CN101109901A - Curable composition, color filter and process for production thereof - Google Patents

Curable composition, color filter and process for production thereof Download PDF

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Publication number
CN101109901A
CN101109901A CNA2007101045512A CN200710104551A CN101109901A CN 101109901 A CN101109901 A CN 101109901A CN A2007101045512 A CNA2007101045512 A CN A2007101045512A CN 200710104551 A CN200710104551 A CN 200710104551A CN 101109901 A CN101109901 A CN 101109901A
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group
compound
acid
solidification compound
adhesiveness
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CN101109901B (en
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相泽妙子
岛田和人
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • 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
    • 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
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Abstract

The invention provides a curable composition, color filter and process for production thereof, which has good patterning ability and excellent adhesive ability to the hard surface as baseplate, in the present of colorant of high concentration. The said curable composition comprises (A) a radical photopolymerization compoud intramolecularly with an ethylene nature unsaturated double bond and an adhesion group to hard material and (B) photopolymerization initiator. The adhesion group is preferably selected from an acid radical, an ester group of acid, acid onium salt, acid metal salt, a substituent that generates a silanol group by hydrolysis, an onium group, a phenolic hydroxyl group, a dipolar ion nature group, and a chelated group. The said curable composition is propitious to form colored parttern with filter. The said filter is formed by colored parttern with resolution formed by the said curable composition on supportor.

Description

Solidification compound, color filter and manufacture method thereof
Technical field
The solidification compound, color filter and the manufacture method thereof that are applicable to the making color filter that the present invention relates in liquid crystal display cells (LCD) and solid-state imager (CCD, CMOS etc.) etc., use.
Background technology
Color filter is the indispensable component parts of LCD and solid-state imager.
If LCD and CRT are compared as display device, then because it is a compact, and aspect of performance be on an equal basis more than, so replacing CRT as television image, personal computer picture, other display device.In addition, in recent years, the exploitation trend of LCD is large-scale and requires the TV purposes of high image quality to develop towards picture from the smaller monitor purposes in the past of picture area.
Use in the color filter purposes in LCD (LCD), be used for the substrate size that large-scale TV produces, improve the production efficiency when using large substrate, wish under low-yield, to solidify in order to enlarge.In addition,, compare, require higher picture quality with the display of in the past monitor purposes with regard to the LCD of TV purposes.That is, improve contrast and excitation.In order to improve contrast, about the solidification compound that uses in the color filter making, the particle size as the colorant (organic pigment etc.) that uses requires more small particle (for example, to open the 2006-30541 communique with reference to the spy.)。The thing followed is to have the trend of the addition increase of the spreading agent that is used for pigment dispersing.In addition, in order to improve excitation,, require higher amount as colorant (organic pigment) shared containing ratio in the solid state component of solidification compound.Therefore, the trend that exists containing ratio shared in Photoepolymerizationinitiater initiater and the photopolymerization monomer solid state component in solidification compound to reduce.
On the other hand, even use in the color filter purposes, also wish to solidify down low-yield at solid-state imager.In addition, pattern is carrying out filming, and the thing followed is to have improved the pigment concentration in the composition.And then, be in the color filter at pigment, there is the trend of the ratio increase that makes pigment dispersing agent in the composition along with the pigment miniaturization.In addition, in order to solve owing to pigment is that thicker particle produces problems such as irregular colour is even, having proposed with an organic solvent, the dyestuff of solubility replaces the technology (for example, with reference to spy open flat 2-127602 communique) of pigment as colorant.But dyestuff be in the color filter along with the raising of dye strength, the polymerization-inhibiting effects problem that is caused by dyestuff also becomes obvious.Owing to these reasons, under any situation that LCD is used, solid-state imager is used, not only limited be used to make solidification compound solidify must composition be the content of Photoepolymerizationinitiater initiater and photopolymerization monomer, and owing to colorant concentration uprises, so also produce following problems: sensitivity is low and can not obtain sufficient curing, insufficient with the adhesiveness of substrate, desirable pattern forms significant difficulties etc.As countermeasure, proposed to introduce the technology (for example, opening flat 11-38226 communique, No. 2874091 communique of special permission) of silane coupling agent with reference to the spy in order to improve the substrate adhesiveness for this problem.
Summary of the invention
The present invention has considered that above-mentioned problem in the past finishes, contain under the situation of colorant even the object of the present invention is to provide on high concentration ground, also can under high sensitivity, solidify, have good pattern and form property, with solidification compound as the adhesiveness excellence of the hard surface of base material.
In addition, another object of the present invention is to provide possess and use resolving power that solidification compound of the present invention forms and with the color filter of the colored pattern of the adhesiveness excellence of supporter and can make this manufacturing method of color filter with high efficiency.
The present inventor has carried out wholwe-hearted research, found that, by using specific polymerizable compound, can solve above-mentioned problem, thereby finish the present invention.That is it is as follows, to be used to solve the means of above-mentioned problem.
＜1〉a kind of solidification compound is characterized in that, contains: (A) have ethylenical unsaturated double bonds and to the free-radical polymerised compound of the adhesiveness group of hard material and (B) Photoepolymerizationinitiater initiater in molecule.
＜2〉according to＜1〉described in solidification compound, it is characterized in that above-mentioned (A) has ethylenical unsaturated double bonds and in the free-radical polymerised compound of the adhesiveness group of hard material the adhesiveness group of hard material being the ester group that is selected from acidic group, acid, hydrochlorate, acid metal salt, generating among substituting group, base, phenolic hydroxyl, zwitter-ion group and the chelating group of silanol group more than one by hydrolysis in molecule.
＜3〉according to＜1〉described in solidification compound, it is characterized in that, above-mentioned hard material is glass substrate or silicon substrate, and above-mentioned (A) has ethylenical unsaturated double bonds and be the substituting group that generates silanol group by hydrolysis to the adhesiveness group to hard material in the free-radical polymerised compound of the adhesiveness group of hard material in molecule.
＜4〉according to＜1〉described in solidification compound, it is characterized in that above-mentioned (A) has ethylenical unsaturated double bonds and the free-radical polymerised compound of the adhesiveness group of hard material is had a plurality of ethylenical unsaturated double bonds in molecule in molecule.
＜5〉according to＜2〉described in solidification compound, it is characterized in that above-mentioned (A) has ethylenical unsaturated double bonds and the free-radical polymerised compound of the adhesiveness group of hard material is had a plurality of ethylenical unsaturated double bonds in molecule in molecule.
＜6〉according to＜3〉described in solidification compound, it is characterized in that above-mentioned (A) has ethylenical unsaturated double bonds and the free-radical polymerised compound of the adhesiveness group of hard material is had a plurality of ethylenical unsaturated double bonds in molecule in molecule.
＜7〉according to＜4〉described in solidification compound, it is characterized in that above-mentioned (A) has ethylenical unsaturated double bonds and the free-radical polymerised compound of the adhesiveness group of hard material is had acryloyl group in molecule in molecule.
＜8〉according to＜1 〉-＜4〉solidification compound described in any one, it is characterized in that, also contain (C) has absorption maximum in the visible wavelength region of 400-700nm colorant.
＜9〉color filter is characterized in that, has use＜8 on supporter〉described in the colored pattern that forms of solidification compound.
＜10〉manufacturing method of color filter is characterized in that, comprises following operation: coating＜8 on supporter〉described in solidification compound and form the operation of solidification compound layer; By the operation of mask with above-mentioned solidification compound layer exposure; Develop and the operation of formation colored pattern with the above-mentioned solidification compound layer after will exposing.
Wherein, if right＜1〉optimal way of described solidification compound of the present invention gives an example, solidification compound of the present invention is applicable to the manufacturing of the colored pattern in the color filter, from this viewpoint, as hard material as supporter, be preferably selected from glass, silicon substrate is the inorganic material of representative, cellulose diacetate, Triafol T, cellulose propionate, cellulose butyrate, acetylbutyrylcellulose, cellulose nitrate, polyethylene terephthalate, tygon, polystyrene, polypropylene, polycarbonate, resin materials such as Pioloform, polyvinyl acetal, adhesiveness group as sticking on the supporter that is formed by such hard material can list: and this hard material surface between can form and be selected from covalent bond, ionic link, hydrogen bond, polar interaction, interactional functional group among Van der Waals interacts.
Be preferably the group that is selected among the following groups with adhesiveness group: acidic groups such as sulfonic group, phosphonate group, carboxyl as general glass of the supporter of color filter and resin material surface; The ester group that these are sour; The slaine that these are sour; Base such as ammonium, pyridine radicals; Alkoxysilyls etc. generate the substituting group of silanol group by hydrolysis; Zwitter-ion groups such as phenolic hydroxyl, N-oxide-base; Chelating groups such as imino-diacetic acetic acid.
According to the present invention, contain under the situation of colorant even can provide on high concentration ground, also can under high sensitivity, solidify, have good pattern form property, and as the solidification compound of the adhesiveness excellence of the hard surface of base material.
In addition, according to the present invention, the solidification compound of the application of the invention can provide to possess resolving power and with the color filter of the colored pattern of the adhesiveness excellence of supporter and can make this manufacturing method of color filter with high efficiency.
Embodiment
Below, solidification compound of the present invention, color filter and the manufacture method thereof of using this solidification compound to form are described in detail.
[solidification compound]
Solidification compound of the present invention is characterised in that, contain: (A) in molecule, have ethylenical unsaturated double bonds and free-radical polymerised compound of the adhesiveness group of hard material (below, suitable be called " (A) specific aggregation compound ") and (B) Photoepolymerizationinitiater initiater.
At first, to describing as above-mentioned (A) of the essential composition of solidification compound of the present invention with (B).
＜(A) in molecule, have ethylenical unsaturated double bonds and to the free-radical polymerised compound of the adhesiveness group of hard material
Can be used for (A) of the present invention specific aggregation compound is the addition polymerization compound with at least one ethylenical unsaturated double bonds, and is the compound that has in molecule the adhesiveness group of hard material.
As ethylenical unsaturated double bonds, can list: vinyl, unsaturated carboxylic acid are (for example, (methyl) acrylic acid, itaconic acid, butenoic acid, methacrylate, maleic acid etc.) and the ester class of unsaturated phosphonic acids and amide-type, styrene, vinyl ether etc., wherein preferred (methyl) acrylic acid.
(A) of the present invention specific aggregation compound be have at least 1, preferred more than 2, more preferably more than 3, further preferred more than 4, the compound of the above-mentioned ethylenic unsaturated bond more than 5 most preferably, and be the compound that has that at least one describes in detail below to the adhesiveness group of hard material.
That is, (A) the specific aggregation compound is characterised in that, not only has the ethylenic unsaturated bond group, and has the adhering adhesiveness group that can improve the hard material surface that is suitable for this solidification compound of the present invention.
As hard material, it is the material that becomes the supporter base material that can be suitable for solidification compound of the present invention, can list: glass for example, inorganic material such as silicon substrate, perhaps cellulose diacetate, Triafol T, cellulose propionate, cellulose butyrate, acetylbutyrylcellulose, cellulose nitrate, polyethylene terephthalate, tygon, polystyrene, polypropylene, polycarbonate, organic resin materials such as Pioloform, polyvinyl acetal etc., when solidification compound of the present invention is used to form the colored pattern of color filter, can list: be selected from wherein transparent hard material or silicon substrate, wherein preferred glass or silicon substrate.
(A) which kind of adhesiveness group the hard material that the specific aggregation compound can be suitable according to solidification compound suitably selects to introduce.
Such adhesiveness group can be to form with hard material surface to be selected from covalent bond, ionic link, hydrogen bond, polar interaction, the Van der Waals interactional group among interacting, specifically, can list: have the ester group, hydrochlorate, acid metal salt that are selected from acidic group, acid, generate more than one the group of part-structure among substituting group, base, phenolic hydroxyl, zwitter-ion group and the chelating group of silanol group by hydrolysis.
As the example of preferred adhesiveness group, can list: for example be selected from the functional group among sulfonic group, phosphonate group and their ester group or its salt, carboxyl and salt thereof, ammonium, pyridine radicals, acetylacetone based, the substituting group that generates silanol group by hydrolysis.Wherein, preferred ammonium, generate substituting group, phosphonate group and the ester group thereof of silanol group by hydrolysis.
Wherein, consider, preferably can form the substituting group of ionic link, multiple spot hydrogen bond, covalent bond from the viewpoint of interactional intensity.Wherein, have the functional group that is selected among ammonium, phosphonate group and ester group thereof, the alkoxysilyl and not only consider it is preferred, and consider it also is preferred from the viewpoint of the film strength of the development of unexposed portion, exposed portion from the adhering viewpoint of substrate that produces by interactional intensity with substrate.
(A) of the present invention specific aggregation compound is as having ethylenical unsaturated double bonds and to the polymerizable compound of the adhesiveness group of hard material, can listing: the compound of following general formula (A) expression.
[Chemical formula 1]
Figure A20071010455100091
In the above-mentioned general formula (A), M represents to have the position of ethylenical unsaturated double bonds, and L represents organic connection base of n+1 valency, and X represents the adhesiveness group to hard material.N represents the integer of 1-5, and m represents the integer of 1-3.
If the preferred example to the structure represented by M is given an example, then can list: ester class, the amide-type of unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, butenoic acid, methacrylate, maleic acid etc.).In addition, can list: by having the structure that addition reaction that substituent esters of unsaturated carboxylic acids of electrophilicity such as isocyanate group, epoxy radicals or amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol carry out generates; And has the substitution reaction that the esters of unsaturated carboxylic acids of the substituents of leaving away such as halogen radical, tolysulfonyl oxygen base or amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol carry out and the structure that generates.In addition, as other example, also can use the compound group that replaces to unsaturated phosphonic acids, styrene, vinyl ether etc. to replace above-mentioned unsaturated carboxylic acid.Wherein, preferred (methyl) acryloyl group, styrene, vinyl ether structure.The structure that more preferably has (methyl) acryloyl group.
