CN101665637B - Ink and ink set for inkjet recording - Google Patents

Ink and ink set for inkjet recording Download PDF

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CN101665637B
CN101665637B CN 200810175778 CN200810175778A CN101665637B CN 101665637 B CN101665637 B CN 101665637B CN 200810175778 CN200810175778 CN 200810175778 CN 200810175778 A CN200810175778 A CN 200810175778A CN 101665637 B CN101665637 B CN 101665637B
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ink
dyestuff
amino
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CN101665637A (en
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田口敏树
小泽孝
小川学
和地直孝
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Fujifilm Corp
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  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
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Abstract

To provide inks and ink sets for inkjet recording, which have good fastness and good jet-out stability and which give good images with no bleeding trouble, yellow ink, black ink and magenta ink for inkjet printing contain at least two dyes each having an oxidation potential over 1.0 V (vs SCE).

Description

Ink for inkjet recording and ink group
The application is that the PCT international filing date is on October 22nd, 2004, and the PCT international application no is denomination of invention the dividing an application for the application of " ink for inkjet recording and ink group " of PCT/JP2004/016059.
Technical field
The present invention relates to a kind of ink composition for inkjet recording, even it provides the image with good shelf-stability after standing storage, to go out to have good ejection stability with it.
Background technology
In recent years, along with popularizing of computingmachine, not only in office but also in the family, ink-jet printer is widely used in paper, film, fabric and other printing.
Thereby ink jet recording method comprises through using piezoelectric device to system that ink droplet is exerted pressure ejection of ink drops is gone out; The ink heating is bubbled with the system of ejection of ink drops; Use hyperacoustic system and through using electrostatic force to draw and the system of ejecting ink water droplet.For the composition for ink that this ink-vapor recording is used, operable is that water-base ink, oily ink and solid (heat fusing) ink is arranged.Among these inks, because water-base ink is most preferably used in their preparation property, operability, tasteless and security.
Tinting material in this this use of inkjet recording ink must satisfy following requirements: it is good at the dissolution with solvents degree; It is record to high-density; Its tone is good; It is for the fastness of light, heat, air, water and chemical; It is fixed well in image receiving material and is difficult to ooze out; Its stability in storage in ink is good; It is nontoxic; Its purity is high; And it is cheap and easy the acquisition.But the tinting material of seeking highly to satisfy all these requirements is unusual difficulty.
Mention various dyestuff or the pigment that are used for ink-vapor recording, and obtained actual use.But, at present, do not know the tinting material that all satisfies above-mentioned requirements.Up to now, known dyestuff and the pigment in this area, those that for example list among the Color Index (C.I.) possibly be difficult to satisfy simultaneously the color harmony fastness, and this ink for inkjet recording needs.
Developed the jetting ink that comprises dyestuff, contriver of the present invention has been found that heterocycle azo type yellow dyes has good weathering resistance (for example, JP-A-2004-168865).
But contriver of the present invention knows that when these dyestuffs of independent use, the problem that occurs so is that when this dyestuff mixed with other dyestuff, the anti-jail property of the light of gray area was not good.
On the other hand, the merits and demerits of magenta dyestuff depends on their type.Particularly; Some magenta dyestuff possibly have good fastness, but causes oozing out in the image in high humidity, and other some possibly have the fastness of M.L.; But the uptake factor of unit weight is low, therefore worsens the ejection stability of jetting ink.Contriver of the present invention knows that single dyestuff of planting can not satisfy all requirements of jetting ink.
Contriver of the present invention knows that also the problem of aqueous black ink is that their image durability is low.Except carbon black; Known seldom black dyes can itself provide for example letter of high quality black image through them; And contriver of the present invention knows in order to form the black image that needs, must mixing have the multiple different dyes of different absorption spectrums separately.But in this case, contriver of the present invention also knows; Fading rate between the mixing colouring agent maybe be different; And when the dyestuff with wide absorption characteristic has faded and their absorbing wavelength when changing, the quality that comprises the image of black so significantly worsens.
For fear of this problem, can consider the method for mixing of different types dyestuff.But, when mixing has one group of dyestuff of same structure, its problem of causing black image of being to be difficult to obtain having high reflection density so.
On the other hand, the water-soluble black ink must satisfy the absorption characteristic of covering wide wavelength region, therefore, is problem, and promptly their solids concn improves easily, and they possibly worsen the ejection stability of ink.
Summary of the invention
An object of the present invention is to provide a kind of ink for inkjet recording and ink group, it has good fastness to light, heat and ozone, and has good ejection stability, and it provides anti-good images of oozing out.
The object of the invention is reached by the ink for inkjet recording and the ink group of following item 1 to 19.
1, a kind of ink-vapor recording is used yellow ink, and it comprises:
Aqueous medium; With
At least two kinds of dyestuffs, wherein said at least two kinds of dyestuffs have independently of one another: λ max is 390nm to 470nm; The ratio of I (λ max+70nm) and I (λ max) is 0.4 or littler, and wherein I (λ max+70nm) is illustrated in the absorbancy under the wavelength of λ max+70nm, and I (λ max) is illustrated in the absorbancy under the wavelength of λ max; And oxidizing potential with respect to SCE greater than 1.0V,
At least a in wherein said at least two kinds of dyestuffs is the dyestuff by formula (Y1) expression:
(A 11-N＝N-B 11)n-L
Wherein
A 11And B 11Expression can substituted heterocyclic group independently of one another; N representes 1 or 2; And L representes Wasserstoffatoms, monovalence substituting group, singly-bound or divalent linker,
Prerequisite is when n is 1, and L is Wasserstoffatoms or monovalence substituting group, and A 11And B 11It all is the monovalence heterocyclic group; When n was 2, L was singly-bound or divalent linker, A 11Be the monovalence heterocyclic group, and B 11It is divalent heterocyclic group.
2, use yellow ink according to the ink-vapor recording of item 1, at least a in wherein said at least two kinds of dyestuffs is by the formula (Y2) or (Y3) dyestuff of expression:
(Y2) P-N＝N-Q
Wherein represent can substituted aryl for P; And Q representes can substituted heterocyclic group,
(Y3) X-N＝N-Y
Wherein represent separately can substituted aryl for X and Y.
3, use yellow ink according to the ink-vapor recording of item 1 or 2, wherein the dyestuff content by formula (Y1) expression is 50% or higher with respect to all the dyestuff total amounts in the yellow ink.
