CN103254178A - Triazine compound, pigment dispersing aid, pigment dispersion and resist composition - Google Patents

Triazine compound, pigment dispersing aid, pigment dispersion and resist composition Download PDF

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Publication number
CN103254178A
CN103254178A CN2013100546016A CN201310054601A CN103254178A CN 103254178 A CN103254178 A CN 103254178A CN 2013100546016 A CN2013100546016 A CN 2013100546016A CN 201310054601 A CN201310054601 A CN 201310054601A CN 103254178 A CN103254178 A CN 103254178A
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pigment
group
pigment dispersion
triaizine compounds
carbonatoms
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CN103254178B (en
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藤原岳
藤井祐介
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Sanyo Color Works Ltd
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Sanyo Color Works Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/42—One nitrogen atom
    • C07D251/44—One nitrogen atom with halogen atoms attached to the two other ring carbon atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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Abstract

The invention provides a triazine compound used for a pigment dispersing aid, a pigment dispersing aid, a pigment dispersion containing the pigment dispersing aid, and a resist composition that contains the pigment dispersion and is used for forming a color filter which can display color with high brightness. The triazine compound having a particular chemical structure is adopted to serve as the pigment dispersing aid to allow the pigment dispersion to be formed, the pigment dispersion as raw material is utilized to prepare the resist composition, and then the resist composition is utilized to prepare the color filter.

Description

Triaizine compounds, pigment dispersion aids, pigment dispersion and resist composition
Technical field
The present invention relates to a kind of triaizine compounds, pigment dispersion aids, pigment dispersion and resist composition.More specifically, the present invention relates to a kind of novel triaizine compounds that is used as the dispersing of pigments auxiliary agent and uses thereof.
Background technology
Colour filter as one of component parts of colour liquid crystal display device is to be formed with black matrix" (black matrix) and RGB(red, green, blue at glass baseplate surface) the parts of various patterns of 3 primary colors, be used for painted to the shown image of colour liquid crystal display device.The shades of colour pattern of RGB is the resist composition that contains pigment, photoresist, photopolymerization monomer, Photoepolymerizationinitiater initiater, solvent etc. by use, utilizes photolithography to form.
Has strong coherency owing to be used for the pigment of resist composition, so in the media such as solution of water, solvent and resin, be difficult to keep the uniform dispersion state of pigment.Therefore, from keeping the viewpoint of dispersing of pigments, the resist composition does not have sufficient storage stability sometimes.In addition, in pigment when cohesion,, the viscosity of resist composition rises, and thus, not only the resist composition reduces to the coating of glass substrate, and the performance of the colour filter of the shades of colour pattern that is formed by the resist composition also reduces.
In addition, save electric power in order to make colour liquid crystal display device, require to have the higher colour filter of brightness.Generally speaking, colour filter has the thin colour filter brightness trend of rising of thickness.At this moment, in order to ensure the color reproduction of height, need to realize high pigment concentration.But the high densityization of pigment further reduces the storage stability of resist composition and coating, therefore, is difficult to make the colour filter with enough performances.
On the other hand, disperse in medium in order to make pigment, generally use pigment dispersing agent and dispersing auxiliary.Dispersing auxiliary has the effect of regulating pigment and the auxiliary colo(u)rant dispersion of pigment dispersing agent.As dispersing auxiliary, from the good aspect of the adsorption efficiency of surface of pigments is considered, use mostly to have the pigment derivative of the female skeleton identical with pigment.Though pigment derivative has the female skeleton identical with pigment, since different with pigment as the structure of molecule integral body, therefore present and the pigment distinct colors.Therefore, use contains under the situation of pigment dispersion as dispersing auxiliary of pigment derivative, and the transmitted spectrum of colour filter is compared with the transmitted spectrum of the colour filter that only uses pigment, and the former transmitted spectrum of colour filter is wideer, its result, the brightness of the image that colour liquid crystal display device is shown reduces.
At present, having proposed with triazine ring is pigment dispersing agent and the dispersing auxiliary (with reference to patent documentation 1 and patent documentation 2) of female skeleton.In patent documentation 1, record for example pigment dispersing agent shown in the following formula I.In addition, in patent documentation 2, represented for example dispersing auxiliary shown in the following formula II.But from taking into account the viewpoint that improves the dispersiveness of pigment various media and suppress the brightness reduction of the shown image of colour liquid crystal display device, also there is the leeway of further improvement in these compounds.
Figure BDA00002844696500021
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-214515 communique
Patent documentation 2: TOHKEMY 2011-032374 communique
Summary of the invention
Invent problem to be solved
The objective of the invention is to, provide a kind of can as the triaizine compounds of dispersing of pigments auxiliary agent, contain this triaizine compounds pigment dispersion aids, contain the pigment dispersion of this pigment dispersion aids and contain this pigment dispersion and can form the resist composition of colour filter that can the high brightness colour developing.
Be used for solving the method for problem
The present inventor etc. further investigate repeatedly in order to solve above-mentioned problem, found that by using in the visible region and (almost do not observe absorptions in 400～700mm), present white pigment dispersion aids, can suppress the reduction of the brightness that the influence of transmitted spectrum caused owing to pigment dispersion aids.Based on this opinion, the present inventor etc. are research repeatedly further, and the result has successfully obtained having desired characteristic, can be used as the novel triaizine compounds of pigment dispersion aids, thereby has finished the present invention.
That is, the invention provides the triaizine compounds shown in a kind of following general formula (1) (below, as " triaizine compounds (1) ").
Figure BDA00002844696500031
[in the formula (1), R 1The expression group:
Figure BDA00002844696500032
Group:
Figure BDA00002844696500033
Or group:
Figure BDA00002844696500034
R 2The expression group:
Figure BDA00002844696500035
Group:
Figure BDA00002844696500036
Group:
Figure BDA00002844696500037
, hydroxyl or halogen atom.R 3, R 4And R 5Identical or different, alkyl or the alkoxyl group of carbonatoms 1～4, the perhaps R of expression hydrogen atom, carbonatoms 1～4 3And R 4Or R 4And R 5The formation phenyl ring mutually combines.R 6Expression hydrogen atom, the alkyl of carbonatoms 1～4 or the alkoxyl group of carbonatoms 1～4.R 7The alkoxyl group of expression hydrogen atom or carbonatoms 1～4.L is the average importing number of the sulfo group in triaizine compounds (1) 1 molecule, the number of expression 1～2.M and n represent 1～2 integer respectively.]
In above-mentioned general formula (1), sulfo group (SO 3H) and symbol R 6Shown group can replace at the phenyl ring that directly is incorporated into nitrogen-atoms respectively, in addition, and can be at R 3And R 4Or R 4And R 5Mutually combining replaces on the phenyl ring that forms, and can also replace at both phenyl ring.
In above-mentioned triaizine compounds (1), the triaizine compounds shown in the preferred following general formula (2) (below, as " triaizine compounds (2) ").
Figure BDA00002844696500041
[in the formula (2), R 3, R 4And R 5Identical or different, alkyl or the alkoxyl group of carbonatoms 1～4, the perhaps R of expression hydrogen atom, carbonatoms 1～4 3And R 4Or R 4And R 5The formation phenyl ring mutually combines.R 10And R 11Identical or different, the expression group:
Figure BDA00002844696500042
Group: Or group:
Figure BDA00002844696500044
R 7The alkoxyl group of expression hydrogen atom or carbonatoms 1～4.L is the average importing number of the sulfo group in triaizine compounds (2) 1 molecules, the number of expression 1～2.N represents 1～2 integer.]
