CN100590151C - Dye, ink, ink jet recording method, ink sheet, color toner and color filter - Google Patents
Dye, ink, ink jet recording method, ink sheet, color toner and color filter Download PDFInfo
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- CN100590151C CN100590151C CN 200580001188 CN200580001188A CN100590151C CN 100590151 C CN100590151 C CN 100590151C CN 200580001188 CN200580001188 CN 200580001188 CN 200580001188 A CN200580001188 A CN 200580001188A CN 100590151 C CN100590151 C CN 100590151C
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Abstract
To provide a dye which has a good hue, which can form an image showing a high fastness under various using conditions and environmental conditions, and which is particularly suited for an ink, the dyeis represents by formula (1): wherein R1 and R2 each independently represents a monovalent group, Z represents a nitrogen atom or a carbon atom to which a hydrogen atom or a monovalent group is bonded, and M represents a hydrogen atom or a cation, provided that the dye has two azo groups.
Description
Technical field
The present invention relates to a kind of dyestuff, printing ink, ink jet recording method, printing ink sheet, toner and colour filter.
Background technology
In recent years, image recording material mainly is to form the material that coloured image is used, more particularly, generally use ink jet recording materials, heat transfer recording materials, electrophotographic recording material, transfer process (transfer process) photosensitive silve halide material, marking ink and stylus.The colour filter that will be used for equally, writing down or reproduce coloured image is used for imaging device for example at the CCD in photographic equipment field or the LCD or the PDP of field of display.In these coloured image recording materials or colour filter,, use based on the three look dyestuffs (dyestuff or pigment) that add the mixture of colours or subtractive process in order to show or to write down full-colour image.Yet the fact is not have the absorption characteristic that can realize superior color rendering district and can anti-different working conditionss and the grain of envrionment conditions, therefore presses for dyestuff is improved.
The dyestuff of such use requires to have following characteristic usually.Promptly, require them aspect color rendering, to have superior absorption characteristic, the envrionment conditions that they are used has stability, for example photostabilization, thermotolerance, humidity resistance, to the oxidizing gas tolerance of ozone for example, with to the chemical substance tolerance of sulphur dioxide for example, and provide printing ink with excellent storage stability.Therefore, press for have good yellow tone, good light fastness, good heat-resisting moist and to the well tolerable property of reactive gas contained in the environment and dyestuff with excellent storage stability.
Yellow dyes skeleton as being used for the printing ink that ink-vapor recording uses typically has the azo-group dyestuff.As the representative instance of azoic dyestuff, the firm dyestuff with triazinyl pyrazoles skeleton has been described in JP-A-2003-277662.Yet hope can provide the dyestuff of more excellent storage stability.
Summary of the invention
The objective of the invention is to solve the problem that conventional dyes has and reach following target.Promptly, the purpose of this invention is to provide 1) a kind of dyestuff, it has excellent color reprodubility as the dyestuff of three color systems, have enough fast light, heat-resisting, the performance of moisture-proof and the gas of anti-the environment activity, and in printing ink, show excellent storage stability, 2) various coloured compositions, they can be provided at color harmony stability aspect excellence coloured image or coloured material, the marking ink used of spray ink Printing for example, printing ink sheet in the thermal recording material, the toner of electrophotography and at the indicating meter colour filter that for example uses among the CCD of LCD or PDP or imaging device for example, with 3) particularly, printing ink that a kind of ink jet recording method is used and ink-vapor recording, they have excellent storage stability and good tone, and it can form have high fast light, heat-resisting, the image of the performance of moisture-proof and the gas of anti-environment activity the, particularly anti-ozone gas.
For find can provide show good storage stability, show good color be in harmonious proportion have high fast light, anti-ozone, the purpose of the dyestuff of the printing ink of heat-resisting and moisture resistance properties, the inventor has studied pyrazolyl azoic dyestuff derivative in great detail, the compound that found that following formula (1) representative can address the above problem, and has therefore finished the present invention.The mode that addresses the above problem is as described below.
1. the dyestuff of a formula (1) representative:
R wherein
1And R
2Represent univalent perssad independently of one another, the carbon atom that Z represents nitrogen-atoms or links to each other with hydrogen atom or univalent perssad, M are represented hydrogen atom or positively charged ion,
Condition is that this dyestuff has two azo-groups.
2. according to the 1st dyestuff, the dyestuff of its Chinese style (1) representative is the dyestuff of formula (2) representative:
R wherein
3And R
4Represent univalent perssad independently of one another, Ar
1And Ar
2Represent aryl or heterocyclic radical independently of one another, and M represents hydrogen atom or positively charged ion.
3. according to the 2nd dyestuff, Ar wherein
1And Ar
2Represent the group of formula (A) representative independently of one another:
Wherein Ra represents univalent perssad.
4. according to the 1st dyestuff, the dyestuff of its Chinese style (1) representative is the dyestuff of formula (3) representative:
R wherein
5, R
6, R
7And R
8Represent univalent perssad independently of one another, Ar
3Represent divalent linker, M represents hydrogen atom or positively charged ion.
5. according to the 1st dyestuff, the dyestuff of its Chinese style (1) representative is the dyestuff of formula (4) representative:
R wherein
9And R
10Represent univalent perssad independently of one another, Ar
4And Ar
5Represent aryl or heterocyclic radical independently of one another, Ar
6Represent divalent linker, M represents hydrogen atom or positively charged ion.
6. according to the 5th dyestuff, Ar wherein
4And Ar
5Represent the group of formula (A) representative independently of one another:
Wherein Ra represents univalent perssad.
7. printing ink comprises according to each dyestuff of 1-6 item.
8. ink jet recording method comprises that use forms image according to the 7th printing ink.
9. printing ink sheet comprises according to each dyestuff in the 1-6 item.
10. toner comprises according to each dyestuff in the 1-6 item.
11. a colour filter comprises according to each dyestuff in the 1-6 item.
The invention advantage
Dyestuff of the present invention shows excellent storage stability, has excellent absorption characteristic and have the performance of the reactive gas in enough fast light, heat-resisting, moisture-prooves and the anti-environment aspect color reprodubility as three look dyestuffs in printing ink.Equally, these dyestuffs can be used for various coloured compositions, they can be provided in the coloured image or the coloured material of color harmony stability aspect excellence, for example the toner of the marking ink used of spray ink Printing, the printing ink sheet in the thermal recording material, electrophotography, be used for for example for example colour filter of CCD and the dyeing solution that the various fibers that dye are used of LCD or PDP or imaging device of indicating meter.Specifically, use this dyestuff that a kind of ink-jet recording ink and a kind of ink jet recording method with excellent storage stability can be provided, it can form the image of the performance with reactive gas, particularly ozone gas in the high fast light and anti-environment of good color mediation.
Detailed Description Of The Invention
Describe the present invention below in detail.
(azoic dyestuff)
Azoic dyestuff of the present invention is the azoic dyestuff of preceding formula (1) representative.
Below formula (1) is described.
R
1, R
2The substituting group of the aryl of describing later with the univalent perssad of Z representative and this paper is identical.
This dyestuff has two azo-groups at intramolecularly, divides two classes: (1) one class is the dyestuff that has a group at intramolecularly, and this group has two azo-groups as substituting group; (2) another kind of is the dyestuff with two groups, and wherein each group all has an azo-group.As the group of the former azo-group replacement and the group that the latter has azo-group, preferred heterocyclic group.The heterocyclic preferred embodiment that constitutes heterocyclic group comprises 5-pyrazolone ring, 5-amino-pyrazol Huan, azolactone ring, malonylurea ring, pyridine ring, rhodanine ring, pyrazolidinedione ring, Pyrazolopyridine ketone ring and merdramic acid ring.Wherein, preferred 5-pyrazolone ring and 5-amino-pyrazol ring, preferred especially 5-amino-pyrazol ring.
In the present invention, M represents hydrogen atom or positively charged ion.The cationic example of M representative comprises alkalimetal ion, ammonium and quaternary ammonium cation.Wherein, preferred Li, Na, K, NH
4And NR
4, wherein R represents alkyl or aryl, and described alkyl or aryl is identical with the described alkyl or aryl in this paper back.
In the azoic dyestuff of formula (1) representative, the dyestuff of preferred formula (2), (3) or (4) representative.
R in the formula (2)
3The univalent perssad and the R of representative
4The substituting group with the described aryl in this paper back is identical separately for the univalent perssad of representative.Its preferred embodiment comprises alkyl, cycloalkyl, aralkyl, alkoxyl group, aryl, amino, carboxyl (the optional salt that forms) and formamyl, wherein more preferably alkyl (preferably containing 1-5 carbon atom, for example methyl, ethyl, butyl or the tertiary butyl).Identical to these substituent detailed descriptions with the described substituting group in this paper back.