4, a kind of inkjet recording black ink, it comprises:
Aqueous medium; With
At least two kinds of dyestuffs, wherein said at least two kinds of dyestuffs have independently of one another: λ max is 500nm to 700nm; Half breadth in the absorption spectrum of diluting soln is 100nm or higher, and it is 1.0 that described absorption spectrum is made its absorbancy under λ max by stdn,
At least a oxidizing potential in wherein said at least two kinds of dyestuffs is higher than 1.0V with respect to SCE.
5. according to the inkjet recording black ink of item 4, it also comprises the dyestuff that λ max is 350nm to 500nm.
6. according to the inkjet recording black ink of item 4 or 5, wherein at least a dyestuff is the compound by formula (B1) expression:
A 41-N＝N-A 42-N＝N＝A 43
Wherein, A 41, A 42And A 43Expression can substituted aromatic group or heterocyclic group independently of one another; A 41And A 43It is univalent perssad; A 42It is divalent group.
7. according to any one inkjet recording black ink of item 4 to 6, wherein at least a dyestuff is the compound by formula (B2) expression:
P-(N＝N-Qx)y-N＝N-R
Wherein, represent separately can substituted aromatic group for P, Q, R; X representes 1 or bigger integer; Y is 0 or bigger integer.
8, according to the inkjet recording black ink of item 7, the Q in its Chinese style (B2) is the polycyclic aromatic ring.
9. according to the inkjet recording black ink of item 5, be that the dyestuff of 350nm to 500nm is the compound by formula (B1) expression wherein according to the λ max of item 6.
10, a kind of ink-vapor recording is used magenta ink, and it comprises: first dyestuff; With second dyestuff with the structure that is different from first dyestuff, described first dyestuff and second dyestuff have the oxidizing potential greater than 1.0V with respect to SCE independently of one another,
Wherein said first dyestuff is the azoic dyestuff that comprises azo-group, and each end of said azo-group contains heterocycle.
11, use magenta ink according to the ink-vapor recording of item 10, wherein said second dyestuff is an Anthrapyridone dyes.
12, use magenta ink according to the ink-vapor recording of item 10 or 11, wherein said azoic dyestuff is the compound by formula (M1) expression:
Figure G2008101757780D00051
Wherein
A 31Expression 5-unit heterocycle;
B 31And B 32Expression=CR separately 31-or-CR 32=, or B 31And B 32In any expression nitrogen-atoms, and another expression=CR 31-or-CR 32=;
R 35And R 36Represent Wasserstoffatoms, aliphatic group, aromatic group, heterocyclic group, acyl group, carbalkoxy, aryloxy carbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl independently of one another, its each can also contain substituting group;
G 3, R 31And R 32Represent Wasserstoffatoms, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyanic acid, carboxyl, formamyl, carbalkoxy, aryloxy carbonyl, heterocycle oxygen carbonyl, acyl group, hydroxyl, alkoxyl group, aryloxy, heterocyclic oxy group, siloxy-, acyloxy, formamyl oxygen base, alkoxycarbonyloxy, aryloxy carbonyl oxygen base, amino, arylamino, heterocyclic radical amino, amido, urea groups, sulfamyl amino, alkoxycarbonyl amido, aryloxy carbonyl amino, alkyl sulfonyl-amino, arlysulfonylamino, heterocycle sulfuryl amino, nitro, alkylthio, arylthio, alkyl sulphonyl, aryl sulfonyl, heterocycle alkylsulfonyl, alkyl sulphinyl, aryl sulfonyl kia, heterocycle sulfinyl, sulfamyl, sulfo group or heterocycle sulfenyl independently of one another, its each can also be substituted; And
R 31And R 35, or R 35And R 36Can be connected to form 5-or 6-unit ring.
13, use magenta ink according to the ink-vapor recording of item 11 or 12, wherein said Anthrapyridone dyes is the compound by formula (M2) expression:
Figure G2008101757780D00052
Wherein
R representes Wasserstoffatoms, alkyl, hydroxy lower alkyl, cyclohexyl, an alkylamino alkyl or a dialkyl aminoalkyl, or cyanic acid-low alkyl group;
Y representes: the chlorine atom; Hydroxyl; Amino; One alkylamino or dialkyl amido, wherein moieties can contain the substituting group that is selected from sulfonic group, carboxyl and hydroxyl; Aryl alkyl amino; Cycloalkyl amino; Alkoxyl group; Phenoxy, wherein phenyl ring can contain the substituting group that is selected from sulfonic group, carboxyl, kharophen, amino and hydroxyl; Anilino, it can contain one or two substituting group that is selected from sulfonic group, carboxyl; Naphthyl is amino, and wherein naphthyl can be replaced by sulfonic group; Or one alkylamino alkylamino or dialkyl aminoalkyl amino;
X representes crosslinked group; And
Z representes Wasserstoffatoms, alkali metal, alkali earth metal, alkylamino, alkanol amino or ammonium.
14, a kind of ink for inkjet recording group, it comprises: according to item 1 to 3 any one yellow ink, according to any one black ink and at least a according in any one the magenta ink of item 10 to 13 of item 4 to 9.
15, a kind of ink for inkjet recording group, it comprises at least two kinds of magenta inks, and described magenta ink independently comprises oxidizing potential separately with respect to the dyestuff of SCE greater than 1.0V,
Wherein
A kind of magenta ink comprises azoic dyestuff, and it comprises: azo-group; With with two terminal bonded heterocycles of azo group, and
Another kind of magenta ink comprises the dyestuff with the structure that is different from said azoic dyestuff.
16, according to the ink for inkjet recording group of item 15, wherein at least a dyestuff in described at least two kinds of magenta inks is by the dyestuff of representing according to the formula (M1) of item 12 or by the dyestuff of representing according to the formula (M2) of item 13.
17, according to the ink for inkjet recording group of item 15 or 16, wherein said at least two kinds of magenta inks at least a comprises by the dyestuff according to formula (M1) expression of item 12.
18, according to any one ink for inkjet recording group of item 15 to 17, at least a in wherein said at least two kinds of magenta inks comprises by the dyestuff according to formula (M2) expression of item 13.
19, according to any one ink for inkjet recording group of item 15 to 18, at least a the comprising in wherein said at least two kinds of magenta inks: by dyestuff according to formula (M1) expression of item 12; With by dyestuff according to the expression of the formula (M2) of item 13.
The present invention has obtained ink-vapor recording with yellow ink and ink group, and at any time, when they were pure color or mixture colors, it always had good weathering resistance and good jetting stability.
