK-182 | 11 4 - - - - | 11 - 4 - - - | 11 - - 4 - - | 11 - - - 4 - | 11 - - - - 4 | 11 4 - - - - | 11 - 4 - - - | 11 - - 4 - - | 11 - - - 4 - | 11 - - - - 4 |
| (B) alkali soluble resins (part) B-1 B-2 B-3 B-4 B-5 B6 | - - - - 8 - | - - - - 8 - | - - - - 8 - | - - - - 8 - | - - - - 8 - | - - - - - 8 | - - - - - 8 | - - - - - 8 | - - - - - 8 | - - - - - 8 |
| Estimate development residue lateral erosion live width (μ m) | Do not have 6 | Do not have 6 | Do not have 8 | Do not have 6 | Do not have 5 | Do not have 5 | Do not have 5 | Do not have 6 | Do not have 8 | Do not have 5 |
* 60/40 (weight ratio) potpourri of 2:C.I. pigment green 36 and C.I. pigment yellow 150
Table 3-1
| Embodiment | ||||||||||
| 61 | 62 | 63 | 64 | 65 | 66 | 67 | 68 | 69 | 70 | |
| Blue pigment (* 3) (part) spreading agent (part) EFKA-46 BYK-2000 BYK-2001 BYK-164 BYK-182 | 9 4 - - - - | 9 - 4 - - - | 9 - - 4 - - | 9 - - - 4 - | 9 - - - - 4 | 9 4 - - - - | 9 - 4 - - - | 9 - - 4 - - | 9 - - - 4 - | 9 - - - - 4 |
| (B) alkali soluble resins (part) B-1 B-2 B-3 B-4 B-5 B-6 | 8 - - - - - | 8 - - - - - | 8 - - - - - | 8 - - - - - | 8 - - - - - | - 8 - - - - | - 8 - - - - | - 8 - - - - | - 8 - - - - | - 8 8 - - - |
| Estimate development residue lateral erosion live width (μ m) | Do not have 5 | Do not have 5 | Do not have 5 | Do not have 6 | Do not have 6 | Do not have 6 | Do not have 8 | Do not have 8 | Do not have 8 | Do not have 5 |
* 3:C.I. pigment blue 15: 6 and 95/5 (weight ratio) potpourri of C.I. pigment Violet 23
Table 3-2
| Embodiment | ||||||||||
| 71 | 72 | 73 | 74 | 75 | 76 | 77 | 78 | 79 | 80 | |
| Blue pigment (* 3) (part) spreading agent (part) EFKA-46 BYK-2000 BYK-2001 BYK-164 BYK-182 | 9 4 - - - - | 9 - 4 - - - | 9 - - 4 - - | 9 - - - 4 - | 9 - - - - 4 | 9 4 - - - - | 9 - 4 - - - | 9 - - 4 - - | 9 - - - 4 - | 9 - - - - 4 |
| (B) alkali soluble resins (part) B-1 B-2 B-3 B-4 B-5 B-6 | - - 8 - - - | - - 8 - - - | - - 8 - - - | - - 8 - - - | - - 8 - - - | - - - 8 - - | - - - 8 - - | - - - 8 - - | - - - 8 - - | - - - 8 - - |
| Estimate development residue lateral erosion live width (μ m) | Do not have 6 | Do not have 5 | Do not have 6 | Do not have 8 | Do not have 8 | Do not have 5 | Do not have 5 | Do not have 8 | Do not have 8 | Do not have 5 |
* 3:C.I. pigment blue 15: 6 and 95/5 (weight ratio) potpourri of C.I. pigment Violet 23
Table 3-3
| Embodiment | ||||||||||
| 81 | 82 | 83 | 84 | 85 | 86 | 87 | 88 | 89 | 90 | |
| Blue pigment (* 3) (part) spreading agent (part) EFKA-46 BYK-2000 BYK-2001 BYK-164 BYK-182 | 9 4 - - - - | 9 - 4 - - - | 9 - - 4 - - | 9 - - - 4 - | 9 - - - - 4 | 9 4 - - - - | 9 - 4 - - - | 9 - - 4 - - | 9 - - - 4 - | 9 - - - - 4 |
| (B) alkali soluble resins (part) B-1 B-2 B-3 B-4 B-5 B-6 | - - - - 8 - | - - - - 8 - | - - - - 8 - | - - - - 8 - | - - - - 8 - | - - - - - 8 | - - - - - 8 | - - - - - 8 | - - - - - 8 | - - - - - 8 |