As Ar
1Or Ar
2The heterocycle of the heterocyclic group of representative, preferred 5-or 6-unit ring, they can also condense with other ring.Equally, these heterocycles can be aromatic heterocycle or nonaromatic heterocycles.The example comprises pyridine, pyrazine, pyridazine, quinoline, isoquinoline 99.9, quinazoline, cinnolines, 2, quinoxaline, pyrroles (pyrole), indoles, furans, cumarone, thiophene, thionaphthene, pyrazoles, imidazoles, benzoglyoxaline, triazole, azoles, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazoles, isoxazole, benzoisoxazole, tetramethyleneimine, piperidines, piperazine, imidazolidine and thiazoline.Wherein, preferred fragrance heterocycle.Its preferred illustrative examples comprises pyridine, pyrazine, pyridazine, pyrazoles, imidazoles, benzoglyoxaline, triazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole and thiadiazoles.Its preferred example comprises imidazoles, benzoxazole and thiadiazoles, most preferably thiadiazoles (preferred 1,3,4-thiadiazoles or 1,2,4-thiadiazoles).They can have substituting group.Substituent example is identical with the substituting group of the described aryl in this paper back.
Ar
1The aryl and the Ar of representative
2The aryl of representative comprises separately and replacing and unsubstituted aryl.As this replacement or unsubstituted aryl, preferably has the aryl of 6-30 carbon atom.The substituent example of this aryl comprises halogen atom; alkyl; cycloalkyl; aralkyl; thiazolinyl; alkynyl; aryl; heterocyclic radical; cyano group; hydroxyl; nitro; carboxyl (the optional salt that forms); alkoxyl group; aryloxy; silyloxy; heterocyclic oxy group; acyloxy; formamyl oxygen base; alkoxy-carbonyl oxy; aryloxycarbonyl oxygen base; amino (comprising anilino); amido; aminocarbonyl amino; alkoxycarbonyl amino; aryloxycarbonyl amino; sulfamoylamino group; alkyl sulfonyl-amino; arlysulfonylamino; sulfydryl; alkyl sulfide; arylthio; the heterocycle sulfenyl; sulfamyl; sulfo group (the optional salt that forms); the alkyl sulfinyl; the aryl sulfinyl; alkyl sulphonyl; aryl sulfonyl; acyl group; aryloxycarbonyl; alkoxy carbonyl; formamyl; imino-; phosphino-; phosphinyl; phosphinyl oxygen base; phosphinyl amino and silyl.
As Ar
1The aryl and the Ar of representative
2The aryl of representative, the more preferably phenyl of Qu Daiing (this substituting group is carboxyl or sulfo group preferably).
Be described in more detail below the substituting group of aryl.
Halogen atom is chlorine atom, bromine atoms or iodine atom.
Alkyl comprises the alkyl and the unsubstituted alkyl of replacement.As replacing or unsubstituted alkyl, preferably has the alkyl of 1-30 carbon atom.These substituent examples are identical with the substituting group of aryl.Wherein, preferred hydroxyl, alkoxyl group, cyano group, halogen atom, sulfo group (the optional salt that forms) and carboxyl (the optional salt that forms).The example of alkyl comprises methyl, ethyl, butyl, the tertiary butyl, n-octyl, eicosyl, 2-chloroethyl, hydroxyethyl, cyanoethyl and 4-sulfo group butyl.
Cycloalkyl comprises the cycloalkyl and the unsubstituted cycloalkyl of replacement.Replacement or unsubstituted cycloalkyl preferably contain 5-30 carbon atom.This substituent example is identical with the substituting group of aryl.The example of cycloalkyl comprises cyclohexyl, cyclopentyl and 4-dodecyl cyclohexyl.
Aralkyl comprises the aralkyl and the unsubstituted aralkyl of replacement.As replacing or unsubstituted aralkyl, preferably contain the aralkyl of 7-30 carbon atom.This substituent example is identical with the substituting group of aryl.The example of aralkyl comprises benzyl and 2-styroyl.
Thiazolinyl is straight chain, side chain or cyclic, replacement or unsubstituted thiazolinyl.Its preferred embodiment comprises replacement or the unsubstituted thiazolinyl that contains 2-30 carbon atom, for example vinyl, allyl group, prenyl, geranyl, oil base, 2-cyclopentenes-1-base and 2-tetrahydrobenzene-1-base.
Alkynyl is replacement or the unsubstituted alkynyl that contains 2-30 carbon atom, and has enumerated ethynyl and propargyl.
Aryl is replacement or the unsubstituted aryl that contains 6-30 carbon atom, for example phenyl, right-tolyl, naphthyl ,-chloro-phenyl-and neighbour-palmitoyl aminophenyl.
Heterocyclic radical is by removing the univalent perssad that a hydrogen atom forms from fragrance or non-aromatic heterocycles, more preferably containing the 5-or the 6-membered aromatic heterocycle base of 3-30 carbon atom.The example comprises 2-furyl, 2-thienyl, 2-pyrimidyl, 2-[4-morpholinodithio base and morpholinyl.
Alkoxyl group comprises the alkoxyl group and the unsubstituted alkoxyl group of replacement.As replacing or unsubstituted alkoxyl group, preferably contain the alkoxyl group of 1-30 carbon atom.This substituent example is identical with the substituting group of aryl.The example of alkoxyl group comprises methoxyl group, oxyethyl group, isopropoxy, n-octyloxy, methoxy ethoxy, hydroxyl-oxethyl and 3-carboxyl propoxy-.
Aryloxy is replacement or the unsubstituted aryloxy that contains 6-30 carbon atom, and phenoxy group, 2-methylphenoxy, 4-tertiary butyl phenoxy group, 3-nitro-phenoxy and 2-myristoyl amino-benzene oxygen are for example arranged.
Silyloxy is the silyloxy that contains 3-20 carbon atom, and trimethylammonium silyloxy and tertiary butyl dimethyl methyl siloxy are for example arranged.
Heterocyclic oxy group is replacement or the unsubstituted heterocyclic oxy group that contains 2-30 carbon atom, and 1-phenyltetrazole-5-oxygen base and 2-THP trtrahydropyranyl oxygen base are for example arranged.
Acyloxy is methanoyl, contain the replacement or the unsubstituted alkyl ketonic oxygen base of 2-30 carbon atom or contain the replacement or the unsubstituted aryl carbonyl oxygen base of 6-30 carbon atom, and methanoyl, acetoxyl group, new pentane acyloxy, stearoyl-oxy, benzoyloxy, right-p-methoxy-phenyl ketonic oxygen base are for example arranged.
Formamyl oxygen base is replacement or the unsubstituted formamyl oxygen base that contains 1-30 carbon atom; N is for example arranged; N-formyl-dimethylamino oxygen base, N; N-diethylacbamazine acyloxy, morpholinyl carbonyl oxygen base, N, N-two-n-octyl aminocarboxyl oxygen base and N-n-octyl formamyl oxygen base.
Alkoxy-carbonyl oxy is replacement or the unsubstituted alkoxy-carbonyl oxy that contains 2-30 carbon atom, and methoxycarbonyl oxygen base, ethoxy carbonyl oxygen base, tert-butoxycarbonyl oxygen base and n-octyl ketonic oxygen base are for example arranged.
Aryloxycarbonyl oxygen base is replacement or the unsubstituted aryloxycarbonyl oxygen base that contains 7-30 carbon atom, and phenyloxycarbonyl oxygen base, right-methoxyl group phenoxy group ketonic oxygen base and right-n-hexadecane oxygen phenoxyl ketonic oxygen base are for example arranged.
Amino is replacement or the unsubstituted arylamino that contains the replacement or the unsubstituted alkyl amino of 1-30 carbon atom or contain 6-30 carbon atom, amino, methylamino-, dimethylamino, anilino, N-methyl-anilino, diphenyl amino, hydroxyethylamino, carboxy ethyl amino, sulfo group ethylamino and 3 are for example arranged, 5-dicarboxyl anilino.
Amido is formamido group, contain the replacement or the unsubstituted alkyl carbonylamino of 1-30 carbon atom or contain the replacement or the unsubstituted aryl-amino-carbonyl of 6-30 carbon atom, formamido group, kharophen, pivalyl amino, lauroyl amino, benzamido and 3 are for example arranged, 4,5-three-n-octyloxy phenylcarbonyl group amino.