Use two or more dissimilar black dyess through combination, the present invention has obtained having the good absorption characteristic and has had flat spectrographic black ink.Therefore, the present invention has obtained highdensity black image, and has solved up to now in association area about them the problem that the black ink discussed aspect stable exists.
Black ink of the present invention and ink group have good ink jet stability, and the video high density with good durability is provided.
In addition, the present invention has obtained magenta ink and ink group that ink-vapor recording is used, and it provides the image with good shelf-stability, even and its after standing storage, also always have good ejection stability.
Detailed Description Of The Invention
Below, describe the present invention in detail.
The λ max of ink inside of the present invention is a wavelength of measuring the aqueous solution demonstration maximum absorbance of ink inside at absorption spectrum, and wherein the aqueous solution of dilute with water ink is so that the maximum absorbance that has is 1 to 2.
Yellow ink among the present invention is that λ max is the ink that 390nm to 470nm and half breadth are lower than 100nm.
Preferably, the fastness that the yellow dyes that uses among the present invention is considered them particularly the oxidizing potential of the anti-jail property of ozone greater than 1.00V (with respect to SCE).More preferably the oxidizing potential of these dyestuffs is greater than 1.1V (with respect to SCE), most preferably greater than 1.2V (with respect to SCE).Consider their type, especially preferably satisfy the azoic dyestuff of above-mentioned physics requirement.
Any technician of this area can measure the oxidizing potential (Eox) of dyestuff easily.The method of measuring is described in for example P.Delahay, New Instrumental Methods in Electrochemistry, 1954, Interscience Publishers; A.J.Bard etc., Electrochemical Methods, 1980, John Wiley & Sons; A.Fujishima etc., Electrochemical Measurement Methods, 1984, among the Gihodo Publishing.
Particularly, can measure oxidizing potential as follows: with sample dissolution to be analyzed in solvent such as N or acetonitrile to concentration be 1 * 10 -6To 1 * 10 -2Mol/ liter, this solvent contain supporting electrolyte such as sodium perchlorate and perchloric acid tetrapropyl ammonium, and measure its oxidizing potential value with respect to SCE (SCE) through cyclic voltammetry.Because the influence of liquid junction potential or the resistance of sample solution it on, the value of oxidizing potential can deviation dozens of millivolt, but it can use standard model (for example, quinhydrones) to calibrate.In the sort of mode, the repeatability of the potential value of guaranteeing to measure thus.
In the present invention, comprising 0.1 mole of dm -3Supporting electrolyte, (at this, the concentration of dyestuff is 0.001 mole of dm in the perchloric acid tetrapropyl ammonium N -3) the middle oxidizing potential (with respect to SCE) of measuring dyestuff, to limit this current potential clearly.
The electronic migration property of Eox value representation from the sample to the electrode.Sample (have oxidizing potential those) with big Eox value is meant that electronics more is difficult to move to electrode from them, or promptly, sample more is difficult to oxidized.With respect to the structure of compound, introduce electron-withdrawing group and make compound have oxidizing potential, make them have negative oxidizing potential and introduce electron-donating group.In the present invention, it is desirable to electron-withdrawing group is introduced the skeleton of dyestuff, make dyestuff have oxidizing potential thus, so that reduce dyestuff and ozone, a kind of reactivity of electrophilic reagent.
Except having good fastness, the yellow dyes that also it is desirable to be used for the present invention has good color tone, and more preferably, the long wavelength side of the absorption spectrum pattern of dyestuff has the afterbody profile of rapid end.Therefore; The λ max that it is desirable to yellow dyes is 390-470nm, the absorbancy at λ max+70nm place, I (λ max+70nm) with in the absorbancy at λ max place; I's (λ max) is 0.4 or littler than degree I (λ max+70nm)/I (λ max); More preferably 0.2 or littler, more more preferably 0.15 or littler, more more preferably 0.10 or littler.
Can regulate the ratio of absorbancy with above-mentioned suitable mode through so concrete design dye molecule so that two azo components can be even as far as possible with the transition moment that sandwiches the coupling component that contains azo-group wherein.The absorbing wavelength of definition and absorbancy are those that in solvent (water or ETHYLE ACETATE), measure here.
For the oxidizing potential and the dyestuff of absorbency characteristics that satisfy as above, use those of following formula (Y1) in the present invention:
(Y1) (A 11-N＝N-B 11)n-L
In (Y1), A 11And B 11The heterocyclic group that expression independently of one another can be optionally substituted.Preferred heterocycle is 5-unit or 6-unit heterocycle.It can have the polynuclear plane of single ring architecture or two or more mutual condensed rings; Maybe can be aromatic heterocycle or non-aromatic heterocyclic.Preferably, constitute the heterocyclic heterocyclic atom and comprise N, O and S atom.N is selected from 1 or 2 integer, and more preferably 2.L representes and A 11Or B 11At its suitable any position bonded substituting group.When n was 1, L was singly-bound or divalent linker so.When n was 2, two A can be identical or different so, and two B can be identical or different.
In formula (Y1), for A 11Heterocycle any in preferably following: 5-pyrazolone, pyrazoles, triazole 、 azolactone 、 isoxazolidinone, malonylurea, pyridone, pyridine, rhodanine, pyrazolidinedione, Pyrazolopyridine ketone, Meldrum ' s acid; Or condensed heterocycle, described annelated heterocycles is to form through these heterocycles and any other aromatic ring or heterocyclic condensation.Especially, preferred 5-pyrazolone, 5-amino-pyrazol, pyridone, 2,6-diamino-pyridine and pyrazolo azole, more preferably 5-amino-pyrazol, 2-hydroxyl-6-pyridone and Pyrazolotriazole.
For B 11Heterocycle; Preferably pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline 99.9, quinazoline, cinnolines, 2, quinoxaline, pyrroles, indoles, furans, cumarone, thiophene, thionaphthene, pyrazoles, imidazoles, benzoglyoxaline, triazole 、 oxazole 、 isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazoles, benzoisoxazole, tetramethyleneimine, piperidines, piperazine, tetrahydroglyoxaline, thiazoline.In these, more preferably pyridine, quinoline, thiophene, thionaphthene, pyrazoles, imidazoles, benzoglyoxaline, triazole 、 oxazole 、 isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazoles, benzoisoxazole; And more preferably quinoline, thiophene, pyrazoles, thiazole, benzoxazole, benzoisoxazole, isothiazole, imidazoles, benzothiazole, thiadiazoles again; And more preferably pyrazoles, benzothiazole, benzoxazole, imidazoles, 1,2 again, 4-thiadiazoles, 1,3,4-thiadiazoles.