In above-mentioned triaizine compounds (2), more preferably R 10And R 11Identical or different, the expression group:
Figure BDA00002844696500045
Or group: , R 7The alkoxyl group of expression hydrogen atom or carbonatoms 1～4, n represents 1～2 integer.
And, in above-mentioned triaizine compounds (2), be more preferably R 10And R 11Compound for identical group.
In above-mentioned general formula (2), sulfo group (SO 3H) can replace at the phenyl ring that directly is incorporated into nitrogen-atoms, in addition, also can be at R 3And R 4Or R 4And R 5Mutually combining replaces on the phenyl ring that forms, and can also replace at both phenyl ring.
In addition, in above-mentioned triaizine compounds (1), the triaizine compounds shown in the preferred following general formula (3) (below, as " triaizine compounds (3) ").
Figure BDA00002844696500047
[in the formula (3), R 3, R 4And R 5Identical or different, alkyl or the alkoxyl group of carbonatoms 1～4, the perhaps R of expression hydrogen atom, carbonatoms 1～4 3And R 4Or R 4And R 5The formation phenyl ring mutually combines.R 6Expression hydrogen atom, the alkyl of carbonatoms 1～4 or the alkoxyl group of carbonatoms 1～4.L is the average importing number of the sulfo group in triaizine compounds (3) 1 molecules, the number of expression 1～2.M represents 1～2 integer.X represents hydroxyl, halogen atom or group:
Figure BDA00002844696500051
R 10The expression group:
Figure BDA00002844696500052
Group:
Figure BDA00002844696500053
Or group:
Figure BDA00002844696500054
R 7The alkoxyl group of expression hydrogen atom or carbonatoms 1～4.N represents 1～2 integer.]
In above-mentioned triaizine compounds (3), preferred R 10Triaizine compounds as following radicals.
Group:
Figure BDA00002844696500055
In above-mentioned general formula (3), sulfo group (SO 3H) and symbol R 6Shown group can replace at the phenyl ring that directly is incorporated into nitrogen-atoms respectively, in addition, and can be at R 3And R 4Or R 4And R 5Mutually combining replaces on the phenyl ring that forms, and can also replace at both phenyl ring.
In addition, the invention provides a kind of pigment dispersion aids, it contains above-mentioned triaizine compounds (1).
In addition, the invention provides a kind of pigment dispersion, it contains pigment, pigment dispersing agent, above-mentioned pigment dispersion aids and solvent.In this pigment dispersion, the volume average particle size of preferred pigments is 10～100nm.In addition, in this pigment dispersion, the content of preferred pigments is 30～80 weight % that the total solids of pigment dispersion becomes component, and with respect to pigment 100 weight parts, contains pigment dispersing agent 10～60 weight parts, contains pigment dispersion aids 1～25 weight part.
And, the invention provides a kind of resist composition, it contains above-mentioned pigment dispersion and photosensitive compounds.
The effect of invention
According to the present invention, provide a kind of and can be suitable as the triaizine compounds (1) that the dispersing of pigments auxiliary agent uses.Contain the pigment dispersion aids of this triaizine compounds (1) by use, can access and pigment is scattered in the various media equably and the pigment dispersion that forms.In addition, contain the resist composition that uses the pigment dispersion that this triaizine compounds (1) obtains can be suitable for making can the high brightness colour developing colour filter.Use the colour filter that resist composition of the present invention makes can be to the RGB(red, green, blue) 3 primary colors carry out the colour developing of high brightness, particularly under the situation of the colour developing of green, brightness raises significantly, so preferred.
Embodiment
[triaizine compounds (1)]
Triaizine compounds of the present invention (1) can be used as the dispersing of pigments auxiliary agent.That is, triaizine compounds of the present invention (1) can act synergistically with pigment dispersing agent, and pigment is disperseed in various media equably.Therefore, owing to contain the pigment dispersion of triaizine compounds of the present invention (1) and the rising that the resist composition suppresses condensing again of pigment and viscosity, so have good storage stability.Wherein, under the situation of resin type dispersion agent and usefulness, make the effect of dispersing of pigments raising and the particular significant effect of cohesion again of inhibition pigment in triaizine compounds of the present invention (1) and the pigment dispersing agent.
And, because triaizine compounds of the present invention (1) presents white in the visible region, so can utilize the colour filter that is formed by the resist composition that contains triaizine compounds of the present invention (1), making can be carried out the colour liquid crystal display device of the colour developing of high brightness.
In above-mentioned general formula (1)～(3), as the alkyl of carbonatoms 1～4, can enumerate: the alkyl of the carbonatoms 1～4 of straight chain shape such as methyl, ethyl, n-propyl, sec.-propyl, Zhong Bingji, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl or a chain.As the alkoxyl group of carbonatoms 1～4, can enumerate: the alkoxyl group of the carbonatoms 1～4 of straight chain shape such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, secondary propoxy-, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy or a chain.As halogen atom, can enumerate: chlorine, bromine, iodine, fluorine etc.
In triaizine compounds of the present invention (1), be more preferably triaizine compounds (2) and triaizine compounds (3).
With regard to triaizine compounds (2), use its initial viscosity of pigment dispersion lower, and suppress the effect height of cohesion again of pigment, therefore, the pigment dispersion storage stability excellence that contains triaizine compounds (2), the rising of the viscosity that is caused by storage is fewer.In addition, the resist composition that contains triaizine compounds (2) by use is made colour filter, can realize high brightnessization in the shown image of colour liquid crystal display device.Among triaizine compounds (2), during the thickening efficiency when considering the storage of the initial viscosity of pigment dispersion and pigment dispersion etc., more preferably R 10And R 11Identical or different, for:
Group: Or group:
Figure BDA00002844696500072
[in the formula, R 7Same as described above with n.]
Triaizine compounds, be more preferably R 10And R 11Triaizine compounds for identical group.Wherein, in triaizine compounds (2), preferred especially R 3, R 4And R 5It all is hydrogen atom.As the concrete example of this triaizine compounds (2), can enumerate the triaizine compounds shown in for example following table 1 (2a)～(2c).
[table 1]
Figure BDA00002844696500073
Triaizine compounds (3) is though the initial viscosity when using it to make pigment dispersion and the thickening efficiency when preserving pigment dispersion are compared high a little with triaizine compounds (2), but all in can the actual scope of using, and, can help the high brightnessization of the shown image of colour liquid crystal display device.Among triaizine compounds (3), when the thickening property when considering the storage of the initial viscosity of pigment dispersion and pigment dispersion, the high brightnessization of image etc., preferred R 10Be group:
Figure BDA00002844696500081
Compound.Wherein, in triaizine compounds (3), preferred R 3, R 4And R 5It all is hydrogen atom.As the concrete example of this triaizine compounds (3), can enumerate the triaizine compounds shown in for example following table 2 (3a)～(3d) etc.
[table 2]
Triaizine compounds of the present invention (1) can be by making for example reaction of the sulfoacid compound (10) shown in the trichlorine melamine (Cyanuric chloride) and following general formula (10), and in compound (11)～(13) shown in following general formula (11)～(13) at least a kind is obtained with resulting reactant reaction.
Figure BDA00002844696500083
[in the formula (10), R 3～R 6, l and m be same as described above.]