In the above-mentioned general formula (A), L represents the organic connection base according to the n+1 valency of quantity (n) decision with part-structure of ethylenical unsaturated double bonds, have the part-structure that is selected among oxygen atom, nitrogen-atoms, sulphur atom or the hydrocarbon ring structure that is formed by carbon number 3-10, aromatic rings, heterocycle, urethane bond, sulfo-urethane bond, ester bond, amido link, urea key, the thiourea key in this structure, they are connection bases of independent formation or the multiple n+1 valency that constitutes.
In such connection base; also can further have substituting group; substituting group as on the connection base that can be incorporated into L can list: fatty group for example; the aromatic series base; heterocyclic radical; halogen atom; hydroxyl; mercapto; cyano group; nitro; aliphatics oxygen base; aromatic series oxygen base; heterocyclic oxy group; the aliphatics sulfenyl; the aromatic series sulfenyl; the heterocycle sulfenyl; the aliphatics sulfonamido; the aromatic series sulfonamido; the heterocycle sulfonamido; acyl group; acyloxy; acylamino-; aliphatics oxygen base carbonyl; aromatic series oxygen base carbonyl; the heterocyclic oxy group carbonyl; aliphatics oxygen base carbonylamino; aromatic series oxygen base carbonylamino; the heterocyclic oxy group carbonylamino; the aliphatics thio-carbonyl-amino; the aromatic series thio-carbonyl-amino; the heterocycle thio-carbonyl-amino; the aliphatics amino carbonyl amino; the amino carbonylamino of aromatic series; the heterocyclic amino group carbonylamino; carbamyl; carbamoyloxy; carbamyl amino; the aliphatics sulfonyl; the aromatic series sulfonyl; the heterocycle sulfonyl; aliphatics oxygen base amino; aromatic series oxygen base amino; heterocyclic oxy group amino; silicyl; aliphatics oxygen base silicyl; siloxy; aliphatics oxygen base ketonic oxygen base; aromatic series oxygen base ketonic oxygen base; heterocyclic oxy group ketonic oxygen base; sulfamoyloxy; the aliphatics sulfonyloxy; the aromatic series sulfonyloxy; anilino-; the aliphatics azo group; the aromatic series azo group; the heterocycle azo base; the aliphatics sulfinyl; the aromatic series sulfinyl; the heterocycle sulfinyl; the aliphatics sulfonyloxy; the aromatic series sulfonyloxy; the heterocycle sulfonyloxy; amino-sulfonyl; sulfo group; phosphoryl; phosphino-amino.
[(A) object lesson of specific aggregation compound]
In the structure of being represented by M, the object lesson [(M-1)-(M-11)] when particularly making the olefinic double bond group be acryloyl group is as follows, but is not limited to this.In addition, acryloyl group can replace to aforesaid propylene acyl group substituting group in addition.In addition, also can have mutually different plural olefinic double bond group in the structure of representing by M.
[Chemical formula 2]
Figure A20071010455100111
[chemical formula 3]
Figure A20071010455100121
X in the above-mentioned general formula (A) is 1 o'clock at m, is preferably selected from the monovalence functional group that is represented by following formula.
[chemical formula 4]
Figure A20071010455100122
In the above-mentioned formula, R 11～R 13Represent hydrogen atom, alkyl, aryl, alkynyl or alkenyl, M respectively independently 1And M 2Represent hydrogen atom, metallic atom or base, X respectively independently -The expression counter anion.
X in the above-mentioned general formula (A) is 2 o'clock at m, is preferably selected from the divalence functional group that is represented by following formula.
[chemical formula 5]
Figure A20071010455100131
In the above-mentioned formula, R 12～R 13Represent hydrogen atom, alkyl, aryl, alkynyl or alkenyl, M respectively independently 2Represent hydrogen atom, metallic atom or ammonium, X respectively independently -The expression counter anion.
X in the above-mentioned general formula (A) is 3 o'clock at m, is preferably selected from the trivalent functional group that following formula is represented.
[chemical formula 6]
Figure A20071010455100132
In the above-mentioned formula, R 13Represent hydrogen atom, alkyl, aryl, alkynyl or alkenyl respectively, X -The expression counter anion.
When the X of above-mentioned general formula (A) has counter anion as part-structure, as these counter anion X -, can list: halide anions such as fluorine anion, cl anion, bromine anions, iodine negative ion for example; Acetate anion, trifluoracetic acid root negative ion, sulfate anion, bisulfate ion negative ion, methanesulfonate negative ion, trifluoromethanesulfonic acid root negative ion, perchlorate's negative ion, tetrafluoroborate negative ion, hexafluoro-phosphate radical negative ion, chlordene metaantimmonic acid root negative ion, hexafluoroantimonic anion negative ion etc.Wherein, consider preferred halide anion, trifluoromethanesulfonic acid root negative ion, methanesulfonate negative ion, sulfate anion, bisulfate ion negative ion, tetrafluoroborate negative ion and hexafluoro-phosphate radical negative ion etc. from the dissolubility of this compound and the viewpoint of stability.As counter anion X -, be all can list same negative ion under any one situation of 1-3 at m.
[(A) synthetic method of specific aggregation compound]
Below, show example, but synthetic method is not limited to this by the synthetic method of (A) specific aggregation compound of general formula (A) expression.
Synthetic method as (A) specific aggregation compound of general formula (A) expression can list: have substituent esters of unsaturated carboxylic acids of electrophilicity or amide-type such as isocyanate group and epoxy radicals and have the simple function of adhesiveness group or addition reaction that polyfunctional alcohols, amine, thio-alcohol carry out; And have the esters of unsaturated carboxylic acids or the amide-type of the substituents of leaving away such as halogen radical, tolysulfonyl oxygen base and have the simple function of adhesiveness group or substitution reaction that polyfunctional alcohols, amine, thio-alcohol carry out.In addition, can list: have electrophilicity substituting groups such as isocyanate group, epoxy radicals and have the compound of adhesiveness group, and have hydroxyl, amino or sulfydryl and have the addition reaction that the compound of at least more than one olefinic double bond carries out.In addition, by (A) specific aggregation compound of general formula (A) expression also can be by having the adhesiveness group amine, thio-alcohol and compound with two above olefinic double bonds carry out Michael addition reaction and synthesize.
An example as (A) of the present invention polymerizable compound, the structure that below shows the M in the above-mentioned general formula (A) is an above-mentioned illustration structure (M-6), in this structure, introduce example [exemplary compounds (1)-(20)] to the adhesiveness radicals X of hard material, but can be above-mentioned (M-1)-(M-11) etc., and can be synthetic with existing synthetic method with the structure appropriate change of the M in the above-mentioned general formula (A).In addition, the present invention is not limited to these.
[chemical formula 7]
Figure A20071010455100151
[chemical formula 8]
Figure A20071010455100161
[chemical formula 9]
[Chemical formula 1 0]
Figure A20071010455100181
[Chemical formula 1 1]
Figure A20071010455100191
[Chemical formula 1 2]
Figure A20071010455100201
[Chemical formula 1 3]
Figure A20071010455100211
An example as (A) of the present invention polymerizable compound, the structural change that shows the M in the above-mentioned general formula (A) is the example [exemplary compounds (21)-(30)] that above-mentioned (M-1)-(M-11) except above-mentioned illustrative structure (M-6) waits, but is not limited to these.
[Chemical formula 1 4]
[Chemical formula 1 5]
Figure A20071010455100231
[Chemical formula 1 6]
Figure A20071010455100241
For these (A) specific aggregation compounds, its structure, be to use separately or be used in combination or the detailed content of using method such as addition can at random be set according to the final performance design of solidification compound and purposes.For example, selected from following viewpoint.
With regard to the sensitivity aspect, preferably many with respect to the unsaturated group mass contg of each molecule structures are under the many situations of unsaturated group mass contg, more than preferred two senses.In addition, in order to improve the curing film strength, be preferably more than the trifunctional, and then, by and also be effective with the method that the compound of different functional number, different polymerizable group (for example acrylate, methacrylate, polystyrene compound, vinyl ether based compound) is regulated sensitivity and intensity.
As adhesiveness group to hard material, for example, when supporter uses glass plate, owing to have a large amount of silanol groups and hydroxyl, so preferably introduce following radicals at glass surface: can with these groups form covalent bonds interactional dialkyl group alkoxysilyl, alkyl dialkoxy silicyl, trialkoxysilyl, can form ammonium, the phosphonic acids that can form the multiple spot hydrogen bond or its ester group of ion dipole interaction etc.
In addition, when cellulose-based materials such as use cellulose diacetate, Triafol T, cellulose propionate, cellulose butyrate, acetylbutyrylcellulose, cellulose nitrate, the preferred adhesiveness groups such as ammonium, phosphonic acids or its ester group of selecting, when synthetic resin such as polyethylene terephthalate, tygon, polystyrene, polypropylene, polycarbonate, Pioloform, polyvinyl acetal are used as hard material, preferably select adhesiveness groups such as phosphonic acids or its ester group.
In addition, for with other composition that in solidification compound, contains (for example, initiating agent, colorant (pigment, dyestuff) etc., binder polymer etc.) compatibility, dispersed, the selection of addition polymerization compound and using method also are important key elements, for example, sometimes by using the low-purity compound or more than two kinds and be used for improving compatibility.In addition, in order to improve the adhesiveness with substrate etc., also can select the ad hoc structure except introducing above-mentioned adhesiveness group sometimes.
In addition, among the present invention, except (A) specific aggregation compound, only otherwise damage effect of the present invention, can and be used in and do not have the general free-radical polymerised compound (E) of adhesiveness group as mentioned above in the molecule.General free-radical polymerised compound (E) as not having the adhesiveness group can list: those compounds that do not have the adhesiveness group in above-mentioned (A) specific aggregation compound in molecule.In addition, can use separately, also can more than two kinds and use.Below, the general free-radical polymerised compound (E) that does not have the adhesiveness group is described.
＜do not have a general free-radical polymerised compound (E) of adhesiveness group 〉
As being used for the general free-radical polymerised compound (E) that does not have the adhesiveness group of the present invention, can use the compound of in this industrial circle, extensively being known as having the compound of ethylenical unsaturated double bonds with being not particularly limited.They for example have monomer, prepolymer, are dipolymer, trimer and oligomer or their potpourri and their chemical specieses such as multipolymer.Example as monomer and multipolymer thereof, can list: unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, butenoic acid, methacrylate, maleic acid etc.) or its ester class, amide-type, preferably use the amide-type of ester, unsaturated carboxylic acid and the aliphatic polyamine compound of unsaturated carboxylic acid and aliphatic polyol compound.In addition, also can use aptly have hydroxyl, the addition reaction product of the substituent esters of unsaturated carboxylic acids of nucleophilicity such as amino, sulfydryl or amide-type and simple function or polyfunctional isocyanate's class or epoxies and with dehydration condensation product of simple function or polyfunctional carboxylic acid etc.In addition, have the addition reaction product of substituent esters of unsaturated carboxylic acids of electrophilicity such as isocyanate group or epoxy radicals or amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol, and the substitution reaction product with the esters of unsaturated carboxylic acids of the substituents of leaving away such as halogen radical, tolysulfonyl oxygen base or amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol is fit to also.In addition, as other example, also can use the compound group that replaces to unsaturated phosphonic acids, styrene, vinyl ether etc. to replace above-mentioned unsaturated carboxylic acid.
Object lesson as the monomer of the ester of aliphatic polyol compound and unsaturated carboxylic acid, as acrylate, have: ethylene glycol diacrylate, the diacrylate triglycol ester, diacrylate 1, the 3-butanediol ester, diacrylate 1, the 4-butanediol ester, the diacrylate propylene glycol ester, diacrylic acid pentyl diol ester, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, hexanediol diacrylate, diacrylate 1,4-cyclohexanediol ester, diacrylate TEG ester, the diacrylate pentaerythritol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, the diacrylate dipentaerythritol ester, six acrylic acid dipentaerythritol ester, three acrylic acid sorbitol esters, tetrapropylene acid sorbitol ester, five acrylic acid sorbitol esters, six acrylic acid sorbitol esters, three (acryloxy ethyl) isocyanuric acid ester, polyester acrylic ester oligomer etc.In addition, also can list: the EO modification body of these compounds or PO modification body.
As methacrylate, can list: dimethacrylate 1, the 4-butanediol ester, the dimethacrylate triglycol ester, the dimethacrylate DOPCP, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, Ethylene glycol dimethacrylate, dimethacrylate 1,3 butylene glycol ester, dimethacrylate hexanediol ester, the dimethacrylate pentaerythritol ester, trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetramethacrylate, the dimethacrylate dipentaerythritol ester, hexamethyl acrylic acid dipentaerythritol ester, trimethyl acrylic acid sorbitol ester, tetramethyl acrylic acid sorbitol ester, two [p-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl] dimethylmethane, two [p-(3-methacryloxy ethoxy) phenyl] dimethylmethane etc., and their EO modification body, perhaps PO modification body.
As itaconate, have: two itaconic acid glycol esters, two itaconic acid propylene glycol esters, two itaconic acids 1,3-butanediol ester, two itaconic acids 1,4-butanediol ester, two itaconic acid tetramethylene glycol esters, two itaconic acid pentaerythritol esters, four itaconic acid sorbitol esters etc.As butenoate, dibutene acid glycol ester, dibutene acid 1 are arranged, 4-butanediol ester, dibutene acid pentaerythritol ester, four butenoic acid sorbitol esters etc.As methacrylate, have: di glycol ester, di pentaerythritol ester, four methacrylate sorbitol esters etc.As maleate, two maleic acid glycol esters, two maleic acid triglycol esters, two maleic acid pentaerythritol esters, four maleic acid sorbitol esters etc. are arranged.