A 11And B 11Can be substituted, the halogen atom of mentioning below their substituent instance comprises, alkyl, naphthenic base, aralkyl, alkenyl, alkynyl, aryl, heterocyclic group, cyanic acid, hydroxyl, nitro, alkoxyl group, aryloxy, siloxy-, heterocyclic oxy group, acyloxy, formamyl oxygen base, alkoxycarbonyloxy, aryloxy carbonyl oxygen base, amino, amido, amino carbonyl amino, alkoxycarbonyl amido, aryloxy carbonyl are amino, sulfamyl is amino, alkyl sulfonyl-amino, arlysulfonylamino, sulfydryl, alkylthio, arylthio, heterocycle sulfenyl, sulfamyl, alkyl sulphinyl, aryl sulfonyl kia, alkyl sulphonyl, aryl sulfonyl, acyl group, aryloxy carbonyl, carbalkoxy, formamyl, imido grpup, phosphino-, phosphinyl, phosphinyl oxygen base, phosphinyl are amino, silyl and ionic hydrophilic radical.
Comprising for the monovalence substituting group of L can be at A 11And B 11In substituted substituting group and below the ionic hydrophilic radical mentioned.
For the divalent linker of L comprise alkylidene group, arylidene, heterocycle residue ,-CO-,-SOn-(n is 0,1 or 2) ,-NR-(R is Wasserstoffatoms, alkyl or aryl) ,-other divalent group of O-and the combination of these linking groups.These groups can have substituting group, for example for A 11And B 11Above mentioned those and below the ionic hydrophilic radical mentioned.
Under the situation of dyestuff as water-soluble dye of use formula (Y1), preferably these dyestuffs contain at least one ionic hydrophilic radical in molecule.Ionic hydrophilic radical comprises for example sulfo group, carboxyl, phosphono and quaternary ammonium group.For described ionic hydrophilic radical, preferably carboxyl, phosphono and sulfo group, more preferably carboxyl and sulfo group.Most preferably, at least one ionic hydrophilic radical is a carboxyl.Carboxyl, phosphono and sulfo group can form salt.The instance of the salifiable counter ion of shape is ammonium ion, alkalimetal ion (for example lithium ion, sodium ion, potassium ion) and organic cation (for example tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl phosphonium ion).For described counter ion, preferably alkalimetal ion.
In the dyestuff of formula (Y1), preferably wherein by following formula (Y4), (Y5) or (Y6) expression A 11-N=N-B 11Those of part.
(Y4)
R wherein 1And R 3Represent Wasserstoffatoms, cyanic acid, alkyl, naphthenic base, aralkyl, alkoxyl group, alkylthio, arylthio, aryl or ionic hydrophilic radical separately; R2 representes Wasserstoffatoms, alkyl, naphthenic base, aralkyl, formamyl, acyl group, aryl or heterocyclic group; And R4 representes heterocyclic group.
(Y5)
Figure G2008101757780D00111
Wherein R5 representes Wasserstoffatoms, cyanic acid, alkyl, naphthenic base, aralkyl, alkoxyl group, alkylthio, arylthio, aryl or ionic hydrophilic radical, Za representes-N=,-NH-or-C (R11)=; Zb and Zc represent independently of one another-N=or-C (R11)=; R11 representes Wasserstoffatoms or nonmetal substituting group, and R6 representes heterocyclic group.
(Y6)
Figure G2008101757780D00112
Wherein R7 and R9 represent Wasserstoffatoms, cyanic acid, alkyl, naphthenic base, aralkyl, aryl, alkylthio, arylthio, carbalkoxy, formamyl or ionic hydrophilic radical independently of one another; R8 representes Wasserstoffatoms, halogen atom, alkyl, alkoxyl group, aryl, aryloxy, cyanic acid, amido, sulfuryl amino, alkoxycarbonyl amido, urea groups, alkylthio, arylthio, carbalkoxy, formamyl, sulfamyl, alkylsulfonyl, acyl group, alkylamino, arylamino, hydroxyl or ionic hydrophilic radical; R10 representes heterocyclic group.
In formula (Y4), (Y5) with (Y6), the alkyl that is used for R1, R2, R3, R5, R7, R8 and R9 comprises substituted alkyl and unsubstituted alkyl.Preferably, alkyl contains 1 to 20 carbon atom.The substituent instance of alkyl is hydroxyl, alkoxyl group, cyanic acid, halogen atom and ionic hydrophilic radical.The instance of alkyl is methyl, ethyl, butyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxy ethyl, cyano ethyl, trifluoromethyl, 3-sulfo group propyl group and 4-sulfo group butyl.
The naphthenic base that is used for R1, R2, R3, R5, R7, R8 and R9 comprises substituted naphthenic base and unsubstituted naphthenic base.Preferred naphthenic base contains 5 to 12 carbon atoms.The substituent instance that is used for naphthenic base is ionic hydrophilic radical.The instance of naphthenic base is a cyclohexyl.The aralkyl that is used for R1, R2, R3, R5, R7, R8 and R9 comprises substituted aralkyl and unsubstituted aralkyl.Preferably, naphthenic base contains 7 to 20 carbon atoms.The substituent instance that is used for aralkyl is ionic hydrophilic radical.The instance of aralkyl is benzyl and 2-styroyl.
The aryl that is used for R1, R2, R3, R5, R7, R8 and R9 comprises substituted aryl and unsubstituted aryl.Preferably, aryl contains 6 to 20 carbon atoms.The substituent instance that is used for aryl comprises alkyl, alkoxyl group, halogen atom, alkylamino and ionic hydrophilic radical.The instance of aryl comprise phenyl, p-methylphenyl, p-methoxyphenyl, Chloro-O-Phenyl and-(3-sulfo group third amino) phenyl.
The alkylthio that is used for R1, R2, R3, R5, R7, R8 and R9 comprises substituted alkylthio and unsubstituted alkylthio.Preferably, alkylthio contains 1 to 20 carbon atom.The substituent instance that is used for alkylthio is ionic hydrophilic radical.The instance of alkylthio is methyl sulphur and ethyl sulphur.The alkylthio that is used for R1, R2, R3, R5, R7, R8 and R9 comprises substituted arylthio and unsubstituted arylthio.Preferred arylthio contains 6 to 20 carbon atoms.The substituent instance that is used for arylthio is alkyl and ionic hydrophilic radical.The instance that is used for arylthio is phenyl thio group and right-tolyl thio group.