Aminocarbonyl amino is replacement or the unsubstituted aminocarbonyl amino that contains 1-30 carbon atom, and formamyl amino, N are for example arranged, N-carbonyl dimethyl ammonium amino, N, N-diethyl amino carbonylamino and morpholinyl carbonyl amino.
Alkoxycarbonyl amino is replacement or the unsubstituted alkoxycarbonyl amino that contains 2-30 carbon atom, and methoxycarbonyl amino, ethoxy carbonyl amino, tert-butoxycarbonyl amino, Octadecane oxygen base carbonylamino and N-methyl-methoxycarbonyl amino are for example arranged.
Aryloxycarbonyl amino is replacement or the unsubstituted aryloxycarbonyl amino that contains 7-30 carbon atom, for example have phenyloxycarbonyl amino, right-chlorophenoxy carbonylamino and-n-octyloxy phenyloxycarbonyl amino.
Sulfamoylamino group is replacement or the unsubstituted sulfamoylamino group that contains 0-30 carbon atom, and sulfamoylamino group, N are for example arranged, N-dimethylamino ylsulfonylamino and N-n-octyl aminosulfonyl amino.
Alkyl sulfonyl-amino or arlysulfonylamino are replacement or the unsubstituted arlysulfonylaminos that contains the replacement or the unsubstituted alkyl sulfuryl amino of 1-30 carbon atom or contain 6-30 carbon atom; methyl sulphonyl amino, butyl sulfuryl amino, phenyl sulfonyl amino, 2 are for example arranged; 3,5-trichlorophenyl sulfuryl amino and right-methyl sulphonyl amino.
Alkyl sulfide is replacement or the unsubstituted alkyl sulphur that contains 1-30 carbon atom, and methyl sulphur, ethyl sulphur and n-hexadecyl sulphur are for example arranged.
Arylthio is replacement or the unsubstituted arylthio that contains 6-30 carbon atom, for example have thiophenyl, right-chlorobenzene sulfenyl and-the anisole sulfenyl.
The heterocycle sulfenyl is replacement or the unsubstituted heterocycle sulfenyl that contains 2-30 carbon atom, and 2-[4-morpholinodithio base sulfenyl and 1-phenyltetrazole-5-base sulfenyl is for example arranged.
Sulfamyl is replacement or the unsubstituted sulfamyl that contains 0-30 carbon atom; N-ethyl sulfamyl, N-(3-dodecyloxy propyl group) sulfamyl, N are for example arranged, N-dimethylamino alkylsulfonyl, N-ethanoyl sulfamyl, N-benzoyl sulfamyl and N-(N '-the phenyl amino formyl radical) sulfamyl.
Alkyl sulfinyl or aryl sulfinyl are replacement or the unsubstituted aryl sulfinyls that contains the replacement or the unsubstituted alkyl sulfinyl of 1-30 carbon atom or contain 6-30 carbon atom, and methyl sulfinyl, ethylsulfinyl-1 base, phenyl sulfinyl and right-aminomethyl phenyl sulfinyl are for example arranged.
Alkyl sulphonyl or aryl sulfonyl are replacement or the unsubstituted aryl sulfonyls that contains the replacement or the unsubstituted alkyl alkylsulfonyl of 1-30 carbon atom or contain 6-30 carbon atom, and methyl sulphonyl, ethylsulfonyl, phenyl sulfonyl and right-aminomethyl phenyl alkylsulfonyl are for example arranged.
Acyl group is formyl radical, contain the alkyl-carbonyl of 2-30 carbon atom, contain the replacement or the unsubstituted aryl carbonyl of 7-30 carbon atom or contain the heterocycle carbonyl of 4-30 carbon atom, and ethanoyl, valeryl, 2-chloracetyl, stearyl-, benzoyl, right-the n-octyloxy phenylcarbonyl group, 2-pyridyl carbonyl and 2-furyl carbonyl are for example arranged.
Aryloxycarbonyl is replacement or the unsubstituted aryloxycarbonyl that contains 7-30 carbon atom, for example have phenyloxycarbonyl, neighbour-chlorophenoxy carbonyl ,-nitro-phenoxy carbonyl and right-tertiary butyl phenyloxycarbonyl.
Alkoxy carbonyl is replacement or the unsubstituted alkoxy carbonyl that contains 2-30 carbon atom, and methoxycarbonyl, ethoxy carbonyl, tert-butoxycarbonyl and Octadecane oxygen base carbonyl are for example arranged.
Formamyl is replacement or the unsubstituted formamyl that contains 1-30 carbon atom; formamyl, N-methylamino formyl radical, N are for example arranged; N-formyl-dimethylamino, N, N-two-n-octyl formamyl and N-(methyl sulphonyl) formamyl.
Phosphino-is replacement or the unsubstituted phosphino-that contains 2-30 carbon atom, and dimethyl phosphino-, diphenylphosphino and methylphenoxy phosphino-are for example arranged.
Phosphinyl is replacement or the unsubstituted phosphinyl that contains 2-30 carbon atom, and phosphinyl, two octyloxy phosphinyls and diethoxy phosphinyl are for example arranged.
Phosphinyl oxygen base is replacement or the unsubstituted phosphinyl oxygen base that contains 2-30 carbon atom, and two phenoxy group phosphine oxide oxygen bases and two octyloxy phosphine oxide oxygen bases are for example arranged.
Phosphinyl amino is replacement or the unsubstituted phosphinyl amino that contains 2-30 carbon atom, and the amino and dimethylamino phosphinyl amino of dimethoxy phosphinyl is for example arranged.
Silyl is replacement or the unsubstituted silyl that contains 3-30 carbon atom, and trimethyl silyl, t-butyldimethylsilyl and phenyl dimetylsilyl are for example arranged.
In the substituting group of aryl, the substituting group with hydrogen can be replaced by above-mentioned substituting group at this hydrogen atom when removing hydrogen atom.The example of this functional group comprises alkyl-carbonyl-amino alkylsulfonyl, aryl-amino-carbonyl alkylsulfonyl, alkyl sulfonyl-amino carbonyl and aryl sulfonyl amino carbonyl.Its specific examples comprises methyl sulphonyl aminocarboxyl, right-the aminomethyl phenyl sulfonyl amino carbonyl, acetylamino alkylsulfonyl and benzoyl-amido alkylsulfonyl.
In the dyestuff of following formula (2) representative, preferred Ar wherein
1And Ar
2Represent the dyestuff of heterocyclic radical independently of one another, more preferably Ar wherein
1And Ar
2Represent the group of following formula (A) independently of one another.
In formula (A), Ra represents univalent perssad.R in the univalent perssad of Ra representative and the formula (1)
1Or R
2The univalent perssad of representative is identical, and wherein preferable range is also identical.More preferably, Ra representative-L-Ph or-(wherein Ph representative replaces or unsubstituted phenyl Ph, wherein the middle R of substituting group and formula (1)
1Or R
2The univalent perssad of representative is identical, L represent divalent linker and with the middle Ar of formula (3)
3Identical).Even more preferably, Ra representative-S-Ph or-Ph (wherein Ph representative replaces or unsubstituted phenyl).
Below formula (3) is described in detail.R
5The univalent perssad and the R of representative
6The representative univalent perssad separately with R
3Or R
4Univalent perssad identical.R
7The univalent perssad and the R of representative
8The substituting group with above-mentioned aryl is identical separately for the univalent perssad of representative.And, R
7And R
8Preferably represent halogen atom, OM (wherein M represents hydrogen atom or positively charged ion), alkoxyl group, alkyl sulfide, arylthio, amino or heterocyclic radical separately.These substituting groups are foregoing identical with this paper.
Ar
3The preferred alkylidene group of divalent group of representative (for example, methylene radical, ethylidene, propylidene, butylidene or pentylidene), alkenylene (for example, vinylidene or propenylidene), alkynylene (for example, ethynylene or inferior proyl), arylidene (for example, phenylene or naphthylidene), divalent heterocycle (for example, 6-chloro-1,3,5-triazine-2,4-two bases, pyrimidine-2,4-two bases, quinoxaline-2,3-two bases or pyridazine-3,6-two bases) ,-O-,-CO-,-NR-(wherein R represents hydrogen atom, alkyl or aryl) ,-S-,-SO
2-,-SO-or their combination (for example ,-NHCH
2CH
2NH-or-NHCONH-).
The alkyl or aryl of alkylidene group, alkenylene, alkynylene, arylidene and divalent heterocycle and R can have one or more substituting groups.This substituent example is identical with the substituting group of aryl.The alkyl of R is previously defined identical with this paper with aryl.