| Estimate development residue lateral erosion live width (μ m) | Do not have 5 | Do not have 5 | Do not have 8 | Do not have 5 | Do not have 5 | Do not have 8 | Do not have 8 | Do not have 8 | Do not have 8 | Do not have 5 |
* 3:C.I. pigment blue 15: 6 and 95/5 (weight ratio) potpourri of C.I. pigment Violet 23
Table 4-1
| Embodiment | ||||||||||
| 91 | 92 | 93 | 94 | 95 | 96 | 97 | 98 | 99 | 100 | |
| Carbon black (part) spreading agent (part) EFKA-46 BYK-2000 BYK-2001 BYK-164 BYK-182 | 20 4 - - - - | 20 - 4 - - - | 20 - - 4 - - | 20 - - - 4 - | 20 - - - - 4 | 20 4 - - - - | 20 - 4 - - - | 20 - - 4 - - | 20 - - - 4 - | 20 - - - - 4 |
| (B) alkali soluble resins (part) B-1 B-2 B-3 B-4 B-5 B-6 | 8 - - - - - | 8 - - - - - | 8 - - - - - | 8 - - - - - | 8 - - - - - | - 8 - - - - | - 8 - - - - | - 8 - - - - | - 8 - - - - | - 8 - - - - |
| Estimate development residue lateral erosion live width (μ m) | Do not have 8 | Do not have 5 | Do not have 6 | Do not have 5 | Do not have 6 | Do not have 5 | Do not have 6 | Do not have 5 | Do not have 5 | Do not have 6 |
Table 4-2
| Embodiment | ||||||||||
| 101 | 102 | 103 | 104 | 105 | 106 | 107 | 108 | 109 | 110 | |
| Carbon black (part) spreading agent (part) EFKA-46 BYK-2000 BYK-2001 BYK-164 BYK-182 | 20 4 - - - - | 20 - 4 - - - | 20 - - 4 - - | 20 - - - 4 - | 20 - - - - 4 | 20 4 - - - - | 20 - 4 - - - | 20 - - 4 - - | 20 - - - 4 - | 20 - - - - 4 |
| (B) alkali soluble resins (part) B-1 B-2 B-3 B-4 B-5 B-6 | - - 8 - - - | - - 8 - - - | - - 8 - - - | - - 8 - - - | - - 8 - - - | - - - 8 - - | - - - 8 - - | - - - 8 - - | - - - 8 - - | - - - 8 - - |
| Estimate development residue lateral erosion live width (μ m) | Do not have 6 | Do not have 5 | Do not have 8 | Do not have 6 | Do not have 5 | Do not have 8 | Do not have 6 | Do not have 5 | Do not have 5 | Do not have 5 |
Table 4-3
| Embodiment | ||||||||||
| 111 | 112 | 113 | 114 | 115 | 116 | 117 | 118 | 119 | 120 | |
| Carbon black (part) spreading agent (part) EFKA-46 BYK-2000 BYK-2001 BYK-164 BYK-182 | 20 4 - - - - | 20 - 4 - - - | 20 - - 4 - - | 20 - - - 4 - | 20 - - - - 4 | 20 4 - - - - | 20 - 4 - - - | 20 - - 4 - - | 20 - - - 4 - | 20 - - - - 4 |
| (B) alkali soluble resins (part) B-1 B-2 B-3 B4 B-5 B-6 | - - - - 8 - | - - - - 8 - | - - - - 8 - | - - - - 8 - | - - - - 8 - | - - - - - 8 | - - - - - 8 | - - - - - 8 | - - - - - 8 | - - - - - 8 |
| Estimate development residue lateral erosion live width (μ m) | Do not have 6 | Do not have 8 | Do not have 6 | Do not have 5 | Do not have 8 | Do not have 5 | Do not have 8 | Do not have 8 | Do not have 5 | Do not have 5 |
Table 5
| Comparative example | |||||
| 1 | 2 | 3 | 4 | 5 | |
| Red pigment (* 1) (part) viridine green (* 2) (part) blue pigment (* 3) (part) carbon black (part) spreading agent (part) EFKA-46 BYK-2000 BYK-2001 BYK-164 BYK-182 | 8 - - - 4 - - - - | - 11 - - - 4 - - - | - - 9 - - - 4 - - | - - - 20 - - - 4 - | 8 - - - - - - - 4 |