The heterocyclic group that is used for R2 is preferably 5-or 6-unit, and it can be that any other ring condenses.For constituting heterocyclic heteroatoms, preferably N, S and O.The heterocycle that is used for this group can be aromatic heterocycle or non-aromatic heterocyclic.Heterocycle can also be substituted.For the substituting group of this ring, refer to above mentioned those of aryl of being used for.Preferably, heterocycle is first, the nitrogenous aromatic heterocycle of 6-, and its preferred embodiment is triazine, pyrimidine and 2.
The halogen atom that is used for R8 comprises fluorine atom, chlorine atom and bromine atoms.The alkoxyl group that is used for R1, R3, R5 and R8 comprises substituted alkoxyl group and unsubstituted alkoxyl group.Preferably, alkoxyl group contains 1 to 20 carbon atom.The substituent instance that is used for alkoxyl group is hydroxyl and ionic hydrophilic radical.The instance of alkoxyl group is methoxyl group, oxyethyl group, isobutoxy, methoxy ethoxy, hydroxyl-oxethyl and 3-carboxyl propoxy-.
The aryloxy that is used for R8 comprises substituted aryloxy and unsubstituted aryloxy.Preferably, aryloxy contains 6 to 20 carbon atoms.The substituent instance that is used for aryloxy is alkoxyl group and ionic hydrophilic radical.The instance of aryloxy is phenoxy, right-methoxyl group phenoxy and neighbour-methoxyl group phenoxy.The instance that is used for the amido of R8 comprises substituted amido and unsubstituted amido.Preferably, amido contains 2 to 20 carbon atoms.The substituent instance that is used for amido is ionic hydrophilic radical.The instance of amido is kharophen, propionamido, benzamido-and 3,5-disulfobenzene formamido group.
The sulfuryl amino that is used for R8 comprises substituted sulfuryl amino and unsubstituted sulfuryl amino.Preferably, sulfuryl amino contains 1 to 20 carbon atom.The instance of sulfuryl amino is that methyl sulphonyl is amino and ethylsulfonyl is amino.The alkoxycarbonyl amido that is used for R8 comprises substituted alkoxycarbonyl amido and unsubstituted alkoxycarbonyl amido.Preferably, alkoxycarbonyl amido contains 2 to 20 carbon atoms.The substituent instance that is used for alkoxycarbonyl amido is ionic hydrophilic radical.The instance of alkoxycarbonyl amido is that ethoxycarbonyl is amino.
The urea groups that is used for R8 comprises substituted urea groups and unsubstituted urea groups.Preferably, urea groups contains 1 to 20 carbon atom.The substituent instance that is used for urea groups is alkyl and aryl.The instance of urea groups is a 3-methyl urea groups, 3,3-dimethyl-urea groups and 3-phenyl urea groups.
The carbalkoxy that is used for R7, R8 and R8 comprises substituted carbalkoxy and unsubstituted carbalkoxy.Preferably, carbalkoxy contains 2 to 20 carbon atoms.The substituent instance that is used for carbalkoxy is ionic hydrophilic radical.The instance of carbalkoxy is methoxycarbonyl and ethoxycarbonyl.
The formamyl that is used for R2, R7, R8 and R9 comprises substituted formamyl and unsubstituted formamyl.The substituent instance that is used for formamyl is an alkyl.The sulfamyl that is used for R8 comprises substituted sulfamyl and unsubstituted sulfamyl.The substituent instance that is used for sulfamyl is an alkyl.The instance of sulfamyl is dimethylamino alkylsulfonyl and two-(2-hydroxyethyl) sulfamyl.
The alkylsulfonyl that is used for R8 is methylsulfonyl and benzenesulfonyl.The acyl group that is used for R2 and R8 comprises substituted acyl group and unsubstituted acyl.Preferably, acyl group contains 1 to 20 carbon atom.The substituent instance that is used for acyl group is ionic hydrophilic radical.The instance of acyl group is ethanoyl and benzoyl-.
The amino that is used for R8 comprises substituted amino and unsubstituted amino.Being used for amino substituent instance is alkyl, aryl and heterocyclic group.Amino instance is methylamino, diethylamino, anilino and 2-chloroanilino.
The heterocyclic group that is used for R4, R6 and R10 can be used for B with formula (Y1) 11Identical optional substituted heterocyclic group is identical.For its preferred embodiment, preferred instance and preferred examples again refer to the above mentioned B of being used for 11Those of group.Particularly, the substituting group that is used for heterocyclic group comprises for example ionic hydrophilic radical, contains alkyl, aryl, alkylthio, arylthio, halogen atom, cyanic acid, sulfamyl, sulfoamino-(sulfonamino), formamyl and the amido of 1 to 12 carbon atom.Alkyl, aryl etc. can further be substituted separately.
In formula (Y5), Za representes-N=,-NH-or-C (R11)-; Zb and Zc represent independently of one another-N=or-C (R11); And R11 representes Wasserstoffatoms or nonmetal substituting group.For the nonmetal substituting group of R11, preferably cyanic acid, naphthenic base, aralkyl, aryl, alkylthio, arylthio and ionic hydrophilic radical.These substituting groups can have and the identical implication of those substituting groups that is used for R1, and their preferred embodiment also can be that those are identical with R1 substituent.What mention below is the instance that comprises the heterocyclic skeleton of two 5 yuan of rings in the formula (Y5).
Figure G2008101757780D00141
The substituent instance that is used for above-mentioned optional substituted group refers to for the heterocycle A in the formula (Y1) 11And B 11Mentioned those of optional substituted group.
When the dyestuff of formula (Y4) to (Y6) was water-soluble dye, so suitable was that they contain at least one ionic hydrophilic radical in molecule.Such preferred coloring agent comprises those of formula (Y4) to (Y6); Wherein any one of R1, R2, R3, R5, R7, R8 and R9 is ionic hydrophilic radical; And those of formula (Y4) to (Y6), wherein R1 to R11 further has ionic hydrophilic radical separately as substituent dyestuff.Ionic hydrophilic radical comprises sulfo group, carboxyl, phosphono and quaternary ammonium group.For ionic hydrophilic radical, preferably carboxyl, phosphono and sulfo group; More preferably carboxyl and sulfo group.Carboxyl, phosphono and sulfo group can form salt.The instance of the salifiable counter ion of shape comprises ammonium ion, alkalimetal ion (for example lithium ion, sodium ion, potassium ion) and organic cation (for example tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl phosphonium ion).For counter ion, alkalimetal ion preferably.