Concrete example as sulfoacid compound (10), for example can enumerate: ORTHO AMINO PHENOL SULPHONIC (2-aniline sulfonic acid), Sulphanilic Acid, para-totuidine-2-sulfonic acid, m-sulfanilic acid, P-nethoxyaniline-2-sulfonic acid, aniline-2,4-disulfonic acid, 2,4-xylidine-6-sulfonic acid etc.Sulfoacid compound (10) is generally 0.5～1.5 mole with respect to the usage quantity of 1 mole of trichlorine melamine, is preferably 0.9～1.1 mole.
The reaction of trichlorine melamine and sulfoacid compound (10) for example in appropriate solvent, under agitation or do not have under the stirring, under the temperature about 5～30 ℃, carry out, about 1～2 hour, finish.As solvent, can use organic solvents such as water for example or acetone, diox, dimethylbenzene, dimethyl formamide, their mixed solvent more than 2 kinds etc.
Make in compound (11)～(13) shown in following general formula (11)～(13) at least a kind with the above-mentioned reactant reaction that obtains like that.
Figure BDA00002844696500091
[in formula (11)～(13), R 7Same as described above with n.]
As the concrete example of compound (11), can enumerate 5-amino-2-Benzimidazolinone.As the concrete example of compound (12), for example can enumerate: 4-aminobenzamide, 3-amino-4-methoxy benzamide etc.Compound (11)～(13) are suitably selected according to the kind of the compound that uses with respect to the usage quantity of 1 mole of the reactant of trichlorine melamine and sulfoacid compound (10), are generally 0.5～2.5 mole, are preferably 0.9～2.2 mole.In the reaction of above-mentioned reactant and compound (11)～(13), also can be with mineral acids such as organic acid such as acetic acid, phenylformic acid, citric acid, fumaric acid, glyconic acid, oxalic acid or hydrochloric acid, sulfuric acid, nitric acid as solvent.Preferably use these acid with the form of the aqueous solution.
Above-mentioned reactant and compound (11)～(13) be reflected in the appropriate solvent, under agitation or do not have and stir down, carry out under about 50～100 ℃ the temperature, about 1～5 hour, finish.As solvent, can use and the solvent phase that in the reaction of trichlorine melamine and sulfoacid compound (10), uses solvent together.Generate triaizine compounds (1) thus.Resulting triaizine compounds (1) can for example utilize and filter, wash, dry so common separation and refining method is easily refining from reaction mixture.
[pigment dispersion aids]
Pigment dispersion aids of the present invention contain be selected from the triaizine compounds (1) more than a kind or 2 kinds, for example can think with the coexistence of pigment under or with the coexistence of pigment and pigment dispersing agent under, have the effect that pigment is improved to the dispersiveness of solvent, and the viscosity that makes dispersing of pigments and storage stability in the pigment dispersion improve, suppress pigment dispersion is followed the effect that the cohesion again of the pigment in the storage etc. rises etc. etc.
Pigment as using pigment dispersion aids of the present invention is not particularly limited, preferred pigment dyestuff.As the concrete example of pigment dyestuff, can enumerate for example: perylene pigments, purple cyclic ketones (perinone) series pigments, quinacridone pigment, the quinacridone quinone pigment, anthraquione pigmentss, embedding dianthrone series pigments, the benzimidazolone series pigments, two diazonium series pigments, azo pigment, indanthrene (Indanthrone) series pigments, phthualocyanine pigment, triaryl carbon series pigments dioxazine series pigments, the aminoanthraquinone series pigments, the diketopyrrolo-pyrrole series pigments, indigo series pigments, the thioindigo series pigments, isoindolinone pigment, the isoindoline series pigments, the pyranthrone series pigments, the iso-violanthrone series pigments, metal complex pigment, quinophthalone series pigments etc.Wherein, You Xuan perylene pigments, purple cyclic ketones series pigments, quinacridone pigment, anthraquione pigmentss, azo pigment, phthualocyanine pigment, dioxazine series pigments, diketopyrrolo-pyrrole series pigments, indigo series pigments, isoindolinone pigment, isoindoline series pigments, metal complex pigment, quinophthalone series pigments etc.
In addition, the pigment dispersing agent as together using with pigment dispersion aids of the present invention is not particularly limited, and for example can enumerate: resin type dispersion agent, surfactant type dispersion agent etc.Among these, from bringing into play the viewpoint that colo(u)rant dispersion effect, pigment that pigment dispersion aids of the present invention brings condense inhibition etc. again, preferred resin type dispersion agent fully.
As the resin type dispersion agent, be not particularly limited, for example can enumerate: oleoresin type dispersion agents such as urethane, polyester, unsaturated polyester acid amides, phosphoric acid ester, poly carboxylic acid and amine salt thereof, ammonium salt, alkylamine salt, polycarboxylate, hydroxyl polycarboxylate, polysiloxane, modified polyacrylate; The marine alga acids, polyvinyl alcohol, hydroxypropylcellulose, carboxymethyl cellulose, Natvosol, methylcellulose gum, Polyvinylpyrolidone (PVP), water-soluble high-molecular compounds such as arab resin, the styrene-propene acid resin, vinylbenzene-methacrylic resin, styrene-propene acid-acrylate resin, the styrene-maleic acid resin, styrene-maleic acid ester resin, methacrylic acid-methacrylate resin, vinylformic acid-acrylate resin, iso-butylene-maleic acid resin, vinyl-ester resin, Abietyl modified maleic acid resins etc. contain the two key resins of ethene, PAH, polyvinylamine, amine such as polymine are water-base resin type dispersion agents such as resin etc.
The resin type dispersion agent is commercially available various commercially available products, concrete example as commercially available product, for example can enumerate: " Solsperse " 3000,9000,13240,17000,20000,24000,26000,28000,32000,32500,41000(is trade(brand)name, Japan Lubrizol(road Bo Run) corporate system), " Disperbyk-" 108,110,112,140,142,145,161,162,163,164,166,167,182,2000,2001,2050,2070,2150, " BYK LPN-" 6919,21116(is trade(brand)name, Bi Ke chemistry (PVC Star Network ケ ミ one) Japan (strain) system), " EFKA-" 4401,4403,4406,4010,4015,4046,4047,4050,4055,4060,4080,5064,5207,5244(is trade(brand)name, the EFKAAdditive corporate system), " AJISPER " PB821(F), PB822, PB880(is trade(brand)name, (the Ajinomoto Fine-Techno Co. of aginomoto fine chemistry Co., Ltd., Inc.) system), HINOACT T-8000(trade(brand)name, fine chemistry Co., Ltd. (Kawaken Fine Chemicals Co., Ltd.) system) is ground in the river, DISPARLON PW-36, " DISPARLON DA-" 325,375,7301(is trade(brand)name, nanmu originally changes into Co., Ltd.'s system) etc.
In the resin type dispersion agent, preferable weight-average molecular weight is about 1000～30000 dispersion agent.
As the surfactant type dispersion agent, be not particularly limited, for example can enumerate: anion active agents such as naphthalene sulfonic acidformaldehyde condensation product salt, aromatic sulphonic acid formaldehyde condensation products, polyxyethylated phosphoric acid ester, tweens such as Voranol EP 2001, cationic active agents such as alkylamine salt, quaternary ammonium salt etc.The surfactant type dispersion agent is also commercially available various materials, as its concrete example, for example can enumerate: " Demol " N, RN, MS, SN-B, " Emulgen " 120,430, " Acetamin " 24,86, kohtamin24P(are trade(brand)name, Kao Corp's system), " Plysurf " AL, A208F(be trade(brand)name, Di-ichi Kogyo Seiyaku Co., Ltd.'s system), " Arquad " C-50, T-28, T-50(be trade(brand)name, LION Co., Ltd. system) etc.