As the example of other ester, for example special public clear 51-47334 of suitable use, spy open the aliphatic alcohol of putting down in writing among the clear 57-196231 be ester class, He Te open clear 59-5240, spy open clear 59-5241, spy open the ester with aromatic series pastern bone frame, the spy that put down in writing among the flat 2-226149 open put down in writing among the flat 1-165613 contain amino ester etc.In addition, above-mentioned ester monomer also can be used as the potpourri use.
In addition, object lesson as the monomer of the acid amides of aliphatic polyamine compound and unsaturated carboxylic acid, methylene-bisacrylamide, di-2-ethylhexylphosphine oxide Methacrylamide, 1 are arranged, 6-hexa-methylene bisacrylamide, 1, the two Methacrylamides of 6-hexa-methylene, diethylene triamine three acrylamides, dimethylbenzene bisacrylamide, the two Methacrylamides of dimethylbenzene etc.Example as other preferred acid amides is a monomer can list: the acid amides of putting down in writing among the special public clear 54-21726 with cyclohexylidene structure is a monomer.
In addition, using the urethane of the addition reaction preparation of isocyanates and hydroxyl is that the addition polymerization compound also is fit to, as this object lesson, can list: the vinyl urethane compound that in a part, contains two above polymerism vinyl that the polyisocyanate compounds of putting down in writing in for example special public clear 48-41708 communique that has two above isocyanate group in a part forms with the vinyl monomer addition of being represented by following general formula (E) that contains hydroxyl etc.
CH 2＝C(R 1)COOCH 2CH(R 2)OH (E)
(wherein, R 1And R 2Expression H or CH 3)
In addition, open the urethane acrylate class of record in clear 51-37193 number, special fair 2-32293 number, special fair 2-16765 number as the spy, and the urethane compound class with oxirane pastern bone frame of record in special public clear 58-49860 number, special public clear 56-17654 number, special public clear 62-39417 number, special public clear 62-39418 number is fit to also.In addition, opening clear 63-277653 number, spy the spy opens clear 63-260909 number, spy and opens in flat 1-105238 number and put down in writing, by using the addition polymerization compounds that in molecule, has amino structure or sulfide structure, can obtain the very excellent solidification compound of film speed.
As other example, can list: as opening the polyester acrylate class put down in writing in clear 48-64138 number, special public clear 49-43191 number, special public clear 52-30490 number each communique the spy, making epoxy resin and the reaction of (methyl) acrylic acid and polyfunctional acrylate and the methacrylates such as epoxy acrylate class that obtain.In addition, also can list: the specific unsaturated compound of record and the special vinyl phosphonate based compound of opening record in flat 2-25493 number etc. in special public clear 46-43946 number, special fair 1-40337 number, special fair 1-40336 number.In addition, in some cases, the suitable structure that contains perfluoroalkyl of using the spy to open record in clear 61-22048 number.Also can use in the Japanese bonding will vol.20 of association, No.7, the 300-308 page or leaf (1984) compound of introducing as photo-curable monomer and oligomer in addition.
Among the present invention, add when not having the general free-radical polymerised compound (E) of adhesiveness group, consider, preferably contain plural ethylenic unsaturated bond, more preferably contain the ethylenic unsaturated bond more than three from the viewpoint of solidifying sensitivity.Wherein preferably contain (methyl) acrylate structural more than two, more preferably contain more than three, most preferably contain (methyl) acrylate structural more than four.In addition, the viewpoint of just solidifying the development of sensitivity and unexposed portion is considered, preferably contains EO modification body.In addition, the viewpoint of just solidifying sensitivity and exposed portion intensity considers preferably to contain urethane bond.
From above viewpoint, as preferred compound, can list: bisphenol a diacrylate, bisphenol a diacrylate EO modification body, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, diacrylate TEG ester, the diacrylate pentaerythritol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, dipentaerythritoltetraacrylate, five acrylic acid dipentaerythritol ester, six acrylic acid dipentaerythritol ester, three acrylic acid sorbitol esters, tetrapropylene acid sorbitol ester, five acrylic acid sorbitol esters, six acrylic acid sorbitol esters, three (acryloxy ethyl) isocyanuric acid ester, pentaerythritol tetracrylate EO modification body, six acrylic acid dipentaerythritol ester EO modification bodies etc., in addition, as commercially available product, preferred urethane oligomers UAS-10, UAB-140 (adret state basic policy パ Le プ corporate system), DPHA-40H (Japanese chemical drug corporate system), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (common prosperity corporate system).
Wherein, more preferably bisphenol a diacrylate EO modification body, pentaerythritol triacrylate, pentaerythritol tetracrylate, five acrylic acid dipentaerythritol ester, six acrylic acid dipentaerythritol ester, three (acryloxy ethyl) isocyanuric acid ester, pentaerythritol tetracrylate EO modification body, six acrylic acid dipentaerythritol ester EO modification bodies etc., as commercially available product, more preferably DPHA-40H (Japanese chemical drug corporate system), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (common prosperity corporate system).
In addition, solidification compound of the present invention, consider from the viewpoint of the intensity of the development of solidifying sensitivity, unexposed portion, exposed portion, except (A) specific aggregation compound, also preferably contain general free-radical polymerised compound (E) with adhesiveness group according to following ratio.(A) the specific aggregation compound with respect to (E) have other polymerizable compound of olefinic double bond and (A) mass ratio of the gross mass of specific aggregation compound [(A)/(A)+(E)] be preferably 0.01-1,0.01-0.5 more preferably, more preferably 0.01-0.3 most preferably is 0.01-0.15.When [(A)/(A)+(E)] when being lower than 0.1, can not obtain sufficient substrate adhesiveness.
In addition, (E) has other polymerizable compound of olefinic double bond and (A) be preferably 1-90% in the solid state component of gross mass in the present composition of specific aggregation compound, more preferably 1-80%, more preferably 1-70%.
Especially, when the colored pattern that solidification compound of the present invention is used for color filter forms, preferred 5-50% in the scope of above-mentioned content, more preferably 7-40%, further preferred 10-35%.
In addition, (B) Photoepolymerizationinitiater initiater with respect to (E) have olefinic double bond can and the polymerizable compound of usefulness and (A) mass ratio of the gross mass of specific aggregation compound [(B)/(A)+(E)] be preferably 0.1-0.8, more preferably 0.2-0.7 most preferably is 0.3-0.6.
These (A) compositions and (E) other free-radical polymerised compound consider from viewpoints such as size that the polymerization of oxygen is hindered, resolution, tunicle, variations in refractive index, surface adhesions, can select suitable structure, prescription, addition arbitrarily.
＜(B) Photoepolymerizationinitiater initiater 〉
Solidification compound of the present invention contains (B) Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater among the present invention is to decompose by light, thereby causes, promote above-mentioned (A) specific free-radical polymerised compound polymeric compounds, preferably has the compound of absorption for the 300-500nm zone at wavelength.In addition, Photoepolymerizationinitiater initiater can use separately or also use more than two kinds.
As Photoepolymerizationinitiater initiater, can list: for example organic halogenation compound, oxadiazole compound, carbonyls, ketal compound, benzoin compound, acridine compound, organic peroxy compound, azo-compound, coumarin compound, triazo-compound, Metallocenic compound, six aryl united imidazoles, organic boronic compound, disulfonic acid compound, oxime ester compound, salt compound, acylphosphanes (oxide) compound.
As the organic halogenation compound, specifically, can list: if woods etc., " Bull Chem.Soc Japan " 42,2924 (1969), No. 3905815 instructions of United States Patent (USP), special public clear 46-4605 number, the spy opens clear 48-36281 number, the spy opens clear 55-32070 number, the spy opens clear 60-239736 number, the spy opens clear 61-169835 number, the spy opens clear 61-169837 number, the spy opens clear 62-58241 number, the spy opens clear 62-212401 number, the spy opens clear 63-70243 number, the spy opens clear 63-298339 number, M.P.Hutt " Journal of Heterocyclic Chemistry " 1 (No3), (1970) compound of record in can list especially: trihalomethyl replaces De oxazole compound, the s-triaizine compounds.
As the s-triaizine compounds, be more suitable for be at least one one, two or three halogen substituent methyls are combined in the s-pyrrolotriazine derivatives on the s-triazine ring, specifically, can list: for example 2,4,6-three (chloromethyl)-s-triazine, 2,4,6-three (dichloromethyl)-s-triazine, 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4,6-two (trichloromethyl)-s-triazine, 2-n-pro-pyl-4,6-two (trichloromethyl)-s-triazine, 2-(α, α, β-trichloromethyl)-4,6-two (trichloromethyl)-s-triazine, 2-phenyl-4,6-two (trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-two (trichloromethyl)-s-triazine, 2-(3, the 4-epoxy-phenyl)-4,6-two (trichloromethyl)-s-triazine, 2-(rubigan)-4,6-two (trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl)-2, the 4-butadienyl]-4,6-two (trichloromethyl)-s-triazine, 2-styryl-4,6-two (trichloromethyl)-s-triazine, 2-(to methoxyl-styrene)-4,6-two (trichloromethyl)-s-triazine, 2-(to the isopropoxystyrene base)-4,6-two (trichloromethyl)-s-triazine, 2-(p-methylphenyl)-4,6-two (trichloromethyl)-s-triazine, 2-(4-methoxyl naphthyl)-4,6-two (trichloromethyl)-s-triazine, 2-phenyl sulphur-4,6-two (trichloromethyl)-s-triazine, 2-dibenzylsulfide-4,6-two (trichloromethyl)-s-triazine, 2,4,6-three (two bromomethyls)-s-triazine, 2,4,6-three (trisbromomethyl)-s-triazine, 2-methyl-4,6-two (trisbromomethyl)-s-triazine, 2-methoxyl-4,6-two (trisbromomethyl)-s-triazine etc.
Zuo Wei oxadiazole compound, can list: 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(cyano styrene base)-1,3,4-oxadiazole, 2-trichloromethyl-5-(naphthalene-1-yl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-styryl) styryl-1,3,4-oxadiazole etc.
As carbonyls, can list: benzophenone, Michler's keton, 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, the 2-chlorobenzophenone, 4-bromine benzophenone, benzophenone derivates such as 2-carboxyl benzophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2, the 2-diethoxy acetophenone, the 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-aminomethyl phenyl acetone, 1-hydroxyl-1-Methylethyl-(p-isopropyl phenyl) ketone, 1-hydroxyl-1-(dodecylphenyl) ketone, 2-methyl-(4 '-(methyl mercapto) phenyl)-2-morpholino-1-acetone, 1,1,1-trichloromethyl-(to butyl phenyl) ketone, 2-benzyl-2-dimethylamino-acetophenone derivs such as 4-morpholino butyrophenone, thioxanthones, 2-ethyl thioxanthones, the 2-isopropyl thioxanthone, the 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2, the 4-diethyl thioxanthone, 2, thioxanthone derivates such as 4-diisopropyl thioxanthones, (dimethylamino)-ethyl benzoate, to benzoate derivatives such as lignocaine ethyl benzoate etc.
As ketal compound, can list: benzyl methyl ketal, benzyl-'beta '-methoxy ethyl diethyldithiocarbamate acetal etc.
As the benzoin compound, can list: m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl benzoic ether etc.
As the acridine compound, can list: 9-phenylacridine, 1,7-two (9-acridinyl) heptane etc.
As the organic peroxy compound, can list: trimethyl hexanone peroxide for example, acetylacetone peroxide, 1,1-two (tert-butyl hydroperoxide)-3,3, the 5-trimethyl-cyclohexane, 1,1-two (tert-butyl hydroperoxide) cyclohexane, 2,2-two (tert-butyl hydroperoxide) butane, tert butyl hydroperoxide, cumene hydroperoxide, the hydroperoxidation diisopropyl benzene, 2,5-dimethylhexane-2,5-dihydro-peroxidase, 1,1,3,3-tetramethyl butyl hydroperoxides, tert-butyl group cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, 2,5-oxalyl (oxanoyl) hydroperoxides.Succinic acid peroxide, benzoyl peroxide, peroxidating 2, the 4-dichloro-benzoyl, diisopropyl peroxydicarbonate, two-2-ethylhexyl peroxide, two carbonic esters, two-2-ethoxyethyl group peroxide, two carbonic esters, dimethoxy isopropyl peroxide two carbonic esters, two (3-methyl-3-methoxyl butyl) peroxide two carbonic esters, the t-butyl peroxy acetic acid esters, the t-butyl peroxy pivalate, t-butyl peroxy neodecanoic acid ester, the t-butyl peroxy caprylate, the t-butyl peroxy laurate, the tertiary carbon acid esters, 3,3 ' 4,4 '-four-(t-butyl peroxy carbonyl) benzophenone, 3,3 ' 4,4 '-four-(uncle's hexyl peroxide carbonyl) benzophenone, 3,3 ' 4,4 '-four-(p-isopropyl cumyl peroxide carbonyl) benzophenone, carbonyl two (t-butyl peroxy dihydro two phthalate esters), carbonyl two (uncle's hexyl peroxide dihydro two phthalate esters) etc.
As azo-compound, can list: for example special azo-compound put down in writing in the flat 8-108621 communique etc. of opening.
As coumarin compound, can list: for example 3-methyl-5-amino-((s-triazine-2-yl) amino)-3-phenyl cumarin, 3-chloro-5-lignocaine-((s-triazine-2-yl) amino)-3-phenyl cumarin, 3-butyl-5-dimethylamino-((s-triazine-2-yl) amino)-3-phenyl cumarin etc.