More preferably, divalent alkyl be the alkylidene group that contains 10 or carbon atom still less, contain 10 or carbon atom still less alkenylene, contain 10 or carbon atom still less alkynylene, contain 6-10 carbon atom arylidene ,-S-,-SO-,-SO
2-or they combination (for example ,-SCH
2CH
2S-or-SCH
2CH
2CH
2S-).
The total number of carbon atoms of divalent linker is 0-50 preferably, more preferably 0-30, most preferably 0-10.
Below formula (4) is described.R
9Univalent perssad and R
10Univalent perssad separately with formula (2) in R
3Or R
4Univalent perssad identical.Ar
4Aryl and the heterocyclic radical and the Ar of representative
5Ar in the aryl of representative and heterocyclic radical and the formula (2)
1Or Ar
2The aryl of representative is identical with heterocyclic radical, wherein preferred heterocyclic radical.Ar
6Ar in the divalent linker of representative and the formula (3)
3Divalent linker identical.
In the dyestuff of formula (2), (3) or (4) representative, the dyestuff of preferred formula (2) representative.
In the present invention, in formula (1), (2), the compound of (3) or (4) representative requires under the hydrophilic situation, preferably this compound have at intramolecularly two or more, more preferably 2-10, preferred especially 3-6 hydrophilic radical.Yet under the situation that does not make water as medium, this compound can not have hydrophilic radical.
As hydrophilic radical, can use any ionic dissociation group.Its specific examples comprises sulfo group, carboxyl (comprising its salt), hydroxyl (the optional salt that forms), phosphono (the optional salt that forms) and quaternary ammonium salt, wherein preferred sulfo group, carboxyl and hydroxyl (salt that comprises them).
Consider color reprodubility, the dyestuff of formula (1), (2), (3) or (4) representative is at H
2Has preferred 380-490nm among the O, more preferably 400-480nm, the especially preferably maximum absorption wavelength (λ max) of 420-460nm.
The specific examples (illustrative dyestuff 1-57) of the dyestuff of following display type (1), (2), (3) or (4) representative.Yet the dyestuff that the present invention uses is not limited only to them.
Below specific examples be to represent by the structure of free acid, but the state that they can its salt uses.The preferred embodiment of the counter ion of this salt comprises basic metal (for example, lithium, sodium and potassium), ammonium and organic cation (for example, pyridine, tetramethyl-ammonium and guanidine (guanidinium)).
Dyestuff of the present invention can be synthetic according to the method for the described synthetic dyestuff 1 in this paper back.
Purposes as for dyestuff of the present invention, described and be used to form image, the image recording material of coloured image particularly, particularly recording materials, transfer printing (transfer) type photosensitive silve halide material, marking ink and the stylus of the ink jet recording materials described in detail later of this paper, thermal recording material, pressure-sensitive recording materials, electrophotography, the recording materials of preferred ink jet recording materials, thermal recording material and electrophotography, more preferably ink jet recording materials.
Equally, dyestuff of the present invention can be coated to record and reproduce on the colour filter of coloured image, and it is used for for example CCD or indicating meter the dye dyeing solution of various fibers of LCD and PDP and being used to for example of solid-state imaging.
By select physicals that wherein substituting group can adjust dyestuff of the present invention for example solubleness, dispersiveness and hot movability to adapt to purposes.Equally, dyestuff of the present invention can use with dissolved state, emulsive emulsion state or solid dispersed state according to the system that uses.
(printing ink)
Printing ink of the present invention is meant the printing ink that contains at least a dyestuff of the present invention.Printing ink of the present invention can contain medium, and is using under the situation of solvent as medium, and printing ink is ink-jet recording ink especially preferably.Printing ink of the present invention can use oleophylic medium or water-bearing media to dissolve and/or be distributed in this medium as medium and with dyestuff of the present invention and make.The preferred printing ink that uses water-bearing media.As required, printing ink of the present invention can contain other additive in the scope of not damaging effect of the present invention.The example of other additive comprises known additives (described in the JP-A-2003-306623) for example anti-drying dose (wetting agent), anti-fading agent, emulsion stabilizer, penetration enhancer, UV light absorber, sanitas, anti-Fungicide, pH regulator agent, surface tension modifier, defoamer, viscosity modifier, dispersion agent, dispersion stabilizer, rust-preventive agent and sequestrant.Under the situation that is water-based ink, the additives that these are different directly join in the ink solutions.Using under the situation of oil-soluble colourant as dispersion, after the preparation dye dispersion, joining in the dispersion usually, but can in the preparation these oil-soluble colourant be joined oil phase or aqueous phase.
Under situation about dyestuff of the present invention being distributed in the water-bearing media, coloured particulate that preferably will contain dyestuff and oil-soluble polymers is distributed to JP-A-11-286637, JP-A-2001-240763 (Japanese patent application 2000-78491), in the water-bearing media described in JP-A-2001-262039 (Japanese patent application 2000-80259) and the JP-A-2001-247788 (Japanese patent application 2000-62370), the dyestuff of the present invention that perhaps will be dissolved in the high boiling organic solvent is dispersed in JP-A-2001-262018 (Japanese patent application 2000-78454), JP-A-2001-240763 (Japanese patent application 2000-78491), in the aqueous solution described in JP-A-2001-335734 (Japanese patent application 2000-203856) and the Japanese patent application 2000-203857.Dyestuff of the present invention is being distributed under the situation of water-bearing media, can preferably using concrete using method, oil-soluble polymers, high boiling organic solvent, additive and the consumption thereof described in the patent documentation of front.In addition, the solid dispersed that azoic dyestuff of the present invention can the particulate state.When disperseing, can use dispersion agent or tensio-active agent.As dispersing apparatus, can use simple agitator or homogenizer, the whipping device in pipeline, grinding machine (for example, colloidal mill, ball mill, sand mill, supper micron mill, roller mill or agitator), ultrasonic equipment or high-pressure emulsification equipment (high pressure homogenizer; The example of the equipment of concrete commercially available acquisition comprises GAULIN clarifixator, microfluidization device and DeBEE2000).Preparation method as above-mentioned ink for ink-jet recording, except above-mentioned patent documentation, provided detailed description in JP-A-5-148436, JP-A-5-295312, JP-A-7-97541, JP-A-7-82515, JP-A-7-118584, JP-A-11-286637 and JP-A-2001-271003 (Japanese patent application 2000-87539), they can be used for preparing the printing ink of the present invention that ink-vapor recording is used.
As aforesaid water-bearing media, can use and contain the mixture of water as main component and water-miscible organic solvent as required.The example of the water-miscible organic solvent that uses comprises the organic solvent described in the JP-A-2003-306623.In addition, the water-miscible organic solvent can two or more mix use.
The printing ink of relative 100 weight parts, dyestuff of the present invention is with preferred 0.1-120 weight part, more preferably 0.2-10 weight part, even more preferably the amount of 0.5-9 weight part is included in the printing ink of the present invention that ink-vapor recording uses.In addition, be used for the printing ink of the present invention that ink-vapor recording is used, other dyestuff can be being mixed use with dyestuff of the present invention.Mixing under the situation of using two or more dyestuffs, the total amount of dyestuff is preferably in above-mentioned scope.
Printing ink of the present invention not only can be used for forming monochrome image, and can be used for forming full-colour image.In order to form full-colour image, can use magenta ink, cyan ink and Yellow ink.Equally, in order to adjust tone, can also use black ink.
And the printing ink of the present invention that is used for ink-vapor recording can comprise dyestuff of the present invention and other dyestuff except that dyestuff of the present invention.As operable yellow dyes, utilizable magenta dye and utilizable cyan dye can use any dyestuff, and can utilize those dyestuffs described in the JP-A-2003-306623 0090-0092 section.The example of operable black material comprises tetrazo, trisazo-and Tetrakisazo dyes and sooty dispersion.
(ink jet recording method)
Ink jet recording method of the present invention is on known image receiving material, promptly in common paper, resin coating paper, JP-A-8-169172 for example, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153989, JP-A-10-217473, JP-A-10-235995, JP-A-10-337947, ink-vapor recording dedicated paper described in JP-A-10-217597 and the JP-A-10-337947, film, ink-vapor recording and electrophotographic recording paper, cloth, glass, apply energy by the printing ink of using to ink-vapor recording on metal or the pottery and form image.In addition, as ink jet recording method of the present invention, can be referring to the explanation of JP-A-2003-306623 0093-0105 section.