Pigment dispersing agent can use a kind separately, perhaps can be used in combination more than 2 kinds.
The usage quantity of pigment dispersion aids is not particularly limited, and with respect to pigment 100 weight parts, is preferably 1～25 weight part, more preferably 3～20 weight parts.When the content of pigment dispersion aids was lower than 1 weight part, existence can not be brought into play the trend of the effect of pigment dispersion aids fully.When the content of pigment dispersion aids surpasses 25 weight parts, the rising increase, resist composition that has the viscosity of pigment dispersion described later operability in the preparation and the trend that the coating of resist composition reduces when making colour filter.
Pigment dispersion aids of the present invention can and be selected from also using more than a kind or 2 kinds in the pigment dispersion aids such as having known pigment derivative now in the scope of not damaging its effect.
[pigment dispersion]
Pigment dispersion of the present invention contains pigment, pigment dispersing agent, above-mentioned pigment dispersion aids and solvent.Pigment dispersion of the present invention not only can be used the raw material of composition as resist, but also can be used as various printing ink (ink) and ink raw materials.
As pigment, be not particularly limited, can all use illustrative pigment in the explanation of above-mentioned pigment dispersion aids, preferred pigment is also identical.More specifically, for example can enumerate: C.I. Pigment red 254, C.I. Pigment red 177, C.I. pigment orange 36, C.I. Pigment green 58, C.I. pigment green 36, C.I. pigment Green 7, C.I. Pigment Yellow 73 150, C.I. pigment yellow 13 9, C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 185, C.I. pigment Blue 15: 6, C.I. pigment Violet 23, C.I. pigment orange 38, C.I. pigment orange 43, C.I. pigment orange 71 etc.Pigment can use a kind separately, or is used in combination more than 2 kinds.
The volume average particle size of pigment is not particularly limited, and is preferably 10～100nm, more preferably 20～50nm.When the volume average particle size of pigment was lower than 10nm, the coherency of pigment was strong excessively, even use triaizine compounds (1), also had the trend that can not obtain the pigment dispersion that pigment disperses equably.On the other hand, when the volume average particle size of pigment surpassed 100nm, the storage stability of pigment dispersion reduced, and also had the incidental trend of cohesion of pigment in the presence of triaizine compounds (1).
The volume average particle size of pigment can pass through to use Multisizer3(trade(brand)name, Beckman Ku Erte (Beckman coulter) corporate system), be full of the ISOTON2(trade(brand)name, measuring with electrolytic solution, Beckman Coulter Inc. system) beaker in, stir lentamente on one side on one side with the pigment of dropper dropping as sample, after the reading of the densitometer of Multisizer3 is adjusted to about 10%, use the aperture (Aperture) of 400 μ m to measure.
The content of the pigment in the pigment dispersion is not particularly limited, and the total solids that is preferably pigment dispersion becomes 30～80 weight % of component, more preferably 40～70 weight %.Like this, when fully improving the content of pigment, can improve the colour developing concentration of for example using colour filter that pigment dispersion makes etc. to film.In addition, the volatile quantity of the solvent when filming can be suppressed to form, therefore, the load for environment can be alleviated.
As pigment dispersing agent, be not particularly limited, can all use illustrative resin type dispersion agent and surfactant type dispersion agent in the explanation of above-mentioned pigment dispersion aids.Wherein, from the viewpoint that the colo(u)rant dispersion effect of bringing into play pigment dispersion aids of the present invention fully and pigment condense inhibition etc. again, preferred resin type dispersion agent.
The content of the pigment dispersing agent in the pigment dispersion is not particularly limited, and with respect to pigment 100 weight parts, is preferably 10～60 weight parts, more preferably 20～50 weight parts.When the content of pigment dispersing agent was lower than 10 weight parts, existence can not be brought into play the trend of the effect of pigment dispersing agent fully.On the other hand, when the content of pigment dispersing agent surpasses 60 weight parts, the viscosity of pigment dispersion is risen, have the trend that makes the property handled (suitability) variation.
As dispersing auxiliary, can use the pigment dispersion aids of the invention described above.Pigment dispersion aids of the present invention can not make the viscosity of pigment dispersion significantly rise, and keeps the uniform dispersion of pigment.And, can be in the scope of the effect of the excellence of not damaging pigment dispersion aids of the present invention, with the common various dispersing auxiliaries such as present known pigment derivative that use of pigment dispersion aids of the present invention.
The content of the pigment dispersion aids in the pigment dispersion is not particularly limited, and with respect to pigment 100 weight parts, is preferably 1～25 weight part, more preferably 3～20 weight parts.When the content of pigment dispersion aids was lower than 1 weight part, existence can not be brought into play the trend of the effect of pigment dispersion aids fully.When the content of pigment dispersion aids surpasses 25 weight parts, the rising increase, resist composition that has the viscosity of pigment dispersion operability and the trend that reduces of the coating of the resist composition of colour filter when making in the preparation.
As solvent, be not particularly limited, can use in aqueous solvent and the non-aqueous solvent any.As aqueous solvent, can enumerate usually high functional group such as the wetting ability that has hydroxyl compound, have the compound of polyethylene glycol backbone etc.As non-aqueous solvent, for example can enumerate: ester series solvent, ether series solvent, ketone series solvent etc.As the concrete example of solvent, for example can enumerate: methoxy propyl yl acetate, propylene glycol methyl ether acetate (PMA), propylene glycol monomethyl ether (PM), ethylene glycol butyl ether, water etc.Solvent can use a kind separately, or is used in combination more than 2 kinds.
Pigment dispersion of the present invention can contain the additive of present known colo(u)rant dispersion body and function as required.As such additive, for example can enumerate: pH regulator agent, antioxidant, UV light absorber, sanitas, mould inhibitor etc.
Pigment dispersion of the present invention can be for example by making above-mentioned pigment, pigment dispersing agent, dispersing auxiliary, solvent and additive as required disperse to obtain with known dispersion machines such as ball mill, sand mills.The viewpoint of the inhibition of rising from the keeping of dispersing of pigments, dispersing of pigments, viscosity, the solid component concentration that pigment dispersion of the present invention preferably lumps together pigment, pigment dispersing agent and pigment dispersion aids is adjusted into the scope of 15～30 weight % of pigment dispersion total amount.
[manufacturing of miniaturization pigment]
With regard to triaizine compounds (1), by in the presence of it, carrying out the miniaturization of pigment, can form finer granules of pigments.Particularly, for example, utilize lyonium salt mill (ソ Le ベ Application ト ソ Le ト ト リ ミ Application グ, solvent salt trimming) when pigment is carried out miniaturization, with pigment, solvent, grind agent etc., triaizine compounds (1) is dropped in the mixing roll.Operation is in addition only similarly carried out with common mixing operation, just can access with the situation of not adding triaizine compounds (1) and compare finer granules of pigments.
The method of this moment just is not particularly limited so long as make pigment and the method for triaizine compounds (1) coexistence, in addition, can also use other additives such as resin, pigment derivative.