As triazo-compound, can list: the organic azide of putting down in writing in No. 2848328 instructions of United States Patent (USP), No. 2852379 instructions of United States Patent (USP) and No. 2940853 instructions of United States Patent (USP), 2,6-two (4-nitrine benzal)-4-ethyl cyclohexanone (BAC-E) etc.
As Metallocenic compound, can list: the spy opens clear 59-152396 communique, the spy opens clear 61-151197 communique, the spy opens clear 63-41484 communique, Te Kaiping 2-249 communique, Te Kaiping 2-4705 communique, the various titanocene compounds of Te Kaiping 5-83588 communique record, two phenyl of dicyclopentadienyl-Ti-for example, dicyclopentadienyl-Ti-two-2,6-two fluorobenzene-1-base, dicyclopentadienyl-Ti-two-2,4-two fluorobenzene-1-base, dicyclopentadienyl-Ti-two-2,4,6-trifluoro-benzene-1-base, dicyclopentadienyl-Ti-two-2,3,5,6-phenyl tetrafluoride-1-base, dicyclopentadienyl-Ti-two-2,3,4,5,6-phenyl-pentafluoride-1-base, dimethyl cyclopentadienyl group-Ti-two-2,6-two fluorobenzene-1-base, dimethyl cyclopentadienyl group-Ti-two-2,4,6-trifluoro-benzene-1-base, dimethyl cyclopentadienyl group-Ti-two-2,3,5,6-phenyl tetrafluoride-1-base, dimethyl cyclopentadienyl group-Ti-two-2,3,4,5,6-phenyl-pentafluoride-1-base, Te Kaiping 1-304453 communique, the iron of putting down in writing in the Te Kaiping 1-152109 communique-aromatic hydrocarbons complex compound etc.
As six aryl united imidazoles, can list: for example, special fair 6-29285 communique, No. the 3479185th, United States Patent (USP), No. the 4311783rd, United States Patent (USP), United States Patent (USP) waits all cpds of putting down in writing in each instructions No. 4622286, be in particular 2,2 '-two (o-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (o-bromophenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (o, p-dichlorophenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (o-chlorphenyls)-4,4 ', 5,5 '-four (m-methoxyphenyl) bisglyoxaline, 2,2 '-two (o, o '-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (o-nitrobenzophenones)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (o-aminomethyl phenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (o-trifluorophenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline etc.
As the organic boronic salt compound, can list as object lesson: for example the spy opens clear 62-143044 number, the spy opens clear 62-150242 number, Te Kaiping 9-188685 number, Te Kaiping 9-188686 number, Te Kaiping 9-188710 number, the spy opens 2000-131837 number, the spy opens 2002-107916 number, No. the 2764769th, Japan's special permission, special Willing waits each communique 2000-310808 number, and Kunz, the organic borate of record among the Martin " Rad Tech ' 98.Proceeding April 19-22; 1998, Chicago " etc., Te Kaiping 6-157623 communique, Te Kaiping 6-175564 communique, organic boron sulfonium salt complex compound of putting down in writing in the Te Kaiping 6-175561 communique or organic boron oxo sulfonium salt complex compound, Te Kaiping 6-175554 communique, organic boron iodo-complexes of putting down in writing in the Te Kaiping 6-175553 communique, that puts down in writing in the Te Kaiping 9-188710 communique has a machine boron phosphonium salt complex compound, Te Kaiping 6-348011 communique, Te Kaiping 7-128785 communique, Te Kaiping 7-140589 communique, Te Kaiping 7-306527 communique, organic boron transition metal coordination complexes of Te Kaiping 7-292014 communique etc. etc.
As disulfonic acid compound, can list: the spy opens the compound etc. that clear 61-166544 communique, spy are opened record such as 2002-328465 instructions.
As oxime ester compound, can list: J.C.S.Perkin II (1979) 1653-1660), J.C.S.Perkin II (1979) 156-162), Journal of Photopolymer Science and Technology (1995) 202-232, spy open the compound of 2000-66385 communique record; The spy opens the compound of 2000-80068 communique, the record of special table 2004-534797 communique etc.
As salt compound, can list: S.I.Schlesinger for example, Photogr.Sci.Eng., 18,387 (1974), people such as T.S.Bal, Polymer, two diazo salts of record in 21,423 (1980); The ammonium salt of middle records such as United States Patent (USP) No. 4069055 instructions, spy open flat 4-365049 number; Record De phosphonium salt in No. the 4069055th, United States Patent (USP), No. 4069056 instructions of United States Patent (USP); No. the 104143rd, European patent, No. the 339049th, United States Patent (USP), United States Patent (USP) No. 410201 each instructions, spy open flat 2-150848 number, spy and open salt compounded of iodine of putting down in writing in flat 2-296514 number each communique etc.
Going for salt compounded of iodine of the present invention is diaryl group iodized salt, considers from the viewpoint of stability, is preferably replaced by sub-property bases of power supply such as two above alkyl, alkoxy, aryloxy group.In addition, as the form of other preferred sulfonium salt, a substituting group of preferred triarylsulfonium salt has cumarin, anthraquinone ring and have the salt compounded of iodine etc. of absorption more than 300nm.
As going for sulfonium salt of the present invention, can list: No. the 370693rd, European patent, No. the 390214th, European patent, No. the 233567th, European patent, No. the 297443rd, European patent, No. the 297442nd, European patent, No. the 4933377th, United States Patent (USP), No. the 161811st, United States Patent (USP), No. the 410201st, United States Patent (USP), No. the 339049th, United States Patent (USP), No. the 4760013rd, United States Patent (USP), No. the 4734444th, United States Patent (USP), No. the 2833827th, United States Patent (USP), No. the 2904626th, Deutsche Bundespatent, No. the 3604580th, Deutsche Bundespatent, the sulfonium salt of putting down in writing in No. 3604581 each instructions of Deutsche Bundespatent, consider from the aspect of the sensitivity of stability, preferably replaced by the electrophilic base.As the electrophilic base, preferred Hammett value is greater than 0.As preferred electrophilic base, can list: halogen atom, carboxylic acid etc.
In addition, as other preferred sulfonium salt, can list: a substituting group of triarylsulfonium salt has cumarin, anthraquinone ring and have the sulfonium salt of absorption more than 300nm.As other preferred sulfonium salt, can list: triarylsulfonium salt has aryloxy group, arylthio have absorption as substituting group and more than 300nm sulfonium salt.
In addition, as salt compound, can list: people such as J.V.Crivello, Macromolecules, 10 (6), 1307 (1977), people such as J.V.Crivello, J.Polymer Sci., Polymer Chem.Ed., people such as the selenium salt of 17,1047 (1979) middle records, C.S.Wen, Tech, Proc.Conf.Rad.Curing ASIA, the salt of putting down in writing among the p478 Tokyo, Oct (1988) such as arsenic salt etc.
As acylphosphanes (oxide) compound, can list: Irgacure 819, the Darocure 4265 of Ciba Speciality Chemicals corporate system, Darocure TPO etc.
As (B) Photoepolymerizationinitiater initiater that uses among the present invention; consider from the viewpoint of exposure sensitivity, be preferably selected from the trihalomethyl triaizine compounds; the benzyl dimethyl ketal compound; alpha-hydroxyacetone compounds; the alpha-amido ketonic compound; the acylphosphanes based compound; the phosphine oxide based compound; Metallocenic compound; oxime compound; the triallyl imidazole dimer; the salt based compound; the benzothiazole based compound; the benzophenone based compound; acetophenone based compound and derivant thereof; cyclopentadiene-benzene-iron complex and salt thereof; Lu is for Jia oxadiazole compound; compound among the 3-aryl substituted cumarin compound.
More preferably; trihalomethyl triaizine compounds, alpha-amido ketonic compound, acylphosphanes based compound, phosphine oxide based compound, oxime compound, triallyl imidazole dimer, salt based compound, benzophenone based compound, acetophenone based compound, most preferably trihalomethyl triaizine compounds, alpha-amido ketonic compound, oxime compound, triallyl imidazole dimer, benzophenone based compound.
The content of (B) Photoepolymerizationinitiater initiater that contains in the solidification compound of the present invention is preferably 0.1-50 quality % with respect to the whole solid state component of solidification compound, and more preferably 0.5-30 quality % is preferably 1-20 quality % especially.In this scope, can obtain good sensitivity and pattern formation property.
＜(C) colorant 〉
By in solidification compound of the present invention, using colorant, can form coloured firming body of forming by solidification compound, and go for the colored pattern formation of Image forming material and color filter.
The colorant that adds as required in solidification compound of the present invention is not particularly limited, and known in the past various dyestuffs or pigment can use a kind of or mix and use more than two kinds.As this colorant, consider from the viewpoint of permanance such as thermotolerance, photostability, be preferably pigment.
As the pigment that can be used for solidification compound of the present invention, can use known in the past various inorganic pigments or organic pigment.In addition, if consider no matter be inorganic pigment or organic pigment, during all preferred high-transmission rate this point, then preferably use thin as far as possible pigment; If consider that operability, the mean grain size of above-mentioned pigment are preferably 0.01-0.1 μ m, more preferably 0.01-0.05 μ m.In addition, as above-mentioned inorganic pigment, can list: metal oxide, with the metallic compound that metallic complex salt is represented particularly, can list: the metal oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc. and the composite oxides of above-mentioned metal.
As above-mentioned organic pigment, for example can list:
C.I. pigment yellow 11,24, and 31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C.I. pigment orange 36,38,43,71;
C.I. pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C.I. pigment violet 19,23, and 32,39;
C.I. pigment blue 1,2,15,15:1,15:3,15:6,16,22,60,66;
C.I. pigment Green 7,36,37;
C.I. pigment brown 25,28;
C.I. pigment black 1,7;
Carbon black etc.
Among the present invention, can especially preferably use the pigment that in the structural formula of pigment, has alkaline N atom.These pigment with alkaline N atom show good dispersiveness in composition of the present invention.Not fully aware of for its reason, but be because photonasty polymerization composition and pigment compatibility are had desirable influence by inference.
As the pigment that can preferably use in the present application, can list following pigment.But the present invention is not limited to these.
C.I. pigment yellow 11,24, and 108,109,110,138,139,150,151,154,167,180,185;
C.I. pigment orange 36,71;
C.I. pigment red 122,150,171,175,177,209,224,242,254,255,264;
C.I. pigment violet 19,23, and 32;
C.I. pigment blue 15: 1,15:3,15:6,16,22,60,66;
C.I. pigment black 1
These organic pigments can use separately or various being used in combination in order to improve excitation.Below show the object lesson of combinations thereof.For example, as red pigment, can use anthraquione pigmentss, perylene pigment, diketopyrrolopyrrolecocrystals series pigments separately or be that yellow uitramarine, isoindoline are that yellow uitramarine, quinophthalone are that yellow uitramarine, Huo person's perylene are that red pigment is mixed and used etc. their at least a and bisdiazo.For example, as anthraquione pigmentss, can list: C.I. paratonere 177; Zuo is a perylene pigment, can list: C.I. paratonere 155, C.I. paratonere 224; As the diketopyrrolopyrrolecocrystals series pigments, can list: C.I. paratonere 254, consider preferably to mix from the viewpoint of color reproduction with C.I. pigment yellow 13 9.In addition, the mass ratio of red pigment and yellow uitramarine is preferably 100: 5-100: 50.When above-mentioned mass ratio is 100: 4 when following, be difficult to sometimes suppress the light transmission of 400-500nm and can not improve excitation.And when above-mentioned mass ratio be 100: 51 when above, predominant wavelength becomes near the short wavelength sometimes, becomes big with departing from of NTSC target tone.Especially, as above-mentioned mass ratio, optimal scope is 100: 10-100: 30.And, during the red pigment combination with one another, can adjust according to colourity.
In addition,, can use the halo phthualocyanine pigment separately as green pigment, perhaps itself and bisdiazo be yellow uitramarine, quinophthalone be yellow uitramarine, azomethine be yellow uitramarine or or isoindoline be that yellow uitramarine mixes and uses.For example, as such example, preferred C.I. pigment Green 7,36,37 and the mixing of C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180 or C.I. pigment yellow 185.The mass ratio of green pigment and yellow uitramarine is preferably 100: 5-100: 150.As above-mentioned mass ratio preferred especially 100: 30-100: 120 scope.
As the pigment of blueness, can use phthualocyanine pigment separately, perhaps it is that violet pigment mixes use Yu dioxazine.For example preferred C.I. pigment blue 15: 6 and the mixing of C.I. pigment Violet 23.The mass ratio of blue pigment and violet pigment is preferably 100: 0-100: 30, and more preferably below 100: 10.
In addition, as the pigment that black matrix" is used, can use or mix use carbon, titanium carbon, iron oxide, titanium dioxide separately, the combination of preferred carbon and titanium carbon.In addition, the mass ratio of carbon and titanium carbon is preferably 100: 0-100: 60 scope.
When composition of the present invention is used as color filter, consider that from the viewpoint of the even contrast of irregular colour the primary particle size of pigment is preferably 10-100nm, 10-70nm more preferably, more preferably 10-50nm most preferably is 10-40nm.
In addition, when composition of the present invention is used as color filter, consider, preferably use the dyestuff of uniform dissolution in composition from the viewpoint of the even contrast of irregular colour.