When forming image, for give gloss or or water-repellancy or improve weathering resistance, can use the polymer latex compound simultaneously.About latex compounds being joined the time of image receiving material, can before or after adding tinting material, add, perhaps can when adding tinting material, carry out.Therefore,, latex compounds can be joined image-receiving sheet or join printing ink, perhaps latex compounds only can be used as the fluent material of polymer latex as for the implantation site that adds of latex compounds.Particularly, can preferably use the method described in JP-A-2002-166638 (Japanese patent application 2000-363090), JP-A-2002-121440 (Japanese patent application 2000-315231), JP-A-2002-154201 (Japanese patent application 2000-354380), JP-A-2002-144696 (Japanese patent application 2000-343944), JP-A-2002-080759 (Japanese patent application 2000-268952), Japanese patent application 2000-299465 and the Japanese patent application 2000-297365.
(toner)
The amount of dyestuff of the present invention has no particular limits in the toner of per 100 weight parts, but preferred 0.1 weight part or higher, more preferably 1-10 weight part, most preferably 2-10 weight part.
As the adhesive resin that the toner that adds dyestuff of the present invention is used, can use all tackiness agents commonly used arbitrarily.The example comprises styrene base resin, acrylic resin, styrene/acrylic resin and vibrin.
In order to improve mobile purpose or, can in toner, to add inorganic fine powder or organic particulate in addition in order to control static electric charge.Preferred fine particles of silica and the titanium dioxide particulate that uses the surface to cross with the coupling agent treatment that contains alkyl.In addition, they have the number average primary particle diameter of preferred 10-500nm, and join in the toner with the amount of 0.1-20 weight %.
As releasing agent, can use releasing agent commonly used arbitrarily.The example comprises for example for example Microcrystalline Wax, carnauba wax, sazol wax and paraffin of low-molecular polypropylene, low molecular polyethylene and ethylene-propylene copolymer and wax of alkene.Its add-on in toner is 1-5 weight % preferably.
Can add charge control agent as required, consider that color forms performance, does not preferably have toner.The example comprises those charge control agents of quaternary ammonium salt structure and those charge control agents of calixarene (calixarene) structure.
As carrier, only can use any non-coating carrier that constitutes by magneticsubstance (for example iron or ferrite) particle and comprise that surface coated has the carrier of coating resin of the particles of magnetic material of resin.The relative volume average grain, the median size of carrier is 30-150 μ m preferably.
The formation method that applies toner of the present invention has no particular limits, and the example comprise by repeat to form coloured image and its formation method of transfer printing (transfer), by continuously transfer printing the method for the formation coloured image of the image that forms on the electronic photographic photo-receptor and by will the image continuously transfer printing that forms on the electronic photographic photo-receptor to the intermediate transfer body to form coloured image on this intermediate transfer body and this coloured image to be transferred to for example method of the formation coloured image on the paper of image-forming component.
(heat record (transfer printing) material)
Thermal recording material is made of a printing ink sheet, and this printing ink sheet comprises the carrier that is coated with dyestuff of the present invention and tackiness agent on it and the image receiving sheet of the dyestuff fixing that will as one man move with the heat energy that adds from thermal head according to image recording signal.This printing ink sheet can be by with compound of the present invention with tackiness agent is dissolved in the solvent or with particulate described compound is dispersed in and prepares ink solutions in the solvent, this ink solutions is applied on the carrier, and forms the ink solutions of coating is dry.The amount of the printing ink that is coated with on the carrier has no particular limits, but preferred 30-1000mg/m
2As preferred adhesive resin, printing ink solvent, carrier and image receiving sheet, can preferably use the material described in the JP-A-7-137466.
Using thermal recording material as can write down the thermal recording material of full-colour image the time, preferably by coating contains the cyan ink sheet of hot diffusible cyan dye that can form cyan image continuously on carrier, the yellow oil ink sheet that contains the magenta ink sheet of hot diffusible magenta dye that can form magenta color image and contain hot diffusible yellow dyes that can form yellow image forms full-colour image.Can also form the printing ink sheet that contains the material that forms black image equally, as required.
(colour filter)
As the method that forms colour filter, have at first to form the painted then method of pattern and form method of patterning, described in JP-A-4-163552, JP-A-4-128703 and JP-A-4-175753 by photo-resist by photo-resist.As the method for under situation about dyestuff of the present invention being joined in the colour filter, using, can use any means.As a preferred method, the formation method of the colour filter that can be described as comprising the steps: will comprise thermoset composition, quinone diazide, linking agent, dyestuff and solvent eurymeric (positive-working) composition exposure and by mask be applied on the matrix, with exposed portion develop form positive resist pattern, will whole positive resist pattern exposure, then with the resist pattern photographic fixing (setting) that exposes, described in JP-A-4-175753 and JP-A-6-35182.Can obtain former color base colour filter of RGB or YMC compensation color base colour filter by forming black matix equally, in a conventional manner.This colour filter to the consumption of dyestuff also without limits, but the amount of preferred 0.1-50 weight %.
As the thermosetting resin that is used to form colour filter, quinone diazide, linking agent and solvent and their consumption can preferably use those materials described in the aforementioned patent document and their consumption.
Embodiment
Embodiment
Describe the present invention in more detail with reference to the following examples, but the present invention should not be construed as and is limited to this.
Embodiment 1
As exemplary embodiments, the synthetic method of dyestuff 1 is described below.Each step among the synthetic embodiment can be carried out according to known synthetic method (can referring to the specification sheets of JP-A-2003-277662 and Japanese patent application 2003-286844).
(synthetic embodiment)
(1) with the NaHCO of 18.5g
3H with 185ml
2O is heated to 40 ℃, and the solution in the acetone of the compound a that wherein adds 18.4g at 48ml, then stirs 1 hour.Reaction soln is concentrated after the amount that reduces acetone,, and at room temperature this mixture was stirred 3 hours to the hydrazine that wherein adds 40g.Filter and collect sedimentary thus crystallization, obtain the compound b of 14g.
(2) the 1N NaOH of 10ml is joined the compound b of 10.5g, the compound c of 20g and the H of 330ml
2In the mixture of O, with gained mixture heating up 3 hours.This reaction mixture is filtered, and filtrate is used the acetate acidifying.Filter and collect sedimentary thus crystallization, obtain the compound d of 4g.
(3) with the Verbindung diazotization of 15g and under 5 ℃, join the compound d of 3g, the CH of 100ml
3The CH of OH and 16g
3In the mixture of COOK.Filter and collect sedimentary thus crystallization, and obtain the dyestuff 1 of 4.9g through column chromatography.
λmax451.7nm(H
2O)、ε：5.88x10
4(dm
3·cm/mol)。
Can synthesize other dyestuff in the same manner.
Embodiment 2
The synthetic embodiment of synthetic dyestuff 20 is described below.Synthetic method that can be by implementing synthetic dyestuff 1 is synthetic dyestuff 20 similarly.These synthetic dyestuff are at H
2λ max among the O is shown in table 1.
Table 1
Embodiment 3
With pure water (resistance value: 18M Ω or bigger) join and make 1 liter in the following component, under heating, the gained mixture was stirred 1 hour.Afterwards, under reduced pressure the microfilter by 0.25 μ m filters this mixture and makes Yellow ink solution Y-101.
(prescription of Yellow ink Y-101)
(solid ingredient)
Dyestuff 1 40g/l of the present invention
Proxel (producing) 1.5g/l by Zeneca
Urea 20g/l
(liquid ingredient)
Triglycol single-butyl ether (DGB) 100g/l
Glycerine (GR) 115g/l
Triglycol (TEG) 100g/l
2-Pyrrolidone 35g/l
Trolamine (TEA) 8g/l
Surfynol STG(SW) 10g/l
Except change dyestuff as shown in table 2 below, prepare ink solutions Y-102 in the mode identical with the preparation of ink solutions Y-101.
In this case, comparative dye a shown in the use table 2 and b prepare ink solutions 101 and 102 ink solutions as a comparison.
When changing dyestuff, the addition of dyestuff be adjusted to ink solutions Y-101 in moles such as dyestuff.
The printing ink that the ink-vapor recording of preparation is used in embodiment (ink solutions Y101 and Y102) and the Comparative Examples (ink solutions 101 and 102) carries out following evaluation.The results are shown in table 2.