[resist composition]
Resist composition of the present invention contains above-mentioned pigment dispersion and photosensitive compounds.Photosensitive compounds is for being used for photolithographic organic compound.As photosensitive compounds, can all use to can be used in photolithographic photosensitive compounds, the photosensitive compounds of optimal way can contain photoresist, Photoepolymerizationinitiater initiater, photopolymerization monomer and/or optical polymerism prepolymer (dipolymer, trimer and oligopolymer) etc.
As pigment dispersion, use the pigment dispersion of the invention described above.The content of the pigment dispersion in the resist composition is not particularly limited, viewpoints such as development from the colour filter that finally obtains, become the part by weight of component as pigment with respect to the total solids of resist composition, preferably be made as 5～70 weight %, more preferably be made as 15～60 weight %.When the part by weight of pigment is lower than 5 weight %, there is the trend be difficult to make the colour filter that can help to show the image with desired lightness, brightness and contrast.When the part by weight of pigment surpasses 70 weight %, the trend that the characteristic of the reduction of existence generation pigment-dispersing and viscosity rising, the coating when colour filter is made and the colour filter of resist composition reduces.
As photoresist, so long as can be used in photolithographic resin, just be not particularly limited, for example can enumerate: ethene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, the ethylene-vinyl multipolymer, polystyrene, acrylonitritrile-styrene resin, ABS resin, polymethacrylate resin, the ethylene methacrylic acid resin, polyvinyl chloride, chlorinated vinyl chloride, polyvinyl alcohol, cellulose acetate propionate, cellulose acetate butyrate, polymeric amide (nylon 6, nylon 66, nylon 12 etc.), polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl acetal, polyether-ether-ketone, polyethersulfone, polyphenylene sulfide, polyarylester, polyvinyl butyral acetal, Resins, epoxy, phenoxy resin, polyimide, polyamidoimide, polyetherimide, resol, urea-formaldehyde resin etc.
In addition, as photoresist, can use the monomer that contains the ethene unsaturated double-bond (below be made as " vinyl monomer ") and carboxylic acid is the multipolymer of monomer.As vinyl monomer, for example can enumerate: (methyl) alkyl acrylate, (methyl) vinylformic acid benzyl ester, (methyl) glycidyl acrylate, vinylbenzene, alpha-methyl styrene, N-vinyl-2-Pyrrolidone etc.In (methyl) alkyl acrylate, moieties is the straight chain shape of carbonatomss 1～10 such as methyl, ethyl, n-propyl, sec.-propyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, positive decyl, 2-hydroxyethyl or the alkyl of a chain.Vinyl monomer can use a kind or be used in combination more than 2 kinds separately.Be monomer as carboxylic acid, can enumerate: the acid anhydrides of vinylformic acid, methacrylic acid, acrylic acid dipolymer, methylene-succinic acid, Ba Dousuan, toxilic acid, fumaric acid, vinylacetate, these materials etc.Carboxylic acid is that monomer can use a kind separately, or is used in combination more than 2 kinds.
In addition, in the present invention, can use commercially available resin as photoresist.As commercially available resin, for example can enumerate: acrylic resin (" Aronix M-" 5600,6200,7100,9050, be trade(brand)name, Toagosei Co., Ltd's system) etc.
The content of the photoresist in the resist composition is not particularly limited, and when adding photoresist in the resist composition, the total solids that is preferably the resist composition becomes 10～60 weight % of component, more preferably 15～50 weight %.When the content of photoresist is lower than 10 weight %, the film toughness that is formed at the pattern on the glass substrate is insufficient, the trend that exists long durability to reduce, on the other hand, when the content of photoresist surpasses 60 weight %, dispersing of pigments is insufficient in the resist composition, has the trend that is difficult to form the pattern with desired characteristic when making colour filter.
As Photoepolymerizationinitiater initiater; so long as produce the initiator of free radical by the irradiation of ultraviolet homenergic; just be not particularly limited; for example can enumerate: the bitter almond oil camphor ethyl isobutyl ether; benzoin iso-propylether; benzophenone; 4; two (dimethylamino) benzophenone of 4'-; 4; two (diethylamino) benzophenone of 4'-; the benzoyl phenylformic acid; the benzoyl methyl benzoate; 4-benzoyl-4'-dimethyl diphenyl sulfide; benzyl methyl ketal; the dimethylaminomethyl benzoic ether; 2-n-butoxy ethyl-4-dimethylaminobenzoic acid ester; the ESCAROL 507 isopentyl ester; 3; 3'-dimethyl-4-methoxy benzophenone; benzoyl methyl-formiate (メ チ ロ ベ Application ゾ イ Le フ ォ ー メ ー ト); 2-methyl isophthalic acid-(4-(methyl sulfo-) phenyl)-2-morpholino propane-1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone; 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone; the 1-hydroxycyclohexylphenylketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone; the 2-clopenthixal ketone; 2; the 4-diethyl thioxanthone; 2; 4-di-isopropyl thioxanthone; 2,4-dimethyl thioxanthone; isopropyl thioxanthone; 1-chloro-4-propoxy-thioxanthone etc.
In the present invention, can use commercially available Photoepolymerizationinitiater initiater, for example can enumerate: " Irgacure " 184,369,651,907(are trade(brand)name, the vapour Bart plants chemical company (Ciba Specialty Chemicals Inc.) system), DAROCUR(trade(brand)name, Merck (Merck) corporate system), ADEKA1717(trade(brand)name, (strain) ADEKA system) etc. ketone based compound, 2, two (Chloro-O-Phenyl)-4 of 2'-, 5,4', 5'-tetraphenyl-1, two imidazole compounds such as the two imidazoles (dark fund changes into Co., Ltd.'s system) of 2'-etc.Photoepolymerizationinitiater initiater can use a kind separately, or is used in combination more than 2 kinds.
The content of the Photoepolymerizationinitiater initiater in the resist composition is not particularly limited, and the total solids that is preferably the resist composition becomes 0.05～10 weight % of component, more preferably 0.5～5 weight %.When the content of Photoepolymerizationinitiater initiater was lower than 0.05 weight %, the light solidified of resist composition was insufficient, the trend that exists the operability in the production process that utilizes photolithographic colour filter to reduce.In addition, there are the development of colour filter and the trend that sensitivity reduces.When the content of Photoepolymerizationinitiater initiater surpasses 10 weight %, exist in the storage of resist composition, in the resist composition, generate condensation product or throw out, use the development of colour filter of its making and the trend that sensitivity reduces.
As photopolymerization monomer, can all use the photopolymerization monomer that uses in this field, for example can enumerate: the ester class of above-mentioned unsaturated carboxylic acid such as unsaturated carboxylic acids such as vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, iso-crotonic acid, toxilic acid, (methyl) methyl acrylate, (methyl) Hydroxyethyl Acrylate, (methyl) benzyl acrylate and derivative thereof; (methyl) acrylic amides such as (methyl) acrylamide, N-hexyl (methyl) acrylamide, vinyl (methyl) acrylamide, allyl group (methyl) acrylamide; Ethyl vinyl ether, 2-chloroethyl vinyl ether, vinyl ethers such as butyl vinyl ether; Vinyl esters such as vinyl-acetic ester, butyric acid vinyl ester, phenylformic acid vinyl ester; Vinylbenzene, vinyl toluene, to styrenics such as acetoxy-styrene; Vinyl ketones such as alkyl vinyl ketone, phenyl vinyl ketone; Olefines such as ethene, propylene, iso-butylene, divinyl, isoprene; Unsaturated acid imides such as maleinamide, N-acryl acrylamide, N-ethanoyl Methacrylamide, N-propionyl acrylamide; N-vinyl pyrrolidone, vinyl cyanide, methacrylonitrile etc.Photopolymerization monomer can use a kind separately, or is used in combination more than 2 kinds.In these photopolymerization monomers, the amides of ester, unsaturated carboxylic acid and the aliphatic polyamine compound of preferred unsaturated carboxylic acid and aliphatic polyol compound.