As being not particularly limited, can use in the past as the known dyestuff of color filter as the dyestuff of the colorant that in solidification compound of the present invention, contains.For example, can use the spy to open clear 64-90403 communique, the spy opens clear 64-91102 communique, Te Kaiping 1-94301 communique, Te Kaiping 6-11614 communique, the spy steps on No. 2592207, No. 4808501 instructions of United States Patent (USP), No. 5667920 instructions of United States Patent (USP), No. 5059500 instructions of United States Patent (USP), Te Kaiping 5-333207 communique, Te Kaiping 6-35183 communique, Te Kaiping 6-51115 communique, Te Kaiping 6-194828 communique, Te Kaiping 8-211599 communique, Te Kaiping 4-249549 communique, Te Kaiping 10-123316 communique, Te Kaiping 11-302283 communique, Te Kaiping 7-286107 communique, the spy opens the 2001-4823 communique, Te Kaiping 8-15522 communique, Te Kaiping 8-29771 communique, Te Kaiping 8-146215 communique, Te Kaiping 11-343437 communique, Te Kaiping 8-62416 communique, the spy opens the 2002-14220 communique, the spy opens the 2002-14221 communique, the spy opens the 2002-14222 communique, the spy opens the 2002-14223 communique, Te Kaiping 8-302224 communique, Te Kaiping 8-73758 communique, Te Kaiping 8-179120 communique, disclosed pigment in the Te Kaiping 8-151531 communique etc.
As chemical constitution, can use dyestuffs such as pyrazoles azo system, aniline azo system, triphenyl methane system, anthraquinone system, Anthrapyridone system, benzal base system, oxonols system, pyrazoles triazole azo system, pyridone azo system, cyanine system, phenothiazines, pyrroles's pyrazoles azomethine system, xanthene system, phthalocyanine system, chromene system, indigo system.
In addition, under the situation of the resist system that carries out water or alkaline development, consider, can suitably use acid dyes and/or its derivant sometimes from remove deluster the not pattern of illuminated portion and/or the viewpoint of dyestuff fully by developing.
In addition, also can advantageously use direct dyes, basic-dyeable fibre, mordant dye, acid mordant dyes, azoic dyes insoluble azo dyes, disperse dyes, oil-soluble dyes, food dye and/or their derivant etc.
Above-mentioned acid dyes so long as have sulfonic acid or acidic groups such as carboxylic acid just, be not particularly limited, can consider with respect to organic solvent and developer solution dissolubility, with alkali compounds become salt, absorbance, with composition in all necessary performance such as interaction, photostability, thermotolerance of other composition select.
Below, listed the object lesson of acid dyes, but the present invention is not limited to these.For example, can list:
The purple N of acid alizarine;
Acid black 1,2,24,48;
Blue VRS, 7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103,112,113,120,129,138,147,150,158,171,182,192,210,242,243,256,259,267,278,280,285,290,296,315,324:1,335,340;
Acid chrome violet K;
Acid fuchsin;
Acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
Acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169,173;
Azogeramine, 4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88,91,92,94,97,103,111,114,129,133,134,138,143,145,150,151,158,176,182,183,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349,382,383,394,401,412,417,418,422,426;
Acid violet 6B, 7,9,17,19;
Indian yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112,113,114,116,119,123,128,134,135,138,139,140,144,150,155,157,160,161,163,168,169,172,177,178,179,184,190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;
Direct yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129,136,138,141;
Direct orange 34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107;
Direct red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250;
Direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104;
Direct blue 57,77,80,81,84,85,86,90,93,94,95,97,98,99,100,101,106,107,108,109,113,114,115,117,119,137,149,150,153,155,156,158,159,160,161,162,163,164,166,167,170,171,172,173,188,189,190,192,193,194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252,256,257,259,260,268,274,275,293;
Direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82;
Mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,50,61,62,65;
Mordant dyeing orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47,48;
Mordant rouge 1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37,38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94,95;
Mordant dyeing purple 2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53,58;
Mordant dyeing indigo plant 2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39,40,41,43,44,48,49,53,61,74,77,83,84;
Viridon 1,3,4,5,10,15,19,26,29,33,34,35,41,43,53;
Food Huang 3;
And the derivant of these dyestuffs.
In the above-mentioned acid dyes, also preferred following their dye derivate of dye well:
Acid black 24;
Acid blue 23,25,29,62,80,86,87,92,138,158,182,243,324:1;
Acid orange 8,51,56,74,63;
Azogeramine, 4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
Acid violet 7;
Indian yellow 17,25,29,34,42,72,76,99,111,112,114,116,134,155,169,172,184,220,228,230,232,243;
ACID GREEN 25 etc.
In addition, except above-mentioned dyestuff, also preferred azo is, xanthene is, phthalocyanine is an acid dyes, the also preferred C.I. solvent blue 44,38 that uses; C.I. the solvent orange 45; Acid dyes and their dye derivates such as rhodamine B, rhodamine 110.
Wherein, as (C) colorant, be preferably the colorant that is selected among triallyl methane series, anthraquinone system, azomethine system, benzal base system, oxonols system, cyanine system, phenothiazines, pyrroles's pyrazoles azomethine system, xanthene system, phthalocyanine system, chromene system, indigo system, pyrazoles azo system, aniline azo system, pyrazoles triazole azo system, pyridone azo system, the Anthrapyridone system.
Content during as use colorant in solidification compound of the present invention preferably is 5-80 quality %, more preferably 10-70 quality %, more preferably 20-70 quality % in the whole solid state component of solidification compound.
Especially, when solidification compound of the present invention was used for the colored pattern formation of color filter, the content of colorant was preferably in above-mentioned content range more than the 20 quality %, more preferably more than the 30 quality %.
If colorant is very few, then when making color filter, has the trend of the colourity that can not obtain to be fit to by solidification compound of the present invention.On the other hand, if colorant is too much, then can not carries out photocuring fully and reduce as film strength the trend that the development tolerance narrows down when perhaps having alkaline development.
Solidification compound of the present invention can also contain the following optional member that is described in detail as required in (C) composition of (A) composition that contains above explanation and (B) composition and interpolation as required.Below, the optional member that can contain solidification compound of the present invention describes.
＜(D) spreading agent 〉
When solidification compound of the present invention contains pigment as (C) colorant, consider preferred (D) spreading agent that adds from the viewpoint that improves this dispersing of pigments.
As the spreading agent that uses among the present invention (pigment dispersing agent), can list: macromolecule dispersing agent [for example, polyamidoamine and salt thereof, poly carboxylic acid and salt thereof, high molecular unsaturated acid ester, modified polyurethane, modified poly ester, poly-(methyl) acrylate of modification, (methyl) acrylic acid series copolymer, naphthalene sulfonic acid-formaldehyde condensation product] and polyxyethylated phosphate, polyoxyethylene alkyl amine, alkanolamine, pigment derivative etc.
Macromolecule dispersing agent can be further divided into straight chain shape macromolecule, terminal-modified type macromolecule, graft type macromolecule, block type polymer from its structure.
Macromolecule dispersing agent is adsorbed on the surface of pigment, plays a role so that prevent aggegation again.Therefore, can list as preferred construction: have terminal-modified type macromolecule, graft type macromolecule, block type polymer to the position of surface of pigments anchoring.On the other hand, pigment derivative is passed through the surface of pigments modification, thereby has the effect that promotes macromolecule dispersing agent absorption.
As the object lesson that can be used for pigment dispersing agent of the present invention, can list: BYKChemie corporate system " Disperbyk-101 (polyamidoamine phosphate); 107 (carboxylates); 110 (multipolymers that contain acidic group); 130 (polyamide); 161; 162,163,164,165,166,170 (high-molecular copolymers) "; " BYK-P104, P105 (high molecular unsaturated polyester carboxylic acid), EFKA corporate system " EFKA4047; 4050; 4010; 4165 (polyurethane series); EFKA4330; 4340 (segmented copolymers), 4400,4402 (modified polyacrylates), 5010 (polyesteramides), 5765 (high molecular polycarboxylates), 6220 (aliphatic polyesters), 6745 (phthalocyanine derivates) 6750 (AZO pigments derivant) "; aginomoto Fine Techno corporate system " Ajisper PB821, PB822 "; common prosperity company chemistry corporate system " Flowren TG-710 (urethane oligomers) "; " Polyflow No.50E, No.300 (acrylic acid series copolymer) "; nanmu originally changes into corporate system " Disparon KS-860,873SN, 874, #2150 (aliphatics polybasic carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725 "; KAO. Corp. SA's system " Demol RN, N (naphthalene sulfonic acid formaldehyde condensation polymer), MS, C, SN-B (aromatic sulphonic acid formaldehyde condensation products) "; " HOMOGENOL L-18 (polymeric polycarboxylic acid) "; " Emulgen 920,930,935,985 (polyoxyethylene nonylplenyl ethers) "; " Acetamine 86 (stearmide acetic acid esters) "; Lubrizol corporate system " SOLSPAS 5000 (phthalocyanine derivates), 22000 (AZO pigments derivants), 13240 (polyesteramines), 3000,17000,27000 (macromolecules that partly have funtion part endways), 24000,28000,32000,38500 (graft type macromolecules) "; daylight Chemical person corporate system " Nikol T106 (polyoxyethylene sorbitol monooleate) "; MYS-IEX (polyoxyethylene monostearate) " etc.
These spreading agents can use separately, also can be used in combination more than two kinds.Among the present invention, especially preferably pigment derivative and macromolecule dispersing agent are used in combination.
As the content of the spreading agent among the present invention, be 1-100 quality % with respect to pigment optimization, more preferably 3-100 quality %, more preferably 5-80 quality %.
Specifically, when using macromolecule dispersing agent,, be the scope of 5-100 quality % with respect to pigment optimization as its use amount, the scope of 10-80 quality % more preferably.In addition, when using pigment derivative,, be the scope of 1-30 quality % with respect to pigment optimization as its use amount, the scope of 3-20 quality % more preferably is preferably the scope of 5-15 quality % especially.
Among the present invention, use is during as the pigment of colorant and spreading agent, consider from the viewpoint of solidifying sensitivity, colour saturation, the content summation of colorant and spreading agent is preferably 30-90 quality % with respect to the whole solid state component that constitutes solidification compound, more preferably 40-85 quality %, more preferably 50-80 quality %.
＜(F) sensitizer 〉
For the free-radical generating efficient that improves radical initiator, the long wavelengthization of wavelength photoreceptor, solidification compound of the present invention also can contain (F) sensitizer, as being used for sensitizer of the present invention, preferably carry out the compound of sensitizing with electron transfer structure or energy transfer structure for above-mentioned Photoepolymerizationinitiater initiater.
As being used for sensitizer of the present invention, can list: belong to the following compounds of enumerating, and the compound that has absorbing wavelength in the wavelength region may of 300-450nm.
As the example of preferred sensitizer, can list: belong to following compounds, and have the compound of absorbing wavelength in the 330-450nm zone.
For example, can list: the polynuclear aromatic same clan (for example, luxuriant and rich with fragrance, anthracene, pyrans, pyrene, benzo [9,10] phenanthrene, 9,10-dialkoxy anthracene), the xanthene class (for example, fluorescein, eosin, erythrosine, rhodamine B, rose-red), thioxanthene ketone (isopropyl thioxanthone, diethyl thioxanthone, chloro thioxanthone), cyanine class (sulfo-carbocyanine for example, the oxo carbocyanine), the merocyanine class (for example, merocyanine, the carbonyl merocyanine), phthalocyanines, thiazide (for example, thionine, methylenum careuleum, toluidine blue), acridine (for example, acridine orange, chloroflavin, acridine yellow), the anthraquinone class (for example, anthraquinone), salt (for example in the squaric acid, the squaric acid inner salt), acridine orange, Coumarins (for example, 7-lignocaine-4-methylcoumarin), the oxo cumarin, phenothiazines, the azophenlyene class, styryl benzene class, azo-compound, diphenyl methane, triphenyl methane, the diphenylethyllene benzene class, carbazoles, porphyrin, spiro-compound, quinoline a word used for translation ketone, indigo, styryl, the pyralium salt compound, the methylene azole compounds, the pyrazoles triazole compounds, benzothiazole compound, the barbituric acid derivant, the Malony Ithiourea derivant, acetophenone, benzophenone, thioxanthones, aromatic ketone compounds such as Michler's keton, heterogeneous ring compounds such as N-Fang oxazolidinone etc.; Also can list: No. 568993 instructions of European patent, No. 4508811 instructions of United States Patent (USP), United States Patent (USP) No. 5227227 instructions, spy open the compound etc. that 2001-125255 communique, spy are opened record in the flat 11-271969 communique etc.
As the example of preferred sensitizer, can list: the compound of following general formula (I)-(V) expression.
[Chemical formula 1 7]
Figure A20071010455100461
General formula (I)
(in the formula (I), A 1Expression sulphur atom or NR 50, R 50Expression alkyl or aryl, L 2Expression and adjacent A 2Form the nonmetallic atom group of the alkalescence nuclear of pigment, R jointly with adjacent carbon atom 51, R 52Represent hydrogen atom or monovalence nonmetallic atom group respectively independently, R 51, R 52Also can be bonded to each other and form the acid core of pigment.W represents oxygen atom or sulphur atom.)
[Chemical formula 1 8]
Figure A20071010455100462
General formula (II)
(in the formula (II), Ar 1And Ar 2Represent aryl respectively independently, by by-L 3The key of-formation is connected.L wherein 3Expression-O-or-S-.In addition, the group synonym shown in W and the general formula (XIV).
[Chemical formula 1 9]
Figure A20071010455100471
General formula (III)
(in the formula (III), A 2Expression sulphur atom or NR 59, L 4Expression and adjacent A 2Form the nonmetallic atom group of the alkalescence nuclear of pigment, R jointly with carbon atom 53, R 54, R 55, R 56, R 57And R 58Represent monovalence nonmetallic atom group, R respectively independently 59Expression alkyl or aryl.)