In addition, in table 2, the Yellow ink that joins the ink-jet printer PM920C that EPSON makes by the printing ink that each ink-vapor recording is used with in the cartridge also the monochrome image pattern and the gray image pattern that change gradually of print image density estimate " tone ", " photostabilization ", " anti-ozone (gas) property " and " thermotolerance ".At the image receiving sheet, print image is gone up in " Kotaku " (for being fit to the developing out paper of EPSON ink-jet printer), and picture quality and image stability are estimated.
(evaluation test)
＜tone 〉
Naked eyes divide Three Estate A (best), B (well) and C (poor) evaluation map picture.Also shown the λ max value on developing out paper " Kotaku ".
＜photostabilization 〉
At once image density Ci after measure printing by reflection densitometer (X-rite 310TR).Then, and weatherometer (weather meter) xenon lamp that use Atlas makes (85,000lux) to image irradiation 7 days, and measure image density Cf, thereby keeping, definite dyestuff estimates than Cf/Cix100.In reflection density is that three points of 1,1.5 and 2 are estimated dyestuff respectively and kept ratio.With show under three density dyestuff keep than be 70% or bigger sample be evaluated as A, be evaluated as B with showing under two density in three density that dyestuff keeps than the sample less than 70%, and will show under all three density that dyestuff keeps than being evaluated as C for the sample less than 70%.
＜anti-ozone (gas) property 〉
The developing out paper of imaging was left standstill 10 days in ozone gas density is adjusted to the box of 5ppm, and use reflection densitometer (X-rite 310TR) to measure this paper before leaving standstill under the ozone gas environment and image density afterwards, thereby determine that dyestuff keeps ratio.In addition, be that three points of 1,1.5 and 2 are measured reflection density respectively in density.By the ozone gas monitor (model of making by APPLICS: OZG-EM-01) the ozone gas density of detection in box.
Divide Three Estate to estimate.Promptly, with show under all three density dyestuff keep than be 80% or bigger sample be evaluated as A, be evaluated as B with showing under one or two density in three density that dyestuff keeps than the sample less than 80%, and be evaluated as C showing under all three density that dyestuff keeps than the sample less than 70%.
＜thermotolerance 〉
Use reflection densitometer (X-rite 310TR) working sample before storage under the condition of 80 ℃ and 70%RH 10 days and image density afterwards be used for estimating.Be that three points of 1,1.5 and 2 are measured dyestuffs and kept ratio in reflection density respectively.With show under all three density dyestuff keep than be 90% or bigger sample be evaluated as A, be evaluated as B with showing under two density in three density that dyestuff keeps than the sample less than 90%, and be evaluated as C showing under all three density that dyestuff keeps than the sample less than 90%.
＜ink stability 〉
The ink solutions that obtains was above preserved 6 days down at 70 ℃, kept than being used for by the liquid chromatogram measuring dyestuff and estimate.With show dyestuff keep than be 95% or bigger ink solutions be evaluated as A, will show that dyestuff keeps than being 85% to be evaluated as B to the ink solutions less than 95%, and will show that dyestuff reservation ratio is evaluated as C less than 85% ink solutions.
Tabulation shows thus obtained result below.
Table 2
| Sample | Dyestuff | Tone (λ max) | Photostabilization | Ozone resistance | The anti-property held | Ink stability | Remarks |
| Y101 | 1 | A (455nm) | A | A | A | A | The present invention |
| Y102 | 4 | A (453nm) | A | A | A | A | The present invention |
| 101 | a | A (446nm) | A | A | A | B | Comparative Examples |
| 102 | b | A (448nm) | A | A | A | C | Comparative Examples |
Be clear that by top tabulation result displayed, use that all factors all are excellent in all systems of printing ink of the present invention.Specifically, compare with the system of Comparative Examples, they have excellent ink stability.
Comparative dye a
Comparative dye b
Embodiment 4
Use with embodiment 3 in the identical printing ink of use and identical printer at FujiPhoto Film Co., Ltd. print image on the ink jetting paper of the photograph glossy paper " Gasai " of Zhi Zaoing, carry out then with embodiment 3 in identical evaluation, obtain with embodiment 3 in identical result.
Embodiment 5
(preparation of ink solutions D)
Under 70 ℃ the sodium dioctyl sulfosuccinate of the dyestuff of the present invention of 62.5g and 7.04g is dissolved in the mixture of ethyl acetate of the following high boiling organic solvent (s-11) of following high boiling organic solvent (s-2), 5.63g of 4.22g and 50ml.Under stirring, in this mixture solution, add deionized water, make the oil-in-water-type coarse dispersion with magnetic stirrer.Then, under the pressure of 600bar, make the gained crude mixture by microfluidization device (MICROFLUIDEX INC) thus reduce the size of oil droplets for 5 times.And, in rotatory evaporator, make the gained emulsion remove step until the smell that can not find ethyl acetate through solvent.In the miniemulsion of thus obtained hydrophobic dye, add the glycol ether of 140g, the glycerine of 50g, SURFYNOL 465 (the Air Products﹠amp of 7g; Chemicals) and the deionized water of 900ml, make ink solutions D.This printing ink has the viscosity of 8.5 pH, 4.1mPaS and the surface tension of 33mN/m.
(preparation of ink solutions 103)
Except the comparative dye shown in the table 3 of the dyestuff of the present invention that uses among the ink solutions D being changed into equimolar amount, prepare ink solutions 103 in the mode identical with ink solutions D.This ink solutions has the pH identical with ink solutions D, identical viscosity and identical surface tension.
(image recording and evaluation)
Ink solutions D and comparative ink solution 103 are carried out following evaluation.The results are shown in following table 3.
In addition, in table 3, " tone (λ max) ", " photostabilization ", " anti-ozone (gas) property ", " thermotolerance " have respectively and identical implication described in the embodiment 3 with " ink stability ".
Table 3
| Sample | Dyestuff | Tone (λ max) | Photostabilization | Ozone resistance | Thermotolerance | Ink stability |
| D | 6 | A (450nm) | A | A | A | A |
| 103 | Comparative dye C4 | B (430nm) | C | C | A | A |
Comparative dye C
Be clear that from table 3 printing ink of the present invention that is used for ink-vapor recording has excellent tone, photostabilization, ozone resistance, thermotolerance and ink stability.
Embodiment 6
Use with embodiment 5 in used identical printing ink and same printer at Fuji PhotoFilm Co., Ltd. print image on the ink jetting paper of the photograph glossy paper " Gasai " of Zhi Zaoing, carry out the evaluation identical then, obtain the result identical with embodiment 5 with embodiment 5.
Embodiment 7
With the dyestuff of the present invention 5 of 3 weight parts and the toner resin (copolymer in cinnamic acrylic ester of 100 weight parts; Commodity Himer TB-1000F by name is (by Sanyo ChemicalIndustries, Ltd. produce)) mix to be incorporated in the ball mill and pulverize, be heated to 150 ℃ then and carry out melt kneading, after this mixture cooling, by hammer mill this mixture is pulverized, it is broken to carry out fine powder then in based on the fine crusher of air-injection system.And with the gained fine particle separation, selecting particle diameter is the particle of 1-20 micron, by selected granules preparation toner.(commodity are called EFV250/400 for 10 parts of these toners and 900 parts of carrier iron powders; Make by NihonTeppun) uniform mixing, make photographic developer.Equally, prepare sample in the same manner, only be to use the tinting material shown in the table 4 of 3 weight parts.(commodity are called NP-5000 at the dry method electrophotographic copier to use these photographic developers; By Canon Co., Ltd. makes) common paper is duplicated.
In the following manner, reflected image (image on paper) and the transparent image (OHP image) that forms respectively according to above-mentioned formation method by the photographic developer that contains toner of the present invention carried out evaluation test on paper and OHP.In addition, at 0.7 ± 0.05 (mg/cm
2) scope in estimate based on the amount of sedimentary toner.
Estimate the color harmony photostabilization of thus obtained image.Estimate tone with best, good and these Three Estate naked eyes of difference.Evaluation result is shown in following table 4.In table 4, " A " is meant that the tone of sample is best, and " B " is meant that the tone of sample is good, and " C " is meant the tonal difference of sample.
As for photostabilization, be determined at once image density Ci after the record, use then weatherometer (Atlas C.165) with xenon lamp (85,000lux) to image irradiation 5 days.Then, measure image density Cf, thus determine dyestuff keep than (Ci-Cf)/Ci}x100%, with before the xenon lamp irradiation and the difference of image density afterwards be that the basis is used for estimating.Use reflection densitometer (X-Rite 310TR) to measure image density.The thus obtained following table 4 that the results are shown in.In table 4, show dyestuff keep than be 90% or bigger sample be evaluated as A, show that dyestuff keeps than being evaluated as B for the sample of 90-80%, and will show that dyestuff reservation ratio is to be evaluated as C less than 80% sample.