As the optical polymerism prepolymer, for example can enumerate: the addition reaction that (a) has the substituent unsaturated carboxylate type of nucleophilicity or amides and simple function or polyfunctional isocyanates or epoxies, (b) has the dehydration condensation thing of the substituent unsaturated carboxylate type of nucleophilicity or amides and simple function or polyfunctional carboxylic-acid, (c) have the substituent unsaturated carboxylate type of electrophilicity or amides and simple function or polyfunctional alcohols, the addition reaction of amine or thio-alcohol, (d) have the substituent unsaturated carboxylate type of detachment or amides and simple function or polyfunctional alcohols, the substituted reactant of amine or thio-alcohol etc.In above-mentioned (a)～(d), esters of unsaturated carboxylic acids is replaced into compound group that unsaturated sulfonic acid, vinylbenzene, vinyl ether etc. obtain also can be used as the optical polymerism prepolymer and use.In addition, in above-mentioned (a)～(d), as the nucleophilicity substituting group, hydroxyl, amino, sulfydryl etc. can be enumerated, as the electrophilicity substituting group, isocyanate group, epoxy group(ing) etc. can be enumerated, as the detachment substituting group, can enumerate: halogen atom, tolysulfonyl oxygen base etc.
The content of the photopolymerization monomer in the resist composition and/or optical polymerism prepolymer is not particularly limited, viewpoint from development and the sensitivity of resulting colour filter, the total solids that is preferably the resist composition becomes 5～70 weight % of component, more preferably 10～60 weight %.In many cases, for example improve for the tack that makes the film that formed by the resist composition and glass substrate and use these compounds, also can corresponding other purpose suitably select to use the material with the structure that meets its purpose.
As solvent, can be not particularly limited the solvent that uses the resist composition to use, for example can enumerate: alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, ethylene glycol, propylene glycol; Terpenes such as α-terpinol, β-terpinol etc.; Ketones such as acetone, methyl ethyl ketone, pimelinketone, N-N-methyl-2-2-pyrrolidone N-; Toluene, dimethylbenzene, tetramethyl-benzene etc. are aromatic hydrocarbon based; Cellosolve, methylcyclohexane, ethyl cellosolve, Trivalin SF, methyl carbitol, ethyl carbitol, gylcol ethers such as diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether; Acetate esters such as ethyl acetate, butylacetate, cellosolve acetic ester, ethyl cellosolve acetate, butyl cellosolve acetate, Trivalin SF acetic ester, ethyl carbitol acetic ester, acetate of butyl carbitol, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxyl group butylacetic acid ester etc.Wherein, preferred gylcol ether and acetate esters, more preferably propylene glycol methyl ether acetate and dihydroxypropane single-ether.These solvents all have commercially available.Solvent can use a kind separately, or is used in combination more than 2 kinds.
The content of the solvent in the resist composition is not particularly limited, when considering the coating of pigment-dispersing, resist composition in the resist composition, the lightness that possesses the shown image of the colour liquid crystal display device of the colour filter that finally obtains, brightness and contrast etc., total solids with respect to the resist composition becomes component 100 weight parts, be preferably 100～900 weight parts, more preferably 200～500 weight parts.When the content of solvent is lower than 100 weight parts, the trend that has viscosity rising, pigment-dispersing and the coating reduction of resist composition, when the content of solvent surpasses 900 weight parts, there is the trend that is difficult to make the colour filter that can help to show the image with desired lightness, brightness and contrast.
Resist composition of the present invention can contain the various additives that the resist composition is used as required.As this additive, for example can enumerate: sensitizing agent, chain-transfer agent, fluorine series organic compound, thermal polymerization, thermopolymerization composition, thermal polymerization inhibitor, weighting agent, tensio-active agent, adhesion promoter, antioxidant, UV light absorber, aggregation inhibitor etc.Additive can use a kind separately, or is used in combination more than 2 kinds.
Resist composition of the present invention can be by adding pigment dispersion, photosensitive compounds (for example being selected from least a kind in photoresist, Photoepolymerizationinitiater initiater, photopolymerization monomer and the optical polymerism prepolymer etc.) in solvent, add other additive as required, make each composition in the resulting mixture dissolve equably and/or disperse and obtain.The dissolving of each composition in the mixture and disperse to utilize known method to implement can be enumerated the method for for example using paint regulator (paint conditioner) etc. to vibrate.
Can use resist composition of the present invention, utilize photolithography to form the pattern of stipulating at the glass baseplate surface of regulation, make colour filter.
Embodiment
Below, enumerate synthesis example, embodiment and comparative example, the present invention is described particularly.Wherein, below, short of specified otherwise, " part " and " % " is set at weight basis.
(synthesis example 1)
[synthesizing of triaizine compounds (2a)]
In 100 parts in water, add 18.4 parts of trichlorine melamines and with 17.3 parts of the ORTHO AMINO PHENOL SULPHONIC (2-aniline sulfonic acid) of the amount of 1 chlorine atomic reaction of trichlorine melamine, make it 10 ℃ of reactions 1 hour.In the reactant that obtains, add and 29.8 parts of the 5-amino of the amount of 2 chlorine atomic reactions of this reactant-2-Benzimidazolinone, make it 85 ℃ of reactions 1 hour.The resulting reactant of leaching and wash resulting residue after, in 100 ℃ thermostatic bath, leave standstill a Dinner and make its drying, obtain 44.7 parts of triaizine compounds (2a).
With the substance assistant laser desorpted ionization of AXIMA CFR plus type-flight time type mass spectrograph ((strain) Shimadzu Seisakusho Ltd. system), be matrix with alpha-cyano-4-hydroxycinnamic acid (CHCA), measure the molion peak value of triaizine compounds (2a) with positive ion mode.Its result observes the peak at m/z=546.Triaizine compounds (2b)～(2c) and molion peak value (3a)～(3d) are obtained in operation similarly in following synthesis example 2～7.