[Chemical formula 2 0]
General formula (IV)
(in the formula (IV), A 3, A 4Respectively independently expression-S-or-NR 62-or-NR 63-, R 63, R 64Represent replacement or unsubstituted alkyl, replacement or unsubstituted aryl respectively independently, L 5, L 6Expression and adjacent A independently respectively 3, A 4Form the nonmetallic atom group of the alkalescence nuclear of pigment, R jointly with adjacent carbon atom 60, R 61Can represent the monovalence nonmetallic atom group respectively independently or be bonded to each other and form the ring of aliphatics or aromatic series.)
[Chemical formula 2 1]
Figure A20071010455100473
General formula (V)
(in the formula (V), R 66Expression can have substituent aromatic ring or heterocycle, A 5Expression oxygen atom, sulphur atom or-NR 67-.R 64, R 65And R 67Represent hydrogen atom or monovalence nonmetallic atom group respectively independently, R 67And R 64, and R 65And R 67Can be bonded to each other respectively to be used to form the ring of aliphatics or aromatic series.)
Preferred object lesson as the compound of general formula (I)-(V) expression can list: compound as follows.
[Chemical formula 2 2]
Figure A20071010455100481
Sensitizer can be used alone, also can be also with more than two kinds.
Consider that from efficiency of light absorption that absorbs the deep and the viewpoint that causes decomposition efficiency the content of sensitizer converts in solid state component and is preferably 0.1-20 quality %, more preferably 0.5-15 quality % in the solidification compound of the present invention.
＜(G) binder polymer 〉
In the solidification compound of the present invention,, can also use binder polymer as required in order to improve diaphragm characteristic etc.Preferably use the wire organic polymer as bonding agent.As such " wire organic polymer ", can choose wantonly and use known compound.In order to carry out water development or weak base water development, preferably being chosen in water or the weak base water is the wire organic polymer of solubility or swellability.The wire organic polymer not only forms agent as diaphragm, and can be according to as the purposes of water, weak base water or organic solvent developer and selected use.For example, if when using water-soluble organic polymer, then can carry out water development.As such wire organic polymer, can list: the free radical polyalcohol that has the carboxylic acid group at side chain, for example specially open clear 59-44615 number, special public clear 54-34327 number, special public clear 58-12577 number, special public clear 54-25957 number, spy and open clear 54-92723 number, spy and open clear 59-53836 number, spy and open those of record in clear 59-71048 number, promptly have the monomer homopolymerization of carboxyl or the resin that copolymerization forms; To have the monomer homopolymerization or the copolymerization of acid anhydrides and make hydrolysis of acid anhydrides unit or half esterization or half amideization and the resin that forms; With used for epoxy resin unsaturated monocarboxylic acid and anhydride modified and epoxy acrylate that form.As the monomer with carboxyl, can list: acrylic acid, methacrylic acid, itaconic acid, butenoic acid, maleic acid, fumaric acid, 4-carboxyl styrene etc. as the monomer with acid anhydrides, can list: maleic anhydride etc.
Also has the acid cellulose derivant that has the carboxylic acid group equally at side chain.Usefully make polymkeric substance and cyclic acid anhydride add material that is shaped as etc. in addition with hydroxyl.
When alkali soluble resin is used as multipolymer, also can use the compound of the above-mentioned monomer of enumerating other monomer in addition as copolymerization.As the example of other monomer, can list the compound of following (1)-(12).
(1) acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate, acrylic acid 3-hydroxypropyl acrylate, acrylic acid 4-hydroxy butyl ester, methacrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxypropyl acrylate, methacrylic acid 3-hydroxypropyl acrylate, methacrylic acid 4-hydroxy butyl ester etc. have the esters of acrylic acid and the methyl acrylic ester of aliphatic hydroxyl.
(2) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, acrylic acid pentyl ester, Hexyl 2-propenoate, 2-EHA, 2-ethyl hexyl acrylate, benzyl acrylate, acrylic acid 2-chloroethene ester, glycidyl acrylate, acrylic acid 3, alkyl acrylates such as 4-epoxycyclohexyl methyl esters, vinyl acrylate, acrylic acid 2-phenyl vinyl acetate, acrylic acid 1-propylene ester, allyl acrylate, acrylic acid 2-allyloxy ethyl ester, acrylic acid alkynes propyl ester.
(3) methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, the methacrylic acid pentyl ester, hexyl methacrylate, methacrylic acid 2-Octyl Nitrite, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid 2-chloroethene ester, glycidyl methacrylate, methacrylic acid 3,4-epoxycyclohexyl methyl esters, the metering system vinyl acetate, methacrylic acid 2-phenyl vinyl acetate, methacrylic acid 1-propylene ester, allyl methacrylate, methacrylic acid 2-allyloxy ethyl ester, alkyl methacrylates such as methacrylic acid alkynes propyl ester.
(4) acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-ethyl acrylamide, N-hexyl methyl acrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N phenyl acrylamide, N-nitrobenzophenone acrylamide, N-ethyl-N phenyl acrylamide, vinyl acrylamide, vinyl Methacrylamide, N, N-diallyl acrylamide, N, acrylamide or Methacrylamides such as N-diallyl Methacrylamide, allyl acrylamide, allyl methyl acrylamide.
(5) vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl group vinyl ether, Vinyl phenyl ether.
(6) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate.
(7) phenylethylenes such as styrene, α-Jia Jibenyixi, methyl styrene, 1-chloro-4-methyl-benzene, p-acetoxy-styrene.
(8) vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone, phenyl vinyl ketone.
(9) olefines such as ethene, propylene, isobutylene, butadiene, isoprene.
(10) N-vinyl pyrrolidone, vinyl cyanide, methacrylonitrile etc.
(11) unsaturated acyl imines such as maleimide, N-acryloyl group acrylamide, N-acetyl group Methacrylamide, N-propiono Methacrylamide, N-(p-chlorobenzene formacyl) Methacrylamide.
(12) combine heteroatomic metha crylic monomer in the α position.For example, can list: the compound of record in special Willing 2001-115595 instructions, the special Willing 2001-115598 instructions etc.
In above-mentioned compound, side chain have allyl, vinyl ester and carboxyl (methyl) acryl resin and special open 2000-187322 communique, spy open put down in writing in the 2002-62698 communique have the alkali soluble resin of two keys at side chain, open the alkali soluble resin that has amide group at side chain put down in writing in the 2001-242612 communique in excellence aspect the balance of film strength, sensitivity, development with the spy, from but preferred.
In addition, special fair 7-12004 number, special fair 7-120041 number, special fair 7-120042 number, special fair 8-12424 number, spy open clear 63-287944 number, spy open clear 63-287947 number, spy open flat 1-271741 number etc. in the urethane that contains acidic group of record be binder polymer, with the spy open the urethane of putting down in writing among the 2002-107918 that has acidic group and two keys at side chain be binder polymer because intensity is very excellent, with regard to the viewpoint of anti-brush, low exposure performance power, be favourable.
In addition, the acetal modified polyvinylalcohol with acidic group that European patent 993966, European patent 1204000, spy open record among the 2001-318463 etc. is binder polymer excellence aspect the balance of film strength, development, from but preferred.
In addition, as other water-soluble wire organic polymer, suitable polyvinylpyrrolidone and the polyethylene oxide etc. of using.In addition, solidify the protection film strength in order to improve, pure soluble nylon and 2, the polyethers of two (4-hydroxy phenyl) propane of 2-and chloropropylene oxide etc. also is favourable.
As the weight-average molecular weight of operable binder polymer in the present invention, be preferably more than 5,000 10,000～300,000 scope more preferably, and with regard to number-average molecular weight, being preferably more than 1000, the more preferably scope of 2000-25 ten thousand.Polydispersity (weight-average molecular weight/number-average molecular weight) is preferably more than 1, more preferably the scope of 1.1-10.
These binder polymers also can be that atactic polymers, block polymer, graft polymer etc. are any.
Operable in the present invention binder polymer can be with known method was synthetic in the past.The solvent that uses when synthetic, can list: tetrahydrofuran, ethylene dichloride, cyclohexanone, MEK, acetone, methyl alcohol, ethanol, glycol monoethyl ether, ethylene glycol monoethyl ether, acetic acid 2-methoxyl ethyl ester, diethylene glycol dimethyl ether, 1-methoxyl-2-propyl alcohol, acetic acid 1-methoxyl-2-propyl ester, N, dinethylformamide, N,N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide (DMSO), water etc.These solvents can use separately or mix more than two kinds and use.
The radical polymerization initiator that uses during as synthetic operable binder polymer in the present invention can list: known compounds such as azo series initiators, peroxide initiator.
＜(H) sensitizer altogether 〉
Solidification compound of the present invention also preferably contains common sensitizer.Among the present invention altogether sensitizer have further raising with respect to the sensitivity of the active radioactive ray of sensitizing coloring matter and initiating agent or suppress the effects such as polymerization obstruction of the polymerizable compound that produces because of oxygen.
As so common sensitizer; can list: amine; 3173 pages (1972) of work such as M.R.Sander " Journal of Polymer Society " the 10th volume for example; special public clear 44-20189 communique; the spy opens clear 51-82102 communique; the spy opens clear 52-134692 communique; the spy opens clear 59-138205 communique; the spy opens clear 60-84305 communique; the spy opens clear 62-18537 communique; the spy opens clear 64-33104 communique; the compound of record etc. among No. 33825, the Research Disclosure; specifically, can list: triethanolamine; p-dimethylaminobenzoic acid ethyl ester; p-formoxyl xylidin; p-methyl mercapto xylidin etc.
As other example that is total to sensitizer, can list: mercaptan and sulfide-based, the for example special clear 53-702 communique, special public clear 55-500806 communique, spy opened opened di-sulphide compounds that mercaptan compound, the spy of flat 5-142772 communique record open clear 56-75643 communique etc., specifically, can list: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-4 (3H)-quinazoline, β-mercaptonaphthalene etc.
In addition, as other example that is total to sensitizer, can list: amino-acid compound (for example, N-phenylglycine etc.), the organometallics of special public clear 48-42965 communique record (for example, tributyl tin acetates etc.), hydrogen donor, the spy of special public clear 55-34414 communique record open the sulphur compound (for example, thioformaldehyde etc.) of flat 6-308727 communique record etc.
Improve the viewpoint of curing rate considers from the balance by polymerization growth rate and chain transfer, the content of these common sensitizers is the scope of 0.1-30 quality % with respect to the quality optimization of the whole solid state component of solidification compound, the more preferably scope of 1-25 quality %, the more preferably scope of 0.5-20 quality %.
＜(I) polymerization inhibitor 〉
Among the present invention, preferably in the manufacturing of solidification compound or in preserving in order to stop compound undesirable thermal polymerization to take place and add the small amount of thermal polymerization inhibitor with ethylenical unsaturated double bonds that can polymerization.
As being used for thermal polymerization inhibitor of the present invention, can list: quinhydrones, p methoxy phenol, BHT, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol, benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-methylene bis (4-methyl-6-tert butyl phenol), the inferior cerium salt of N-nitroso-phenyl hydramine etc.
The addition of thermal polymerization inhibitor is about 0.01-5 quality % with respect to the quality optimization of whole composition.In addition as required, also can add the advanced higher fatty acid derivative of mountain Yu acid and mountain Yu acid amides and so on etc. for the polymerization obstruction that prevents to produce, be present in unevenly on the surface of photographic layer in the dry run after coating because of oxygen.The addition of advanced higher fatty acid derivative is preferably about 0.5-10 quality % of whole composition.
＜other adjuvant 〉
The printing ink that in addition, among the present invention, in order to improve the rerum natura of solidifying diaphragm, also can add inorganic filler, plastifier, can improve the photographic layer surface the known adjuvants such as sense fat agent of wall.
As plastifier for example dioctyl phthalate, phthalandione two (dodecyl) ester, triethylene glycol dicaprylate, phthalandione dimethyl glycol ester, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerine etc. are arranged; under the situation of having used bonding agent, can add below the 10 quality % with respect to the gross mass of compound with ethylenical unsaturated double bonds and cement.
The solidification compound of the invention described above solidifies under high sensitivity, and storage stability is also good.In addition, the hard material surfaces such as substrate that are suitable for solidification compound are shown high adhesiveness.Therefore, solidification compound of the present invention can be preferably uses in fields such as the Image forming material of three-dimensional light appearance, holograph, color filter and so on, printing ink, coating, bonding agent, coating agent.
[color filter and manufacture method thereof]
Below, color filter of the present invention and manufacture method thereof are described.
Color filter of the present invention is characterised in that to have the colored pattern that uses solidification compound of the present invention to form on supporter.
Below, to color filter of the present invention, describe in detail by its manufacture method (manufacturing method of color filter of the present invention).
It is characterized in that comprising following operation: on the supporter coating solidification compound of the present invention and form the solidification compound layer operation (below, suitable abbreviating as " the solidification compound layer forms operation "), the operation of above-mentioned solidification compound layer being exposed by mask (below, suitable abbreviate as " exposure process ") and the above-mentioned solidification compound layer after will expose develop and form the operation (below, " developing procedure " suits to abbreviate as) of colored pattern.
Below each operation in the manufacture method of the present invention is described.
＜solidification compound layer forms operation 〉
In the solidification compound layer forms operation, coating solidification compound of the present invention on supporter and form the solidification compound layer.
As the supporter that can be used for this operation, can list: soda-lime glass, the Pai Ruikesi (pyrex that in liquid crystal display cells etc., uses for example; Registered trademark) glass, quartz glass and adhere on them that nesa coating obtains and the photo-electric conversion element substrate of use in imaging apparatus etc., for example silicon substrate etc. and complementary burning film semiconductor (CMOS) etc.These substrates also form the secret note with each pixel isolation sometimes.
In addition, on these supporters, also can be as required in order to improve with the adhesion of upper layer, to prevent the planarization of material diffusion or substrate surface and undercoat is set.