Estimate the properties of transparency of OHP image according to method described below.By Hitachi, " the 330 type automatic recording spectrophotometer " that Ltd. makes measured the visible spectrum transmittance of image, is not reference with the OHP sheet of toner wherein, determines the spectral transmittance under 650nm thus.With this spectral transmittance measuring as the properties of transparency of OHP image.To show that the spectrum transparency is evaluated as A greater than 80% sample, will show that the spectrum transparency is that the sample of 70-80% is evaluated as B, and will show that spectral-transmission favtor is evaluated as C less than 70% sample.The thus obtained table 4 that the results are shown in.
Table 4
| Dyestuff | Tone | Photostabilization | Properties of transparency | |
| The present invention | 5 | A | A | A |
| Comparative Examples | C.I. solvent yellow 16 2 | B | B | B |
Be clear that from table 4 toner of the present invention realizes having Hi-Fi color reprodubility and high OHP quality is provided, so it is suitable as panchromatic toner.And this toner has good photostabilization, and it can provide the image that can preserve for a long time like this.
Embodiment 8
(preparation of the material of hot dye transfer is provided)
Use the thick polyethylene terephthalate thin film of 6-μ m (making) that the material (5-1) of hot dye transfer is provided as preparing carriers by Teijin, the reverse side of this film is through giving thermotolerance and lubricated processing, and is coated with layer that the down coating composition of surface compositions be used to provide hot dye transfer with the dry thickness of 1.5 μ m according to wrapping wire formula coating method on the surface of film.
Be used to provide the coating composition of the layer of hot dye transfer
Dyestuff 510mmol
Polyvinyl butyral resin is (by the 3g of Denki Kagaku manufacturing
Denka Butyral 5000-A)
Toluene 40ml
Methyl ethyl ketone 40ml
Polymeric polyisocyanate is (by the Takenate 0.2ml of Takeda Yakuhin manufacturing
D110N)
Then, preparation provides the material (5-2) of correlated hot dye transfer in the same manner as described above, except dyestuff 5 is become the comparative dye described in the table 5.
(heat transfer image receives the preparation of material)
Use the thick synthetic paper of 150-μ m (YUPO-FPG-150 that makes by Qji Yuka) as carrier and prepare heat transfer image with dry thickness composition below the coating of wrapping wire formula coating method of 8 μ m and receive material.After interim dry by moisture eliminator in 100 ℃ of stoves drying 30 minutes.
The coating composition that is used for image receiving layer
Vibrin (by the VYLON-280 of Toyobo manufacturing) 22g
Polymeric polyisocyanate is (by Dainippon Ink﹠amp; Chemicals, Inc. makes 4g
The KP-90 that makes)
Amino modified silicone oil is (by the 0.5g of Shin-etsu Silicone manufacturing
KF-857)
Methyl ethyl ketone 85ml
Toluene 85ml
Pimelinketone 15ml
Make the aspect that hot dye is provided to image receiving layer, with thus obtained each material (5-1) of hot dye transfer is provided and (5-2) is superimposed upon heat transfer image receive on the material, and use from the thermal head of the carrier side of the material that hot dye transfer is provided and under the condition of the dot density of the pulse width of thermal head output that 0.25W/ order, 0.15-15 millisecond and 6 points/mm, print, the image receiving layer epigraph sample at image receiving material deposits yellow dyes thus.The maximum colorant density of thus obtained image is shown in table 5.The material (5-1) of hot dye transfer that provides of the present invention forms the clear image that does not have the transfer printing irregularity.Then, (17,000lux) irradiation is 5 days, thereby measures the photostabilization of coloured image with the Xe lamp for thus obtained each record heat transfer image reception material.Measure to show after the irradiation that the A condition reflection density is the A condition mode reflection density of 1.0 part, and be 1.0 to estimate photostabilization for the residual ratio (per-cent) of the reflection density on basis based on reflection density before the irradiation.The results are shown in table 5.
Table 5
Provide hot dye transfer maximum photostabilization remarks
The density of material of dyestuff
5-1 5 1.8 90 the present invention
5-2 comparative dye d 1.8 52 Comparative Examples
Comparative dye d
Foregoing as this paper, compare dyestuff excellence of the present invention with comparative dye.Equally, the tone of the image that forms by dyestuff of the present invention is clear.
Embodiment 9
During colour filter, the eurymeric resist composition that will contain thermosetting resin, quinone diazide, linking agent, dyestuff and solvent is spun on the silicon chip in preparation, and by heating with after the solvent evaporation, by the mask exposure coating to decompose the quinone diazide.After heating, the coating of will exposing is developed and is obtained mosaic pattern as required.By Hitachi, i-x ray exposure x stepper (stepper) the HITACHI LD-5010-I (NA=0.40) that Ltd produces exposes.Equally, as developing solution, use the SOPD or the SOPD-B that produce by Sumitomo Kagaku Kogyo.
＜eurymeric resist preparation of compositions 〉
With 3.4 weight parts by-cresol novolac resin that the mixture of cresols/p-Cresol/formaldehyde (reaction mol ratio=5/5/7.5) obtains is (based on polystyrene, weight-average molecular weight is 4300), the dyestuff of the present invention that shows of the table 1 of the ethyl lactate of the hexa methoxy methylol melamine of the neighbour-naphthoquinones two nitrine-5-sulphonate (average 2 hydroxyls are esterified) by the oxybenzene compound preparation of following formula representative of 1.8 weight parts, 0.8 weight part, 20 weight parts and 1 weight part mixes, and obtains eurymeric resist composition.
Oxybenzene compound
The preparation of＜colour filter 〉
By spin coating thus obtained eurymeric resist composition is applied on the silicon chip, afterwards solvent evaporated.After silicon wafer exposure, 100 ℃ of heating, exposure region is removed in the alkali development then with it, and obtaining resolving power thus is the positive colored pattern of 0.8 μ m.After the whole pattern exposure, this silicon chip was heated 15 minutes down at 150 ℃, acquisition has the colour filter with yellow complementary color.
＜Comparative Examples 〉
The yellow dyes of the present invention that replaces using among the top embodiment by the OleozolYellow 2G that is made by Sumitomo Kagaku Kogyo that uses 1 weight part obtains eurymeric resist composition.By spin coating thus obtained eurymeric resist composition is applied on the silicon chip, then solvent evaporated.After silicon wafer exposure, carrying out alkali development acquisition resolving power is the positive colored pattern of 1 μ m.After whole pattern exposure, under 150 ℃,, obtain yellow filter with this silicon chip heating 10 minutes.
＜estimate
The transparent spectrum of each yellow filter that measure to obtain, and relative evaluation is in the spectrographic acutance of shorter wavelength side and longer wavelength side, it is important at color reprodubility." A " represents good level, and " B " represents the acceptable level, and " C " represents unacceptable level.Equally, use weatherometer (Atlas C.I65) with xenon lamp (85,000lux) to each sample irradiation 7 days, and measure with before the xenon lamp irradiation and image density afterwards, keep than estimating photostabilization based on dyestuff.
Table 6
| Dyestuff | Absorption characteristic | Photostabilization | |
| The present invention | 5 | A | 96％ |
| Comparative Examples | Oleozol Yellow 2G | B | 59％ |
Can see that dyestuff of the present invention is compared with the dyestuff of Comparative Examples, be presented at the bigger spectrum of acutance of shorter wavelength side and longer wavelength side, so color reprodubility be excellent.Equally, see with control compounds and comparing, the photostabilization excellence of dyestuff of the present invention.
Industrial applicibility
Dyestuff of the present invention can be used for various coloured compositions, the coloured image or the coloured material of color harmony stability excellence can be provided, for example the toner of the marking ink used of spray ink Printing, the printing ink sheet in the thermal recording material, electrophotography, be used for indicating meter for example LCD or PDP or be used for the imaging device for example colour filter of CCD and the dyeing solution of the various fibers that dye.
Explain the present invention in detail and with reference to embodiment, but it is evident that to those skilled in the art, under scope and spirit of the present invention, can carry out various improvement and change.
With the application require each foreign patent application of foreign priority and separately the full content of foreign patent application add this paper by reference, be equivalent to all be described in herein.