| Alkali soluble resins (part) B-7 B-8 B-9 | 2 3 4 | 2 3 4 | 2 3 4 | 2 3 4 | 2 3 4 |
| Estimate development residue lateral erosion live width (μ m) | Have 35 | Do not have and have 45 | Do not have and have 40 | Have 50 | Have 45 |
* 80/20 (weight ratio) potpourri of 1:CI. paratonere 245 and C.I. paratonere 177
* 60/40 (weight ratio) potpourri of 2:C.I. pigment green 36 and C.I. pigment yellow 150
* 3:C.I. pigment blue 15: 6 and 95/5 (weight ratio) potpourri of C.I. pigment Violet 23
Claims (5)
1. radiation-ray sensitive composition, it contains (A) colorant, (B) alkali soluble resins, (C) multi-functional monomer and (D) optical free radical propellant, and be used to form dyed layer, wherein (B) alkali soluble resins contains polyester, and have the ester ring type hydrocarbon skeleton on the main chain of described polyester, and have the polymerism unsaturated link on the side chain.
2. the radiation-ray sensitive composition of claim 1, wherein, (B) composition is the polyester shown in the following formula (1):
In the formula (1), each X is separate, the divalent group shown in expression following formula (2) or the formula (3), and each Y is separate, and the residue of four carboxyl gained, each R are removed in expression from organic tetrabasic carboxylic acid
1Separate, expression hydrogen atom or methyl, each R
2Separate, expression hydrogen atom or carboxyl sealer residue, n is the integer of 1-40.
3. claim 1 or 2 radiation-ray sensitive composition, wherein, (D) the optical free radical propellant contains the compound shown in following formula (4) or the formula (5):
In formula (4) and the formula (5), each R
3Separate, straight chain, branching or cyclic alkyl or the phenyl of expression carbon number 1-12, each R
4Separate, straight chain, branching or cyclic alkyl or the phenyl of expression hydrogen atom, carbon number 1-12, each R
5Separate, straight chain, branching or the cyclic alkyl of expression hydrogen atom or carbon number 1-12, each R
6, each R
7With each R
8Separate, straight chain, branching or the cyclic alkyl of expression hydrogen atom or carbon number 1-6; R wherein
3, R
4, R
5, R
6, R
7And R
8The alkyl substituting group of alkoxy, phenyl and halogen atom that can be selected from straight chain, branching or the ring-type of carbon number 1-6 separately replace; R
3And R
4Phenyl can be selected from straight chain, branching or the cyclic alkyl of carbon number 1-6 separately, the straight chain of carbon number 1-6, branching or cyclic alkoxy, the substituting group of phenyl and halogen atom replaces.
4. color filter, this color filter has the dyed layer that is formed by each radiation-ray sensitive composition among the claim 1-3.