As the method that solidification compound of the present invention is coated on the supporter, can suitably use various coating methods such as slit coating, ink-jet method, spin coated, curtain coating coating, roller coat, silk screen print method.
As the coating thickness of solidification compound, be preferably 0.1-10 μ m, more preferably 0.2-5 μ m, more preferably 0.2-3 μ m.
The drying (prebake) that is coated in the Photocurable composition layer on the substrate can be carried out 10-300 second with heating plate, baking oven etc. under 50-140 ℃ temperature.
＜exposure process 〉
At exposure process, above-mentioned solidification compound layer is formed the solidification compound layer that forms in the operation expose by mask with regulation mask pattern.
Exposure in this operation; the pattern exposure that is coated film can be undertaken by following manner: the mask pattern by regulation exposes; only make by light-struck coated film partly solidifiedly, develop, form the pattern-like diaphragm of forming by (3 looks or 4 looks) of all kinds pixel with developer solution.Operable radioactive ray during as exposure especially preferably use ultraviolet rays such as g line, i line.Exposure is preferably 5-1500mJ/cm 2, 10-1000mJ/cm more preferably 2, most preferably be 10-500mJ/cm 2
When color filter of the present invention is when being used for liquid crystal display cells, be preferably 5-200mJ/cm in the above range 2, 10-150mJ/cm more preferably 2, most preferably be 10-100mJ/cm 2In addition, when color filter of the present invention is when being used for solid-state imager, be preferably 30-1500mJ/cm in the above-mentioned scope 2, 50-1000mJ/cm more preferably 2, most preferably be 80-500mJ/cm 2
＜developing procedure 〉
Then, handle, will in above-mentioned exposure, the non-irradiated part of light be eluted in the alkaline aqueous solution, only keep the part of photocuring by carrying out alkaline development.As developer solution, preferably do not cause the organic basic developer solution of the damages such as circuit of substrate.Be generally 20-30 ℃ as development temperature, development time is 20-90 second.
As the alkaline reagent that is used for developer solution, can list: for example ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicylo-organic basic compounds such as [5.4.0]-7-undecylene preferably uses the alkaline aqueous solution that these alkaline reagents are formed with the pure water dilution as 0.001-10 quality %, the mode that is preferably 0.01-1 quality % according to concentration as developer solution.In addition, when using the developer solution of being made up of such alkaline aqueous solution, (rinsing) washed with pure water in the back of developing usually.
Then, remaining developer solution is removed in washing, carries out heat treated (back oven dry) after implementing drying.So can repeat above-mentioned operation successively and make the curing diaphragm each color.Obtain color filter thus.
Back oven dry is the heat treated that is used to make after the development of completion of cure, carries out 100-240 ℃ heat curing usually and handles.When substrate is glass substrate or silicon substrate in the said temperature scope also preferred 200-240 ℃.
This back oven dry is handled and can be used heating plate and heater meanses such as heated air circulation type dryer, high frequency heating machine with aforesaid condition to the coated film after developing, in a continuous manner or intermittent mode carry out.
In addition, in the manufacture method of the present invention, after having carried out the above-mentioned formation of solidification compound layer operation, exposure process and developing procedure, also can have the curing process of colored pattern by heating and/or exposing and be cured that will form as required.
Form operation, exposure process and developing procedure (and the curing process that has as required) by solidification compound layer and only repeat desirable tone number, make the color filter of forming by desirable tone above explanation.
As the purposes of solidification compound of the present invention,, can certainly be applicable to the black matrix" that between the pixel of color filter, is provided with though mainly narrated the purposes that is used as the pixel of color filter on the main body.Black matrix" can form by following method: except in solidification compound of the present invention, add black colorants such as carbon black, titanium be black as colorant, also can carry out pattern exposure, alkaline development in the same manner, promote the black matrix" that is solidified to form of film then by the back oven dry with the method for making of above-mentioned pixel.
Color filter of the present invention is owing to use the solidification compound of the invention described above, formed colored pattern has shown the adhesiveness height with the supporter substrate, because the anti-development excellence of cured composition, so exposure sensitivity excellence, good adhesion with the substrate of exposed portion, and, can form the high-resolution pattern that can produce desirable section shape.Therefore, go for solid-state imagers such as liquid crystal display cells and CCD, be particularly suitable for surpassing the high-resolution CCD element of 1,000,000 pixels and CMOS etc.Color filter of the present invention can be as the color filter that for example divides and be used for being provided with between the lenticule of optically focused at the light accepting part of each pixel that constitutes CCD.
Embodiment
Below, more specifically describe the present invention by embodiment, but the present invention is not limited to following examples.In addition, unless specifically stated otherwise, " % ", " part " they are benchmark with the quality.
Below, show the concrete synthetic method of above-mentioned exemplary compounds (1).Can be used for other (A) specific aggregation compound of the present invention also can be synthetic with identical flow process.In addition, synthetic method is not limited to following method.
[synthesis example 1]: exemplary compounds (1) synthetic
In five acrylic acid dipentaerythritol ester 12g (0.023mol), add acetonitrile 20ml and make its dissolving, add three (2 ethyl hexanoic acid) bismuth 0.16g (0.25mol) and triethoxy (3-isocyanates propyl group) silane 5.9g (0.23mol) then and descend stirring 3 hours at 55-65 ℃.After reaction finishes, reactant liquor is cooled to adds normal hexane 50ml after the room temperature and wash 3 times, tell lower floor.Distillation removes and desolvates, and obtains compound (1) 17g (0.022mol (yield: 95%)).
To the above-mentioned compound that obtains (1), carry out structural confirmation, result by NMR 1H-NMR (400MHz, solvent: deuterochloroform, standard substance: tetramethylsilane) be:
δ6.40(5H、dd)、6.10ppm(5H、dd)、5.85ppm(5H、dd)、5.10ppm(1H、brt)、4.25ppm(6H、s)、4.20ppm(4H、s)、4.16ppm(2H、s)、3.81ppm(6H、q)、3.48ppm(2H、s)、3.45ppm(2H、s)、3.15ppm(2H、m)、1.62ppm(2H、m)、1.23ppm(9H、t)、0.63ppm(2H、m)
More specifically describe solidification compound of the present invention below by embodiment, but the present invention only otherwise exceeding its aim just is not limited to following embodiment.
(embodiment 1)
[the 1. preparation of solidification compound]
Here, describe as the example that used for liquid crystal display element color filter on the way forms the solidification compound that contains colorant (pigment) of usefulness by enumerating preparation.
1-1. the mixing dispersion treatment of pigment
At first, with double roll mill following each composition is carried out mixing dispersion treatment.
C.I. paratonere 254 22 mass parts
C.I. pigment yellow 13 98 mass parts
Resin solution (benzyl methacrylate/methacrylic acid/hydroxyethyl methylacrylate multipolymer, mol ratio: 80/10/10, Mw:10000, solvent: 1-Methoxy-2-propyl acetate 60%, resin solid component concentration: 40 mass parts 40%)
Solvent: 1-Methoxy-2-propyl acetate 20 mass parts
Spreading agent: (trade name: BY-161, BYK company) 2 mass parts
Further in the above-mentioned dispersion thing that obtains, add following compositions and carry out the diffusing processing of diel differential with sand mill.
Solvent: 1-Methoxy-2-propyl acetate (PGMEA) 200 mass parts
1-2. the preparation of solidification compound (coating liquid)
In the pigment after above-mentioned dispersion treatment, further add following compositions, mix, thus preparation solidification compound solution.
Above-mentioned exemplary compounds (1) [(A) specific aggregation compound] 12 mass parts
4-benzo tetrahydrofuran-2,6-two (trichloromethyl)-s-triazine [(B) Photoepolymerizationinitiater initiater] 0.5 mass parts
Surfactant (trade name TETRONIC 150R1, BASF AG)
0.2 mass parts
Solvent: PGMEA 100 mass parts
[the 2. making of color filter]
2-1. the formation of solidification compound layer
The solidification compound that contains above-mentioned pigment is made resist solution, on the glass substrate of 550mm * 650mm, carry out slit coating under the following conditions, under this state, keep then 10 minutes standby, carry out vacuum drying and prebake (prebake) (100 ℃, 80 seconds), thereby the formation solidification compound is filmed (solidification compound layer).
(slit coating condition)
The gap of the opening portion on applicator head top: 50 μ m
Coating speed: 100mm/ second
The gap of substrate and applicator head: 150 μ m
Applied thickness (dry thickness): 2 μ m
Application temperature: 23 ℃
2-2. exposure, development
Then, use the ultrahigh pressure mercury lamp of 2.5kw to use the test photomask exposure of live width 20 μ m to be pattern-like the Photocurable coating film, after the exposure, with organic system developer solution (trade name: CD, FUJIFILM ARCH CO., LTD. 10% aqueous solution system) covers whole of exposed film, static 60 seconds.
2-3. heat treated
After static, spray pure water with the shower shape and take wash-out developer, the coated film that will carry out photocuring processing and development treatment heats 1 hour (back oven dry) in 220 ℃ baking oven.Thus, on glass substrate, form pigmentary resin diaphragm (color filter).
[3. performance evaluation]
Estimate the storage stability of cured composition for color coating liquid of above-mentioned preparation and exposure sensitivity, substrate adhesiveness, development and the pattern section shape that uses the solidification compound coated film (dyed layer) that this cured composition for color forms on glass substrate as follows.The result is as shown in table 1.
3-1. coating liquid storage stability
Above-mentioned coating liquid was at room temperature preserved 1 month, estimated the degree of separating out of foreign matter then according to following criterion by range estimation.
＜criterion 〉
Zero: do not observe and separate out.
△: observe a bit a little and separate out.
*: observe and separate out.
3-2. the exposure sensitivity of coated film (dyed layer)
Exposure is changed into 10-100mJ/cm 2Various exposures expose, be the pattern line-width after the back oven dry that the exposure of 20 μ m is estimated as the exposure sensitivity.The result shows that the value of exposure sensitivity is more little, and sensitivity is high more.
3-3. development, pattern section shape, substrate adhesiveness
Observe by optical microscope and SEM photo, substrate surface and section shape after with usual way the back being dried are confirmed.
In the exposure process, observing does not have the zone (unexposed portion) of irradiates light to have or not residue, thereby estimates development.
＜development 〉
Zero:, confirm not have fully residue at unexposed portion.
△: at unexposed portion, confirm to have a little a residue, but be no problem degree on using.
*: at unexposed portion, confirm obviously to have residue.
Observe the section shape of the pattern that forms.The pattern section shape most preferably is along taper, its less preferred rectangle, not preferred back taper.
Whether as the adhering evaluation of substrate, observing has the damaged generation of pattern.For these assessment items, estimate according to following standard.
＜substrate adhesiveness 〉
Zero: it is damaged not observe pattern fully.
△: it is damaged almost not observe pattern, damaged but the part is observed.
*: it is damaged obviously to observe pattern.
[embodiment 2-9]
Except will in the solidification compound of embodiment 1, the exemplary compounds (1) as (A) specific aggregation compound replacing with the exemplary compounds shown in the following table 1, other carries out according to the step identical with embodiment 1 fully and obtains colored pattern, and carries out the evaluation identical with embodiment 1.The result is as shown in table 1.
[embodiment 10]
Except will be in the solidification compound of embodiment 1 as the exemplary compounds (1) of (A) specific aggregation compound replace with the exemplary compounds shown in the following table 1, the polyethylene terephthalate substrate (being recited as " pet substrate " in the table) that glass substrate is transformed to identical size is as substrate, be transformed to 10000mJ/cm under high-pressure sodium lamp with the back baking operation 2Irradiation process outside, other carries out according to the step identical with embodiment 1 fully and obtains colored pattern, and carries out the evaluation identical with embodiment 1.The result is as shown in table 1.
[comparative example 1]
Except will be in the solidification compound of embodiment 1 replacing with the comparison polymerizable composition, polymerizable composition shown in the following table 1 as the exemplary compounds (1) of (A) specific aggregation compound, other carries out according to the step identical with embodiment 1 fully.The result is as shown in table 1.
[comparative example 2]
Except will be in the solidification compound of embodiment 1 as the exemplary compounds (1) of (A) specific aggregation compound replace with the exemplary compounds shown in the following table 1, the polyethylene terephthalate substrate that glass substrate is transformed to identical size is as substrate, be transformed to 10000mJ/cm under high-pressure sodium lamp with the back baking operation 2Irradiation process outside, other carries out according to the step identical with embodiment 1 fully and obtains colored pattern, and carries out the evaluation identical with embodiment 1.The result is as shown in table 1.
[table 1]
(A) specific aggregation compound or comparison polymerizable compound Supporter Storage stability Exposure sensitivity (mJ/cm 2) Development The substrate adhesiveness The pattern section shape
Embodiment 1 Exemplary compounds (1) Glass substrate ○ 40 ○ ○ Along taper
Embodiment 2 Exemplary compounds (2) Glass substrate ○ 55 ○ ○ Rectangle
Embodiment 3 Exemplary compounds (4) Glass substrate ○ 65 ○ ○ Along taper
Embodiment 4 Exemplary compounds (6) Glass substrate ○ 45 ○ ○ Along taper
Embodiment 5 Exemplary compounds (8) Glass substrate ○ 40 △ ○ Along taper
Embodiment 6 Exemplary compounds (9) Glass substrate ○ 40 ○ ○ Along taper
Embodiment 7 Exemplary compounds (10) Glass substrate ○ 55 ○ ○ Rectangle
Embodiment 8 Exemplary compounds (14) Glass substrate ○ 65 ○ ○ Along taper
Embodiment 9 Exemplary compounds (22) Glass substrate ○ 45 ○ ○ Along taper
Embodiment 10 Exemplary compounds (23) Pet substrate ○ 40 △ ○ Along taper
Comparative example 1 Pentaerythritol tetracrylate Glass substrate ○ 85 △ △ Back taper
Comparative example 2 Six acrylic acid dipentaerythritol ester Pet substrate △ 80 △ × Back taper
Can judge from the result of table 1, used cured composition for color excellent storage stability under its solution state of the embodiment of solidification compound of the present invention, when on supporter, forming image, with respect to having used the relatively comparative example of polymerizable compound of the outer polyfunctional acrylic ester system of the scope of the invention, any one in development, substrate adhesiveness, the pattern section shape is all excellent.In addition we know, by two key density and substrate adhesiveness near the raising substrate, the erosion that is produced by developer solution is inhibited, and the result has improved the exposure sensitivity.