Claims (8)
1, the dyestuff of a kind of formula (2), (3) or (4) representative:
Wherein:
R
3, R
4, R
5, R
6, R
7, R
8, R
9And R
10Representative independently of one another is selected from univalent perssad hereinafter described; Ar
1, Ar
2, Ar
4And Ar
5Representative independently of one another contains aryl or 5 yuan or 6 yuan of heterocyclic radicals of 6-30 carbon atom, and described aryl is randomly replaced by described univalent perssad, and described heterocyclic radical is optional to condense with other ring; Ar
3And Ar
6Representative independently of one another contains the divalent linker of 0-50 carbon atom, and M represents hydrogen atom or positively charged ion;
Described univalent perssad is selected from following group, and randomly also is substituted with and is selected from following group univalent perssad:
Halogen atom,
The alkyl that contains 1-30 carbon atom,
The cycloalkyl that contains 5-30 carbon atom,
The aralkyl that contains 7-30 carbon atom,
The thiazolinyl that contains 2-30 carbon atom,
The alkynyl that contains 2-30 carbon atom,
The aryl that contains 6-30 carbon atom,
The heterocyclic radical that contains 3-30 carbon atom,
Cyano group,
Hydroxyl,
Nitro,
Carboxyl,
The alkoxyl group that contains 1-30 carbon atom,
The aryloxy that contains 6-30 carbon atom,
The silyloxy that contains 3-20 carbon atom,
The heterocyclic oxy group that contains 2-30 carbon atom,
Methanoyl,
The alkyl-carbonyl oxygen base that contains 2-30 carbon atom,
The aryl carbonyl oxygen base that contains 6-30 carbon atom,
The formamyl oxygen base that contains 1-30 carbon atom,
The alkoxy-carbonyl oxy that contains 2-30 carbon atom,
The aryloxycarbonyl oxygen base that contains 7-30 carbon atom,
The alkylamino that contains 1-30 carbon atom,
The arylamino that contains 6-30 carbon atom,
Formamido-,
The alkyl-carbonyl-amino that contains 1-30 carbon atom,
The aryl-amino-carbonyl that contains 6-30 carbon atom,
The aminocarbonyl amino that contains 1-30 carbon atom,
The alkoxycarbonyl amino that contains 2-30 carbon atom,
The aryloxycarbonyl amino that contains 7-30 carbon atom,
The sulfamoylamino group that contains 0-30 carbon atom,
The alkyl sulfonyl-amino that contains 1-30 carbon atom,
The arlysulfonylamino that contains 6-30 carbon atom,
Sulfydryl,
The alkyl sulfide that contains 1-30 carbon atom,
The arylthio that contains 6-30 carbon atom,
The heterocycle sulfenyl that contains 2-30 carbon atom,
The sulfamyl that contains 0-30 carbon atom,
Sulfo group,
The alkyl sulfinyl that contains 1-30 carbon atom,
The aryl sulfinyl that contains 6-30 carbon atom,
The alkyl sulphonyl that contains 1-30 carbon atom,
The aryl sulfonyl that contains 6-30 carbon atom,
Formyl radical,
The alkyl-carbonyl that contains 2-30 carbon atom,
The aryl carbonyl that contains 7-30 carbon atom,
The heterocycle carbonyl that contains 4-30 carbon atom,
The aryloxycarbonyl that contains 7-30 carbon atom,
The alkoxy carbonyl that contains 2-30 carbon atom,
The formamyl that contains 1-30 carbon atom,
Imino-,
The phosphino-that contains 2-30 carbon atom,
The phosphinyl that contains 2-30 carbon atom,
The phosphinyl oxygen base that contains 2-30 carbon atom,
The phosphinyl amino that contains 2-30 carbon atom,
The silyl that contains 3-30 carbon atom.
2, dyestuff as claimed in claim 1, wherein Ar
1, Ar
2, Ar
4And Ar
5Represent the group of formula (A) representative independently of one another:
Wherein the Ra representative is selected from following group univalent perssad; And randomly also be substituted with and be selected from following group univalent perssad:
Halogen atom,
The alkyl that contains 1-30 carbon atom,
The cycloalkyl that contains 5-30 carbon atom,
The aralkyl that contains 7-30 carbon atom,
The thiazolinyl that contains 2-30 carbon atom,
The alkynyl that contains 2-30 carbon atom,
The aryl that contains 6-30 carbon atom,
The heterocyclic radical that contains 3-30 carbon atom,
Cyano group,
Hydroxyl,
Nitro,
Carboxyl,
The alkoxyl group that contains 1-30 carbon atom,
The aryloxy that contains 6-30 carbon atom,
The silyloxy that contains 3-20 carbon atom,
The heterocyclic oxy group that contains 2-30 carbon atom,
Methanoyl,
The alkyl-carbonyl oxygen base that contains 2-30 carbon atom,
The aryl carbonyl oxygen base that contains 6-30 carbon atom,
The formamyl oxygen base that contains 1-30 carbon atom,
The alkoxy-carbonyl oxy that contains 2-30 carbon atom,
The aryloxycarbonyl oxygen base that contains 7-30 carbon atom,
The alkylamino that contains 1-30 carbon atom,
The arylamino that contains 6-30 carbon atom,
Formamido-,
The alkyl-carbonyl-amino that contains 1-30 carbon atom,
The aryl-amino-carbonyl that contains 6-30 carbon atom,
The aminocarbonyl amino that contains 1-30 carbon atom,
The alkoxycarbonyl amino that contains 2-30 carbon atom,
The aryloxycarbonyl amino that contains 7-30 carbon atom,
The sulfamoylamino group that contains 0-30 carbon atom,
The alkyl sulfonyl-amino that contains 1-30 carbon atom,
The arlysulfonylamino that contains 6-30 carbon atom,
Sulfydryl,
The alkyl sulfide that contains 1-30 carbon atom,
The arylthio that contains 6-30 carbon atom,
The heterocycle sulfenyl that contains 2-30 carbon atom,
The sulfamyl that contains 0-30 carbon atom,
Sulfo group,
The alkyl sulfinyl that contains 1-30 carbon atom,
The aryl sulfinyl that contains 6-30 carbon atom,
The alkyl sulphonyl that contains 1-30 carbon atom,
The aryl sulfonyl that contains 6-30 carbon atom,
Formyl radical,
The alkyl-carbonyl that contains 2-30 carbon atom,
The aryl carbonyl that contains 7-30 carbon atom,
The heterocycle carbonyl that contains 4-30 carbon atom,
The aryloxycarbonyl that contains 7-30 carbon atom,
The alkoxy carbonyl that contains 2-30 carbon atom,
The formamyl that contains 1-30 carbon atom,
Imino-,
The phosphino-that contains 2-30 carbon atom,
The phosphinyl that contains 2-30 carbon atom,
The phosphinyl oxygen base that contains 2-30 carbon atom,
The phosphinyl amino that contains 2-30 carbon atom,
The silyl that contains 3-30 carbon atom.
3, dyestuff as claimed in claim 1, wherein said divalent linker are selected from following group:
Contain 10 or the alkylidene group of carbon atom still less, contain 10 or the alkenylene of carbon atom still less, contain 10 or the alkynylene of carbon atom still less, contain the arylidene of 6-10 carbon atom ,-O-,-CO-,-NR-,-S-,-SO-,-SO
2-or the combination of these groups; Wherein R represents hydrogen atom, contains the alkyl of 1-30 carbon atom or contains the aryl of 6-30 carbon atom.
4. printing ink comprises each the dyestuff as claim 1-3.
5. an ink jet recording method comprises and uses printing ink as claimed in claim 4 to form image.
6 one kinds of printing ink sheets comprise each the dyestuff as claim 1-3.
7. toner comprises each the dyestuff as claim 1-3.
8. colour filter comprises each the dyestuff as claim 1-3.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004030288 | 2004-02-06 | ||
| JP030288/2004 | 2004-02-06 | ||
| JP211241/2004 | 2004-07-20 | ||
| JP305665/2004 | 2004-10-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1860185A CN1860185A (en) | 2006-11-08 |
| CN100590151C true CN100590151C (en) | 2010-02-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580001188 Active CN100590151C (en) | 2004-02-06 | 2005-02-03 | Dye, ink, ink jet recording method, ink sheet, color toner and color filter |
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|---|---|
| CN (1) | CN100590151C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5433173B2 (en) * | 2007-06-29 | 2014-03-05 | 富士フイルム株式会社 | Azo pigment, method for producing the azo pigment, pigment dispersion containing the pigment, coloring composition, and ink for ink jet recording |
| WO2012073756A1 (en) * | 2010-11-29 | 2012-06-07 | 保土谷化学工業株式会社 | Charge control agent and toner using same |
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2005
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1860185A (en) | 2006-11-08 |
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