(synthesis example 2)
[synthesizing of triaizine compounds (2b)]
Replace 29.8 parts of 5-amino-2-Benzimidazolinone, use 27.2 parts of 4-aminobenzamides, in addition, similarly operate with synthesis example 1, obtain 47.7 parts of triaizine compounds (2b).m/z＝520。
(synthesis example 3)
[synthesizing of triaizine compounds (2c)]
Replace 29.8 parts of 5-amino-2-Benzimidazolinone, use 16.6 parts of 3-amino-4-methoxy benzamide, in addition, similarly operate with synthesis example 1, obtain 32.5 parts of triaizine compounds (2c).m/z＝582。
(synthesis example 4)
[synthesizing of triaizine compounds (3a)]
In 100 parts in water, add 18.4 parts of trichlorine melamines and with 17.3 parts of the ORTHO AMINO PHENOL SULPHONIC of the amount of 1 chlorine atomic reaction of trichlorine melamine, make it 10 ℃ of reactions 1 hour.23.3 parts of 2-aminophenyl phenylsulfones and the 50% acetic acid 320g of the amount of 1 chlorine atomic reaction of adding and this reactant in the reactant that obtains make it 85 ℃ of reactions 1 hour.The resulting reactant of leaching is also washed after the resulting raffinate, leaves standstill a Dinner and make its drying in 100 ℃ thermostatic bath, obtains 16.6 parts of triaizine compounds (3a).m/z＝499。
(synthesis example 5)
[synthesizing of triaizine compounds (3b)]
The addition of 2-aminophenyl phenylsulfone is changed to 46.6 parts from 23.3 parts, in addition, similarly operate with synthesis example 4, obtain 53.9 parts of triaizine compounds (3b).m/z＝714。
(synthesis example 6)
[synthesizing of triaizine compounds (3c)]
Replace 17.3 parts of ORTHO AMINO PHENOL SULPHONIC, use 17.3 parts of Sulphanilic Acid, in addition, similarly operate with synthesis example 4, obtain 19.2 parts of triaizine compounds (3c).m/z=499。
(synthesis example 7)
[synthesizing of triaizine compounds (3d)]
Replace 17.3 parts of ORTHO AMINO PHENOL SULPHONIC, use 18.7 parts of para-totuidine-2-sulfonic acid, in addition, similarly operate with synthesis example 4, obtain 23.0 parts of triaizine compounds (3d).m/z＝513。
(embodiment 1)
In the mixing machine of inner capacities 500m1, drop into the specified amount of each composition shown in the following table 3, stirred 10 minutes with 2000rpm with dispersion machine, carry out pre-dispersed.
[table 3]
Figure BDA00002844696500201
In by the above-mentioned pre-dispersed thing that obtains, drop into the zirconium oxide bead 768g of diameter 0.5mm, stirred 2 hours with 2000rpm, lead dispersion.Add 48g PMA in the thing in main dispersion that obtains, further stirred 10 minutes with 1500rpm.The final dispersion thing that the obtains strainer (trade(brand)name: PALL HDCII Membrene Fillter, PALL corporate system) with 2.5 μ m sieve apertures is filtered, remove zirconium oxide bead, obtain red pigment dispersion.
(embodiment 2～7)
Replace triaizine compounds (2a), use the triaizine compounds (2b) that obtains in the synthesis example 2～7, (2c), (3a), (3b), (3c) or (3d), in addition, operate similarly to Example 1, obtain the red pigment dispersion of embodiment 2～7.
(reference example 1)
Replace triaizine compounds (2a), use the triaizine compounds (III) of following general formula, in addition, operation obtains red pigment dispersion similarly to Example 1.Wherein, following triaizine compounds (III) is to be the compound of chlorine atom and to be the commercially available general pigment dispersion aids of the mixture of the compound of hydroxyl as symbol Y as symbol Y, therefore, uses in contrast.
Figure BDA00002844696500211
Can access aim colour degree (embodiment 1～7 and reference example 1 to become; The mode of thickness x=0.650) applies each red pigment dispersion of embodiment 1～7 and reference example 1 with spin coater on glass substrate, in the box-shaped drying machine in 90 ℃ of heat dryings 2 minutes 30 seconds (baking in advance), further in the box-shaped drying machine, also cool off in 230 ℃ of heat dryings 30 minutes (afterwards baking), obtain pane of tinted glass (colour filter).
(estimating 1)
[thickening efficiency of pigment dispersion]
Be determined at initial viscosity (kinematic viscosity) A(mPas that just makes good each pigment dispersion afterwards in embodiment 1～7 and the reference example 1).Then, with each pigment dispersion of embodiment 1～7 and reference example 1 under 25 ℃ the environment after firm manufacturing begins to place 1 day well, measure viscosity (kinematic viscosity) B(mPas after the placement of each pigment dispersion).The mensuration of the viscosity of pigment dispersion (kinematic viscosity) is carried out under 25 ℃ environment according to JIS Z8809, use E type viscometer (trade(brand)name: RE-01, Toki Sangyo Co., Ltd.'s system).Thickening efficiency is calculated based on following formula.Thickening efficiency=(placing back viscosity B)/(initial viscosity A).Table 4 expression result, the relative value the when initial viscosity of the embodiment 1～7 in the table 4 is standard (100) as the initial viscosity with the pigment dispersion of reference example 1 is represented.
[mensuration of contrast gradient]
The contrast gradient of the pane of tinted glass (colour filter) after baking behind use contrast gradient determinator mensuration embodiment 1～7 and the reference example 1.The contrast gradient determinator is made of chroma-luminance meter (trade(brand)name=LS-100, Konica Minolta Sensing, Inc. system), lamp (trade(brand)name: HF-SL-100WLCG, the logical Industry Co., Ltd of electricity system) and polaroid (trade(brand)name=POLAX-38S, the Luceo of Co., Ltd. system).
The mode that is spaced apart 1mm with polaroid (POLAX-38S) and pane of tinted glass on backlight arranges polaroid.The polaroid that can rotate is set at an upper portion thereof.After confirming that the brightness of backlight is fully stable, the polaroid that can rotate that is arranged at top is adjusted to the position of Nicol crossed, measures the brightness of pane of tinted glass, then, half-twist is measured the brightness of pane of tinted glass in parallel position.Ratio between two (%) spent as a comparison obtain.Table 4 expression result.The contrast value of embodiment 1～7 in the table 4 as the contrast gradient of the pane of tinted glass that obtains with the pigment dispersion that uses reference example 1 relative value during as standard (100) represent.
[mensuration of brightness (Y)]
The brightness (Y) of the embodiment 1～7 that obtains during following mensuration is above-mentioned and the pane of tinted glass of reference example 1.Pane of tinted glass is fixed in spectral photometric colour measuring meter (trade(brand)name=CM-3700d, Konica Minolta Sensing, Inc. system), the transmission colourity in the XYZ coordinate axle when measuring 2 ° of illuminant-Cs.Adopt the Y value of this moment as brightness (Y).Table 4 expression result.The brightness value of embodiment 1～7 in the table 4 as the brightness of the pane of tinted glass that obtains with the pigment dispersion that uses reference example 1 relative value during as standard (100) represent.
[table 4]
? Triaizine compounds Initial viscosity Thickening efficiency Brightness (Y) Contrast gradient
With reference to rate 1 （III） 1.00 1.03 1.00 1.00
Embodiment 1 （2a） 1.40 1.14 1.21 1.18
Embodiment 2 （2b） 1.14 0.83 1.21 1.01
Embodiment 3 （2c） 1.12 1.07 1.26 1.16
Embodiment 4 （3a） 1.54 1.18 1.19 1.06
Embodiment 5 （3b） 1.70 1.18 1.20 1.04
Embodiment 6 （3c） 2.24 1.29 1.24 1.00
Embodiment 7 （3d） 1.43 1.14 1.21 1.01
As shown in Table 4: the triaizine compounds of the application of the invention, can obtain following colour filter, this colour filter helps the few image of increase of display brightness raising and contrast gradient, namely helps to show distinct color image.
(embodiment 8～9 and comparative example 1～2)
Form (g) except changing to the pigment dispersion shown in the table 5, operation similarly to Example 1, carry out pre-dispersed, main dispersion, PMA to the interpolation of main dispersion thing, stirring and the filtration after the PMA interpolation, obtain veridian dispersion (embodiment 8 and comparative example 1) and blue pigment dispersion (embodiment 9 and comparative example 2).