5. color liquid crystal display device, this color liquid crystal display device possesses the color filter of claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006188850A JP4752648B2 (en) | 2006-07-10 | 2006-07-10 | Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element |
| JP2006188850 | 2006-07-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101105630A true CN101105630A (en) | 2008-01-16 |
Family
ID=38999585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101360146A Pending CN101105630A (en) | 2006-07-10 | 2007-07-10 | Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4752648B2 (en) |
| KR (1) | KR20080005867A (en) |
| CN (1) | CN101105630A (en) |
| SG (1) | SG139651A1 (en) |
| TW (1) | TWI430027B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890660A (en) * | 2011-10-25 | 2014-06-25 | 三菱化学株式会社 | Colored photosensitive resin composition, colored spacer, color filter, and liquid crystal display device |
| CN107250208A (en) * | 2015-03-23 | 2017-10-13 | Jsr株式会社 | Polymer, resin combination and resin-formed body |
| CN108503577A (en) * | 2017-02-28 | 2018-09-07 | 东友精细化工有限公司 | Oxime ester based compound and Photocurable composition comprising it |
| CN109351323A (en) * | 2018-11-09 | 2019-02-19 | 天津碧水源膜材料有限公司 | De- ammonium material of selectivity and the preparation method and application thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5371449B2 (en) * | 2008-01-31 | 2013-12-18 | 富士フイルム株式会社 | Resin, pigment dispersion, colored curable composition, color filter using the same, and method for producing the same |
| JP5538688B2 (en) * | 2008-05-30 | 2014-07-02 | 富士フイルム株式会社 | Colored curable composition, color filter, method for producing the same, and solid-state imaging device |
| TW201035677A (en) * | 2008-12-09 | 2010-10-01 | Sumitomo Chemical Co | Colored photosensitive resin composition |
| JP5489966B2 (en) * | 2009-12-18 | 2014-05-14 | 富士フイルム株式会社 | Light-shielding curable composition, wafer level lens, and light-shielding color filter |
| KR20120120353A (en) * | 2010-02-24 | 2012-11-01 | 제이에스알 가부시끼가이샤 | Color filter and color liquid crystal display element |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4489564B2 (en) * | 2003-11-26 | 2010-06-23 | 新日鐵化学株式会社 | Photosensitive resin composition and color filter using the same |
| JP2005300994A (en) * | 2004-04-13 | 2005-10-27 | Jsr Corp | Radiation sensitive composition for forming colored layer, color filter and color liquid crystal display panel |
| JP4508928B2 (en) * | 2005-03-31 | 2010-07-21 | 新日鐵化学株式会社 | Photosensitive resin composition and color filter using the same |
| WO2006121062A1 (en) * | 2005-05-11 | 2006-11-16 | Toppan Printing Co., Ltd. | Alkali development-type photosensitive resin composition, substrate with protrusions for liquid crystal split orientational control and color filter formed using the same, and liquid crystal display device |
| JP2008003299A (en) * | 2006-06-22 | 2008-01-10 | Tokyo Ohka Kogyo Co Ltd | Colored photosensitive resin composition |
| JP5095147B2 (en) * | 2006-07-10 | 2012-12-12 | Ｊｓｒ株式会社 | Polyester containing terpene phenol units |
-
2006
- 2006-07-10 JP JP2006188850A patent/JP4752648B2/en active Active
-
2007
- 2007-07-09 SG SG200705090-9A patent/SG139651A1/en unknown
- 2007-07-09 KR KR1020070068651A patent/KR20080005867A/en not_active Application Discontinuation
- 2007-07-09 TW TW096124938A patent/TWI430027B/en active
- 2007-07-10 CN CNA2007101360146A patent/CN101105630A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890660A (en) * | 2011-10-25 | 2014-06-25 | 三菱化学株式会社 | Colored photosensitive resin composition, colored spacer, color filter, and liquid crystal display device |
| CN103890660B (en) * | 2011-10-25 | 2019-05-31 | 三菱化学株式会社 | Coloring photosensitive combination, coloring spacer, colour filter and liquid crystal display device |
| CN107250208A (en) * | 2015-03-23 | 2017-10-13 | Jsr株式会社 | Polymer, resin combination and resin-formed body |
| CN107250208B (en) * | 2015-03-23 | 2019-09-20 | Jsr株式会社 | Polymer, resin combination and resin-formed body |
| CN108503577A (en) * | 2017-02-28 | 2018-09-07 | 东友精细化工有限公司 | Oxime ester based compound and Photocurable composition comprising it |
| CN108503577B (en) * | 2017-02-28 | 2021-12-21 | 东友精细化工有限公司 | Oxime ester compound and photocurable composition containing same |
| CN109351323A (en) * | 2018-11-09 | 2019-02-19 | 天津碧水源膜材料有限公司 | De- ammonium material of selectivity and the preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI430027B (en) | 2014-03-11 |
| TW200811598A (en) | 2008-03-01 |
| SG139651A1 (en) | 2008-02-29 |
| JP4752648B2 (en) | 2011-08-17 |
| JP2008015393A (en) | 2008-01-24 |
| KR20080005867A (en) | 2008-01-15 |
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