In formula (Y4), (Y5) and dyestuff (Y6), those of preferred formula (Y4), more preferably those of following formula (Y4-1):
Figure G2008101757780D00151
R wherein 21And R 23Represent Wasserstoffatoms, alkyl, naphthenic base, aralkyl, alkoxyl group or aryl separately; R 22Expression Wasserstoffatoms, aryl or heterocyclic group; One of X and Y represent nitrogen-atoms, another expression-CR 24R 24Expression Wasserstoffatoms, halogen atom, cyanic acid, alkyl, alkylthio, alkyl sulphonyl, alkyl sulphinyl, alkoxyl group oxygen carbonyl, formamyl, alkoxyl group, aryl, arylthio, aryl sulfonyl, aryl sulfonyl kia, aryloxy or amido.These substituting groups can further be substituted.
The preferred embodiment of the dyestuff that uses among the present invention is described among JP-A-2004-83903,2003-277662,2003-277661,2003-128953 and the 2003-41160.Especially, the compound of mentioning below is preferred in the present invention.But, be used for dyestuff of the present invention and be not limited to these.These compounds can be mentioned the patent aspect and prepare with reference to JP-A2-24191 and 2001-279145 with reference to top.
Figure G2008101757780D00161
Figure G2008101757780D00162
Figure G2008101757780D00171
Figure G2008101757780D00172
Figure G2008101757780D00181
Figure G2008101757780D00182
Figure G2008101757780D00183
Figure G2008101757780D00184
Figure G2008101757780D00191
Figure G2008101757780D00192
Figure G2008101757780D00201
Figure G2008101757780D00202
Figure G2008101757780D00211
Figure G2008101757780D00212
Figure G2008101757780D00221
Figure G2008101757780D00222
Figure G2008101757780D00231
Figure G2008101757780D00232
Figure G2008101757780D00241
Figure G2008101757780D00242
Figure G2008101757780D00243
Figure G2008101757780D00244
Figure G2008101757780D00252
Figure G2008101757780D00253
Figure G2008101757780D00254
Figure G2008101757780D00262
Figure G2008101757780D00271
Figure G2008101757780D00281
Preferably, yellow ink of the present invention except that above-mentioned dyestuff, also comprise by formula (Y2) or (Y3) expression and oxidizing potential greater than the another kind of yellow ink of 1.0V (with respect to SCE).
(Y2)?P-N＝N-Q
Wherein P representes optional substituted aryl; And O representes optional substituted heterocyclic group,
(Y3)?X-N＝N-Y
Wherein X and Y represent optional substituted aryl separately.
In formula (Y2), Q representes optional substituted heterocyclic group, and those of its details and above mentioned formula (Y1) are identical.Each optional naturally substituted aryl of X in P in formula (Y2) and the formula (Y1) and Y.In formula (Y2), preferably not that the group of heterocyclic group is an aryl.The preferred embodiment of aryl is phenyl, substituted phenyl, naphthyl and substituted naphthyl.
Can various types of substituting groups be introduced in the compound that here uses.Commutable substituent instance is that alkyl (preferably contain 1 to 20, more preferably 1 to 12, more preferably 1 to 8 carbon atom, for example methyl, ethyl, sec.-propyl, the tertiary butyl, n-octyl, positive decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl again), alkenyl (preferably contain 2 to 20, more preferably 2 to 12; More preferably 2 to 8 carbon atoms, for example vinyl, allyl group, crotyl, 3-pentenyl again), alkynyl (preferably contain 2 to 20, more preferably 2 to 12, more preferably 2 to 8 carbon atoms, for example propargyl, 3-pentynyl again), aryl (preferably contain 6 to 30; More preferably 6 to 20, more preferably 6 to 12 carbon atoms, for example phenyl, right-aminomethyl phenyl, naphthyl again), amino (preferably contain 0 to 20 carbon atom, more preferably 0 to 12, more more preferably 0 to 6 carbon atom, for example amino, methylamino, dimethylamino, diethylamino, diphenyl amino, dibenzyl amino), alkoxyl group (preferably contain 1 to 20; More preferably 1 to 12, more preferably 1 to 8 carbon atom, for example methoxyl group, oxyethyl group, butoxy again), aryloxy (preferably contain 6 to 20, more preferably 6 to 16, more preferably 6 to 12 carbon atoms again; For example phenoxy, 2-naphthyloxy), acyl group (preferably contain 1 to 20, more preferably 1 to 16, more preferably 1 to 12 carbon atom, for example ethanoyl, benzoyl-, formyl radical, valeryl again), carbalkoxy (preferably contain 2 to 20; More preferably 2 to 16, more preferably 2 to 12 carbon atoms, for example methoxycarbonyl, ethoxycarbonyls again), aryloxy carbonyl (preferably contains 7 to 20, more preferably 7 to 16; More preferably 7 to 10 carbon atoms, for example carbobenzoxies again), acyloxy (preferably contain 2 to 20, more preferably 2 to 16, more preferably 2 to 10 carbon atoms again; For example acetoxyl group, benzoyloxy), amido (preferably contain 2 to 20, more preferably 2 to 16, more preferably 2 to 10 carbon atoms, for example kharophen, benzamido-s again), alkoxycarbonyl amido (preferably contain 2 to 20; More preferably 2 to 16, more preferably 2 to 12 carbon atoms again, for example methoxycarbonyl is amino), aryloxy carbonyl is amino (preferably contains 7 to 20, more preferably 7 to 16; More preferably 7 to 12 carbon atoms again, for example carbobenzoxy is amino), sulfuryl amino (preferably contain 1 to 20, more preferably 1 to 16, more preferably 1 to 12 carbon atom again; For example methylsulfonyl is amino, benzenesulfonyl is amino), sulfamyl (preferably contain 0 to 20, more preferably 0 to 16, more preferably 0 to 12 carbon atom, for example sulfamyl, methyl sulfamyl, dimethylamino alkylsulfonyl, phenyl sulfamoyl base again), formamyl (preferably contain 1 to 20; More preferably 1 to 16, more preferably 1 to 12 carbon atom, for example formamyl, methylamino formyl radical, diethylamino formyl radical, phenyl amino formyl radical again), alkylthio (preferably contains 1 to 20, more preferably 1 to 16; More preferably 1 to 12 carbon atom, for example methylthio group, ethylmercapto group again), arylthio (preferably contain 6 to 20, more preferably 6 to 16, more preferably 6 to 12 carbon atoms again; Thiophenyl for example), alkylsulfonyl (preferably contain 1 to 20, more preferably 1 to 16, more preferably 1 to 12 carbon atom, for example methylsulfonyl, tosyl group again), sulfinyl (preferably contain 1 to 20; More preferably 1 to 16, more preferably 1 to 12 carbon atom, for example methanesulfinyl, benzenesulfinyl again), urea groups (preferably contains 1 to 20, more preferably 1 to 16; More preferably 1 to 12 carbon atom, for example urea groups, methyl urea groups, phenyl urea groups again), the phosphinylidyne amido (preferably contain 1 to 20, more preferably 1 to 16, more preferably 1 to 12 carbon atom again; For example diethylammonium phosphinylidyne amido, phenyl phosphinylidyne amido), hydroxyl, sulfydryl, halogen atom (for example fluorine, chlorine, bromine, iodine), cyanic acid, sulfo group, carboxyl, nitro, hydroxamic acid base, sulfino, diazanyl, imino-, heterocyclic group (preferably contain 1 to 30, more preferably 1 to 12 carbon atom, wherein heteroatoms is selected from nitrogen, oxygen and sulphur atom, particularly; Like imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl-, benzothiazolyl, carbazyl and azepine base (axepinyl)), silyl (preferably contain 3 to 40, more preferably 3 to 30, more preferably 3 to 24 carbon atoms, for example trimethyl silyl, triphenyl silyl again).These substituting groups can be by further replacement.If have, two or more substituting groups can be identical or different.If possible, substituting group can mutually combine and form ring.