Below, describe as the example that the color filter of solid-state imager purposes forms the solidification compound that contains colorant (dyestuff) of usefulness by enumerating preparation.
(embodiment 11)
[the 1. preparation of resist liquid]
The composition of following composition is mixed and dissolving preparation resist liquid.
＜form
19.20 parts of propylene glycol monomethyl ether acetate
(PGMEA: solvent)
36.67 parts of ethyl lactates
30.51 parts of binder polymers
[the 40%PGMEA solution of benzyl methacrylate/methacrylic acid/2-hydroxyethyl methacry-late multipolymer (mol ratio=60/22/18)]
12.20 parts of six acrylic acid dipentaerythritol ester
(optical polymerism compound)
0.0061 part of polymerization inhibitor (p methoxy phenol)
Fluorine is 0.83 part in a surfactant
(F-475, big Japanese ink chemical industry (strain) system)
0.586 part of Photoepolymerizationinitiater initiater
(TAZ-107 (Photoepolymerizationinitiater initiater of trihalomethyl triazine system), Midori chemical company system)
[2. having the making of the silicon substrate of undercoat]
With 6 inches silicon chips in baking oven 200 ℃ of left and right sides heat treated 30 minutes.Then, on this silicon chip, be that the mode of 2 μ m applies above-mentioned resist liquid according to dry film thickness, heat drying 1 hour in 220 ℃ baking oven forms undercoat, thereby obtains to have the silicon chip substrate of undercoat again.
[3. containing the preparation (dyestuff system) of the solidification compound of colorant]
With the compound dissolving of following composition A-1, preparation photosensitive composition A-1.
＜composition A-1 〉
80 parts of cyclohexanone (solvent)
5.0 parts of Valifast yellow 1101 (dyestuff (C))
5.0 parts of acid reds 57 (dyestuff (C))
Six acrylic acid dipentaerythritol ester
5.0 parts of general free-radical polymerised compounds (E) that do not have the adhesiveness group
2.0 parts of above-mentioned exemplary compounds (1) [(A) specific aggregation compound]
2.5 parts of Photoepolymerizationinitiater initiaters (B)
(CGI-124, Ciba Speciality Chemicals corporate system; Oxime is a Photoepolymerizationinitiater initiater)
0.5 part of glycerine propoxyl group ester
(number-average molecular weight Mn:1500, molar absorptivity ε=0, leuco compound)
[the 5. making and the evaluation of the color filter that obtains with photosensitive composition]
The formation of-pattern and the evaluation of sensitivity-
The solidification compound A-1 that contains colorant of preparation in above-mentioned 3. is coated on the undercoat of the silicon substrate that has undercoat that obtains in above-mentioned 2., forms solidification compound layer (coated film).Then, use 100 ℃ heating plate to carry out 120 seconds heat treated (prebake) so that the dry film thickness of this coated film is 0.9 μ m.
Then, use i line stepping exposure device FPA-3000i5+ (Canon (strain) system) under the 365nm wavelength, pattern to be passed through the tetragonal Island pattern mask of 2 μ m at 100-1600mJ/cm 2Various exposures under expose.
Then, the silicon substrate that will be formed with the coated film after illuminated is positioned in rotation shower visualizer (DW-30 type, Chemitronics Co., the Ltd system) on the horizontal rotating table, use CD-2000 (Fujifilm Electronic Materials Co.Ltd. system) under 23 ℃, to carry out stirring in 60 seconds and develop, on the silicon chip substrate, form colored pattern.
The silicon substrate that has formed colored pattern is fixed on the above-mentioned horizontal rotating table in the vacuum cup mode, by whirligig these silica-based edges of boards are rotated with rotating speed 50r.p.m., the limit is supplied with pure water by spray nozzle with the shower shape from the top of its rotation center and is carried out the rinsing processing, carries out spray drying then.Afterwards, use and survey long SEM " S-9260A " (Hitachi High-Technologies Co.Ltd. system), measure the size of colored pattern.The exposure that is 2 μ m to pattern line-width is estimated as the exposure sensitivity.The result shows that the value of exposure sensitivity is more little, and sensitivity is high more.The result of measurement for Evaluation is shown in following table 2.
In the exposure process, observing does not have the zone (unexposed portion) of irradiates light to have or not residue, thereby estimates development.
＜development 〉
Zero:, confirm not have fully residue at unexposed portion.
△: at unexposed portion, confirm to have a little a residue, but be no problem degree on using.
*: at unexposed portion, confirm obviously to have residue.
Observe the section shape of the pattern that forms.The pattern section shape is preferably rectangle, is not preferably back taper.
Whether as the adhering evaluation of substrate, observing has the damaged generation of pattern.For these assessment items, estimate according to following standard.
＜substrate adhesiveness 〉
Zero: it is damaged not observe pattern fully.
△: it is damaged almost not observe pattern, damaged but the part is observed.
*: it is damaged obviously to observe pattern.
[embodiment 12-15]
Except the exemplary compounds (1) that will use in above-mentioned [3. the containing the preparation of the solidification compound of colorant] of embodiment 11 replaces with the compound shown in the following table 2, other carries out according to the step identical with embodiment 11 fully and obtains colored pattern, and carries out the evaluation identical with embodiment 11.The result is as shown in table 2.
[comparative example 3]
Except the exemplary compounds (1) that will use in above-mentioned [3. the containing the preparation of the solidification compound of colorant] of embodiment 11 replaces with the comparison polymerizable compound shown in the following table 2, other carries out according to the step identical with embodiment 11 fully.The result is as shown in table 2.
(embodiment 16)
The preparation of solidification compound (pigment system) of the color filter of solid-state imager purposes
1-1. the mixing dispersion treatment of pigment
At first, with double roll mill following each composition is carried out mixing dispersion treatment.
C.I. paratonere 254 22 mass parts
C.I. pigment yellow 13 98 mass parts
Resin solution (benzyl methacrylate/methacrylic acid/hydroxyethyl methylacrylate multipolymer, mol ratio: 80/10/10, Mw:10000, solvent: 1-Methoxy-2-propyl acetate 60%, resin solid component concentration: 40 mass parts 40%)
Solvent: 1-Methoxy-2-propyl acetate 20 mass parts
Spreading agent: (trade name: BY-161, BYK company) 2 mass parts
Further in the above-mentioned dispersion thing that obtains, add following compositions and carry out the diffusing processing of diel differential with sand mill.
Solvent: 1-Methoxy-2-propyl acetate (PGMEA) 200 mass parts
1-2. the preparation of solidification compound (coating liquid)
In the pigment of above-mentioned dispersion treatment, further add following compositions, mix, thus preparation solidification compound solution.
Above-mentioned exemplary compounds (1) [(A) specific aggregation compound] 12 mass parts
4-benzo tetrahydrofuran-2,6-two (trichloromethyl)-s-triazine [(B) Photoepolymerizationinitiater initiater] 0.5 mass parts
Surfactant (trade name: TETRONIC 150R1, BASF AG) 0.2 mass parts
Solvent: PGMEA 100 mass parts
Use this coating liquid, with the embodiment 11 of the solidification compound of above-mentioned " color filter of solid-state imager purposes with the preparation of solidification compound (pigment system) " apply, expose, development and performance evaluation.The result is summarized in the table 2.
[comparative example 4]
Except the exemplary compounds (1) that will use in above-mentioned [preparation of 1-2. solidification compound (coating liquid)] of embodiment 16 changed over shown in following table 2 like that, other carried out according to the step identical with embodiment 16 fully.The result is summarized in the table 2.
[table 2]
(A) specific aggregation compound or comparison polymerizable compound Supporter Storage stability Exposure sensitivity (mJ/cm 2) Development The substrate adhesiveness The pattern section shape
Embodiment 12 Exemplary compounds (1) Silicon substrate ○ 800 ○ ○ Rectangle
Embodiment 13 Exemplary compounds (15) Silicon substrate ○ 550 ○ △ Rectangle
Embodiment 14 Exemplary compounds (18) Silicon substrate ○ 600 ○ ○ Rectangle
Embodiment 15 Exemplary compounds (21) Silicon substrate ○ 850 ○ ○ Rectangle
Embodiment 16 Exemplary compounds (1) Silicon substrate ○ 750 △ ○ Rectangle
Comparative example 3 Pentaerythritol tetracrylate Silicon substrate △ 1400 × △ Back taper
Comparative example 4 Six acrylic acid dipentaerythritol ester Silicon substrate △ 1200 △ △ Rectangle
As can be known from the results of Table 2, even the cured composition for color of embodiment that has used solidification compound of the present invention is when using dyestuff as colorant, also identical as the situation of colorant with use pigment, storage stability is also excellent under its solution state.
In addition we know, when forming image on supporter, with respect to only having used the relatively comparative example of polymerizable compound of the outer polyfunctional acrylic ester system of the scope of the invention, any one in development, substrate adhesiveness, the pattern section shape is also all excellent.In addition, by these results as can be known, by two key density and substrate adhesiveness near the raising substrate, the erosion that is produced by developer solution is inhibited, and the result has improved the exposure sensitivity.

Claims (10)

1. a solidification compound is characterized in that, contains: (A) have ethylenical unsaturated double bonds and to the free-radical polymerised compound of the adhesiveness group of hard material and (B) Photoepolymerizationinitiater initiater in molecule.
2. solidification compound according to claim 1, it is characterized in that described (A) has ethylenical unsaturated double bonds and in the free-radical polymerised compound of the adhesiveness group of hard material the adhesiveness group of hard material being the ester group that is selected from acidic group, acid, hydrochlorate, acid metal salt, generating among substituting group, base, phenolic hydroxyl, zwitter-ion group and the chelating group of silanol group more than one by hydrolysis in molecule.
3. solidification compound according to claim 1, it is characterized in that, described hard material is glass substrate or silicon substrate, and described (A) has ethylenical unsaturated double bonds and be the substituting group that generates silanol group by hydrolysis to the adhesiveness group to hard material in the free-radical polymerised compound of the adhesiveness group of hard material in molecule.
4. solidification compound according to claim 1 is characterized in that, described (A) has ethylenical unsaturated double bonds and the free-radical polymerised compound of the adhesiveness group of hard material is had a plurality of ethylenical unsaturated double bonds in molecule in molecule.
5. solidification compound according to claim 2 is characterized in that, described (A) has ethylenical unsaturated double bonds and the free-radical polymerised compound of the adhesiveness group of hard material is had a plurality of ethylenical unsaturated double bonds in molecule in molecule.
6. solidification compound according to claim 3 is characterized in that, described (A) has ethylenical unsaturated double bonds and the free-radical polymerised compound of the adhesiveness group of hard material is had a plurality of ethylenical unsaturated double bonds in molecule in molecule.
7. solidification compound according to claim 4 is characterized in that, described (A) has ethylenical unsaturated double bonds and the free-radical polymerised compound of the adhesiveness group of hard material is had acryloyl group in molecule in molecule.
8. according to any one described solidification compound of claim 1-4, it is characterized in that, also contain (C) has absorption maximum in the visible wavelength region of 400-700nm colorant.
9. color filter is characterized in that, has the colored pattern that uses the solidification compound described in the claim 8 to form on supporter.
10. manufacturing method of color filter is characterized in that, comprises following operation: the solidification compound of coating described in the claim 8 on supporter and form the operation of cured composition for color layer; By the operation of mask with described solidification compound layer exposure; Develop and the operation of formation colored pattern with the described solidification compound layer after will exposing.
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Family Cites Families (16)

* Cited by examiner, † Cited by third party
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JP2874091B2 (en) * 1995-07-27 1999-03-24 株式会社アイテス Colored photosensitive composition and color filter
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JP4276923B2 (en) * 2003-02-27 2009-06-10 富士フイルム株式会社 Photocurable colored resin composition and color filter using the same
CN100587596C (en) * 2003-03-27 2010-02-03 户田工业株式会社 Transparent coloured composition and colour filter
JP4830310B2 (en) * 2004-02-23 2011-12-07 三菱化学株式会社 Oxime ester-based compound, photopolymerizable composition, and color filter using the same
JP4572664B2 (en) * 2004-05-28 2010-11-04 三菱化学株式会社 Photosensitive composition for liquid crystal split alignment protrusion and liquid crystal display device
JP4720318B2 (en) * 2004-06-28 2011-07-13 住友化学株式会社 Colored photosensitive resin composition
JP5140903B2 (en) * 2004-07-02 2013-02-13 三菱化学株式会社 Colored resin composition, color filter, and liquid crystal display device
JP4526964B2 (en) * 2005-01-27 2010-08-18 旭化成イーマテリアルズ株式会社 Photopolymerizable resin laminate, glass substrate with black matrix using the same, and method for producing color filter
JP4821206B2 (en) * 2005-07-29 2011-11-24 東レ株式会社 Photosensitive coloring composition for color filter and color filter
JP2007279668A (en) * 2006-03-14 2007-10-25 Asahi Kasei Electronics Co Ltd Black matrix and method for producing the same

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