[table 5]
Figure BDA00002844696500231
Triaizine compounds (2c) each composition in addition that uses in the table 5 is specific as follows described.
[pigment]
※ 1Lionol Green6YK; Trade(brand)name, veridian (C.I, pigment green 36), Toyo-chem Co.LTD. system
※ 2Fastogen blue EP-207; Trade(brand)name. 6), Dainippon Ink Chemicals's system copper phthalocyanine is blue pigments (pigment Blue 15 C.1.:
[dispersing auxiliary]
※ 3Solsperse S12000; Trade(brand)name, the pigment derivative with sulfo group, Lubrizol(road Bo Run) corporate system
[resin type dispersion agent]
※ 4BYK-LPN6919(solid component concentration 60.9%); Trade(brand)name, Bi Ke chemistry Japan (strain) system
※ 5BYK-LPN21116(solid component concentration 40.0%); Trade(brand)name, Bi Ke chemistry Japan (strain) system
※ 6RIPOXY SPC-2000(solid component concentration 35%); Trade(brand)name, vinylester resin, Showa Denko K. K's system
(estimating 2)
The pigment dispersion that use obtains in above-described embodiment 8～9 and comparative example 1～2 is made colour filter, estimates its performance.
[making of colour filter]
In the pigment dispersion that is obtained by embodiment 8～9 and comparative example 1～2, add to mix following each composition, preparation resist composition (spin coating liquid, below be made as " SPC liquid ").Wherein, be that the total solids that the mode of 1:1 is adjusted pigment dispersion becomes the total solids of the total of each composition of component and other to become component with the weight ratio, and mix both.
The resist composition is formed:
Figure BDA00002844696500241
Each SPC liquid of obtaining can be obtained target colourity (embodiment 8 and comparative example 1 to become on the square sheet glass of thickness 1mm, 100mm; Y=0.500, embodiment 9 and comparative example 2; The mode of thickness y=0.120) is made with spin coater (trade(brand)name: Spin Coater MS-150A, MIKASA(strain)) coating, in the box-shaped drying machine in 90 ℃ of dryings 2.5 minutes (baking in advance), further in the box-shaped drying machine in 230 ℃ of heat dryings 30 minutes (afterwards baking), obtain each pane of tinted glass (colour filter) of embodiment 8～9 and comparative example 1～2.
[evaluation of colourity (x, y), brightness (Y)]
To each pane of tinted glass of embodiment 8～9 and comparative example 1～2, use colourimeter (trade(brand)name: CM-3700d, Konica Minolta (strain) system) to obtain the tristimulus values of utilizing xyY table color method.Table 6 expression result.
[contrast gradient]
To each pane of tinted glass (colour filter) after baking behind embodiment 8～9 and the comparative example 1～2, with above-mentioned operation similarly, the ratio (%) of the brightness the when brightness when being positioned at the position of Nicol crossed as polaroid is positioned at parallel position with polaroid is obtained contrast gradient (CR).
Table 6 expression result.
[table 6]
Figure BDA00002844696500251
Learn according to table 6: embodiment 8 and 9 brightness (Y value) are big, therefore, the triaizine compounds of the application of the invention (1), the brightness of the image on the colour liquid crystal display device improves, and can realize purpose of the present invention.

Claims (11)

1. triaizine compounds is characterized in that:
It is by following general formula (1) expression,
Figure FDA00002844696400011
In the formula (1), R 1The expression group:
Figure FDA00002844696400012
Group:
Figure FDA00002844696400013
Or group: R 2The expression group: Group:
Figure FDA00002844696400016
Group:
Figure FDA00002844696400017
, hydroxyl or halogen atom; R 3, R 4And R 5Identical or different, alkyl or the alkoxyl group of carbonatoms 1～4, the perhaps R of expression hydrogen atom, carbonatoms 1～4 3With R4 or R 4And R 5The formation phenyl ring interosculates; R 6Expression hydrogen atom, the alkyl of carbonatoms 1～4 or the alkoxyl group of carbonatoms 1～4; R 7The alkoxyl group of expression hydrogen atom or carbonatoms 1～4; L is the average importing number of the sulfo group in triaizine compounds 1 molecule shown in the formula (1), the number of expression 1～2; M and n represent 1～2 integer respectively.
2. triaizine compounds as claimed in claim 1 is characterized in that:
It is by following general formula (2) expression,
Figure FDA00002844696400018
In the formula (2), R 3, R 4And R 5Identical or different, alkyl or the alkoxyl group of carbonatoms 1～4, the perhaps R of expression hydrogen atom, carbonatoms 1～4 3And R 4Or R 4And R 5The formation phenyl ring interosculates; R 10And R 11Identical or different, the expression group:
Figure FDA00002844696400021
Group:
Figure FDA00002844696400022
Or group:
Figure FDA00002844696400023
R 7The alkoxyl group of expression hydrogen atom or carbonatoms 1～4, l is the average importing number of the sulfo group in triaizine compounds 1 molecule shown in the formula (2), the number of expression 1～2; N represents 1～2 integer.
3. triaizine compounds as claimed in claim 2 is characterized in that:
Described R 10And R 11Identical or different, expression
Group:
Figure FDA00002844696400024
Or group:
Figure FDA00002844696400025
R 7The alkoxyl group of expression hydrogen atom or carbonatoms 1～4, n represents 1～2 integer.
4. as claim 2 or 3 described triaizine compounds, it is characterized in that:
Described R 10With described R 11Be identical group.
5. triaizine compounds as claimed in claim 1 is characterized in that:
It is the triaizine compounds shown in the following general formula (3),
Figure FDA00002844696400026
In the formula (3), R 3, R 4And R 5Identical or different, alkyl or the alkoxyl group of carbonatoms 1～4, the perhaps R of expression hydrogen atom, carbonatoms 1～4 3And R 4Or R 4And R 5The formation phenyl ring interosculates; R 6Expression hydrogen atom, the alkyl of carbonatoms 1～4 or the alkoxyl group of carbonatoms 1～4; L is the average importing number of the sulfo group in triaizine compounds 1 molecule shown in the formula (3), the number of expression 1～2; M represents 1～2 integer; X represents hydroxyl, halogen atom or group:
Figure FDA00002844696400027
R 10The expression group:
Figure FDA00002844696400031
Group:
Figure FDA00002844696400032
Or group:
Figure FDA00002844696400033
R 7The alkoxyl group of expression hydrogen atom or carbonatoms 1～4; N represents 1～2 integer.
6. triaizine compounds as claimed in claim 5 is characterized in that:
Described R 10Be following radicals,
Group:
7. pigment dispersion aids is characterized in that:
It contains each described triaizine compounds in the claim 1～6.
8. pigment dispersion is characterized in that:
It contains pigment, pigment dispersing agent, the described pigment dispersion aids of claim 7 and solvent.
9. pigment dispersion as claimed in claim 8 is characterized in that:
The volume average particle size of pigment is 10～100nm.
10. pigment dispersion as claimed in claim 8 or 9 is characterized in that:
The content of described pigment is 30～80 weight % that the total solids of pigment dispersion becomes component, and with respect to described pigment 100 weight parts, contains the described pigment dispersing agent of 10～60 weight parts, contains the described pigment dispersion aids of 1～25 weight part.
11. a resist composition is characterized in that:
It contains each described pigment dispersion and photosensitive compounds in the claim 8～10.
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