What mention below is the formula (Y2) used among the present invention and (Y3) preferred embodiment of dyestuff, and still, the present invention should not limited by these.
YJ-1
C.I. direct yellow 86
YJ-2
C.I. direct yellow 120
Figure G2008101757780D00311
Figure G2008101757780D00321
Ink-vapor recording among preferred the present invention is total up to 0.2 to 20 weight % with the amount that yellow ink comprises above-mentioned azoic dyestuff, more preferably 0.5 to 15 weight %.Again more preferably, the dyestuff of formula (Y1) accounts at least 50 weight % of dyestuff in yellow ink.
Preferably, black dyes ink of the present invention comprises at least two kinds of dyestuffs (L), and the λ max of every kind of dyestuff is 500nm to 700nm, and is normalized in the absorption spectrum that absorbancy under λ max is 1.0 diluting soln half breadth (W at it λ, 1/2) and be 100nm or bigger (being preferably 120nm to 500nm, more preferably 120nm to 350nm).
Preferably, the oxidizing potential of at least a dyestuff (L) that in black dyes, uses is greater than 1.0V (with respect to SCE), more preferably greater than 1.1V (with respect to SCE), again more preferably greater than 1.2V (with respect to SCE), most preferably greater than 1.25V (with respect to SCE).
Any technician of the present invention can easily measure the oxidizing potential (Eox) of dyestuff.In order to measure it, adoptablely here be: for example, in the aqueous solution with dissolving dyestuff wherein or the cyclic voltammetry in the water mixed solvent (CV), change disk electrode method or comb poles method.
In the present invention, in aqueous medium mixing and dissolving or dispersed dye (L) with the preparation black ink.Preferably, the dyestuff of mentioning below black ink comprises.
Can separately dyestuff (L) be used for black ink, as long as it can be through realizing high-quality " close " black image (wherein irrelevant with the light source of observing, B, G and R tone none are strengthened) itself.But, usually, dyestuff and any other dye combinations that can cover the zone that absorbs through dyestuff (L) difference.Particularly, it is desirable to dyestuff (L) and dyestuff (S) combination that in yellow area, has main absorption (and λ max is 350nm to 500nm).Depend on the circumstances, dyestuff (L) can also with any other dye combinations to form black ink.
Preferably, black dyes of the present invention comprises the azoic dyestuff of formula (B1).The azoic dyestuff of formula (B1) comprises dyestuff (L), and its λ max is 500nm to 700nm, and is 100nm at least at its half breadth that is normalized in the absorption spectrum that absorbancy is 1.0 diluting soln.In addition, the azoic dyestuff of formula (B1) comprises that also λ max is the dyestuff (S) of 350nm to 500nm.Preferably, at least a dyestuff (L) in black ink of the present invention is the dyestuff of formula (B1), and more preferably, at least a dyestuff (L) and at least a dyestuff (S) all are the dyestuffs of formula (B1).Again more preferably, the dyestuff of formula (B1) accounts at least 50 weight % of all dyestuffs in ink.
Preferably, black dyes of the present invention also comprises the another kind of azoic dyestuff of formula (B2) except that above mentioned dyestuff.Preferably, the dyestuff of formula (B2) is corresponding to dyestuff (L), and the λ max of described dyestuff (L) is 500nm to 700nm, and is 100nm at least at its half breadth that is normalized in the absorption spectrum that absorbancy is 1.0 diluting soln.Like the dyestuff of cotype (B1), the dyestuff of formula (B2) can also be that λ max is the dyestuff (S) of 350nm to 500nm.
The dyestuff of formula (B2) is the dyestuff that is sorted in the aromatics two azoic dyestuff groups, and is different from the dyestuff of formula (B1), and this is the compound be made up of the hydrocarbon ring fully of color development position wherein.The case description of dyestuff is in Japanese Patent 3,428, and 178 and 2,428,263 and in CN136830-A.
In formula (B1) and dyestuff (B2), preferred especially those that use among the present invention with high oxidation potential and high associating intensity.For this purpose; It is desirable to so design dyestuff,, and can reduce the π-electron density that exists in the main aromatic ring so that more substantial electron-withdrawing group can be in molecule; Or so design; Can promote associating simple structure so that molecule can have, and have group conduct intermolecular substituting group wherein a plurality of, strong interaction, to cause molecular association.
The group of strong interaction is a hydrogen bonding group for example, and preferably they be-COOH ,-OH ,-SO 2NH-,-CONH-, more preferably contain-CONH-.It is desirable to dye molecule and have a plurality of this hydrogen bonding groups therein.Also preferably, the simple structure group that dye molecule is a large amount of can be easily overlapped through these molecules of this group.Described group is for example xenyl and naphthyl.
Dyestuff as for high associativity; When the concentration of aqueous solution at dyestuff in the groove that in photoconduction length is 1cm is when measuring dyestuff spectrum under 0.025mmol/ rises; With when at the concentration of aqueous solution of dyestuff being 50mmol/ rise when down measuring dyestuff spectrum in the groove that is 5cm in photoconduction length, λ max different each other in spectrum so with absorbancy.Particularly, absorbancy changes sharp.Usually, when the absorbancy of highly concentrated solution during divided by the absorbancy of low concentration solution, so preferred it obtain at least 1.0, more preferably at least 1.2, more more preferably at least 1.3.
In the present invention, the mixture that obtains through mixing black dyes and dissolving or dispersion in aqueous medium prepares black ink.The preferred properties of inkjet recording black ink is: 1) its weathering resistance good and/or 2) even do not lose the black balance at the back image that fades yet.In order to make black ink of the present invention can have preferred properties, it is desirable to black ink and satisfy following conditions:
Use black ink, print 48-spot size, the black square symbol of JIS flip-flop 2223, and measure their reflection density (D through state A spectral filter (vision spectral filter) Vis).This is the initial density of sample.Being equipped with an instance of the reflection densitometer of state A spectral filter is the X-Rite photodensitometer.In order to measure " black " density wherein, with data measured D VisBe called standard and observe reflection density.The ozone fading trier that uses institute all to produce 5ppm if having time makes printed product pressure armpit look.Reflection density (D to the sample that fades Vis) 80% o'clock needed time (t) of reaching the initial density of primary sample carries out timing, and by correlation: 0.8=exp (k VisT) derive pressure fading rate constant (k Vis).
Preferably, the velocity constant (k of the black ink among the present invention Vis) be 5.0 * 10 to the maximum -2[hour -1], more preferably be 3.0 * 10 to the maximum -2[hour -1], more preferably be 1.0 * 10 to the maximum again -2[hour -1].
Use black ink of the present invention, print 48-spot size, the black square symbol of JIS flip-flop 2223, and measure except that D through state A spectral filter VisThe reflection density of outer three kinds of color C (cyan), M (carmetta) and Y (yellow).Data measured is initial density D thus R, D GAnd D BThese data D R, D G, D BBe meant C reflection density through red filter, the M reflection density through green filter and the Y reflection density through blue filter respectively.With with top same way as, the ozone fading trier that uses institute all to produce 5ppm if having time fades the printed product pressure.Reflection density D from the sample that fades R, D GAnd D BReach the time of the initial density 80% of original sample, with top same way as, derive and force fading rate constant (k R, k G, k B).The peak of three kinds of velocity constants and the ratio of minimum value (R) (for example, are worked as k RBe peak and k GWhen being minimum value, R=k R/ k G) preferably be at most 1.2, more preferably be at most 1.1, more preferably be at most 1.05 again.
In " the having the 48-spot size of JIS flip-flop 2223, the printed product of black square symbol on it " of using in the above, print image to size is the size of complete cover butter machine hole, so that it can be enough to density measurement.
In order to make the black dyes that uses in the black ink of the present invention have good color tone, fastness and stability in storage, it is desirable to dyestuff and satisfy following physicals:
Performance 1: when the maximum absorption wavelength of absorption spectrum that will be in DMF is called λ max (DNF), 680nm so>λ max (DNF) >=570nm.
Performance 2: oxidizing potential is a positively charged, greater than 1.0V (with respect to SCE).
Performance 3: when the maximum absorption wavelength of absorption spectrum that will be in water is called λ max (water), I λ max (DNF)-λ max (water) I >=30nm so.
Performance 4: when the molar absorption coefficient in DMF is called ε (DMF) and the molar absorption coefficient in water is called ε (water), ε (water)/ε (DMF)≤0.9 so.
Performance 5: in the absorption spectrum of in water, measuring; When the absorbancy in the maximum absorption wave strong point of association dyestuff is called Abs (association); And when the absorbancy of measuring among the DNF in the maximum absorption wave strong point of monomer absorption spectrum is called Abs (monomer), Abs (monomer)/Abs (association)≤0.75 so.
In addition, when dyestuff did not dissolve in 100% DMF, dyestuff dissolved in water (10 weight % or lower DMF solvent), with preparation solution, and with rare this solution of DMF, with the preparation diluting soln.Observed value in this diluting soln is defined as the value among the DMF.
Satisfy above-mentioned physicals, black dyes can have good black color and have anti-jail property of good light and the anti-jail property of ozone, and in addition, their stability in storagies in ink are good.Therefore, such black dyes preferably uses in the present invention.Preferably, ink group of the present invention is characterised in that as follows with ink:
Particularly, use at least two kinds of inks, 15 grades of gradient printed sample of formation are extremely at most up to 30ml/m 2Degree.The peak of pattern reflection density (this is the density value in the saturated position measurement of reflection density, even and the density value that when improving the stamping ink water yield, can not improve again) is than the height on the high density ink side.
Ink group of the present invention satisfy in these conditions any one or a plurality of.Preferably, it satisfies all these conditions.
The dyestuff of formula (B1) is described below:
(B1)A 41-N＝N-A 42-N＝N＝A 43
A wherein 41, A 42And A 43Independent separately expression can be by further substituted aromatic group or heterocyclic group; A 41And A 43It is univalent perssad; And A 42It is divalent group.
More preferably the azoic dyestuff in the formula (B1) is those of following formula (B1-A):
Figure G2008101757780D00371
In formula (B1-A), B 41And B 42Expression=CR separately 41-or-CR 42=, or any one is nitrogen-atoms and another is=CR in them 41-or-CR 42=.
G 4, R 41And R 42Independent separately expression Wasserstoffatoms; Halogen atom; Aliphatic group; Aromatic group; Heterocyclic group; Cyanic acid; Carboxyl; Formamyl; Carbalkoxy; Aryloxy carbonyl; Heterocycle oxygen carbonyl; Acyl group; Hydroxyl; Alkoxyl group; Aryloxy; Heterocyclic oxy group; Siloxy-; Acyloxy; Formamyl oxygen base; Alkoxycarbonyloxy; Aryloxy carbonyl oxygen base; Amino (comprises alkylamino; Arylamino and heterocyclic radical are amino); Amido; Urea groups; Sulfamyl is amino; Alkoxycarbonyl amido; Aryloxy carbonyl is amino; Alkyl sulfonyl-amino; Arlysulfonylamino; The heterocycle sulfuryl amino; Nitro; Alkylthio; Arylthio; The heterocycle sulfenyl; Alkyl sulphonyl; Aryl sulfonyl; The heterocycle alkylsulfonyl; Alkyl sulphinyl; Aryl sulfonyl kia; The heterocycle sulfinyl; Sulfamyl or sulfo group.These groups can be substituted.
R 45And R 46Independent separately expression Wasserstoffatoms, aliphatic group, aromatic group, heterocyclic group, acyl group, carbalkoxy, aryloxy carbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl.These groups can further be substituted.
R 41And R 45, or R 45And R 46Can mutually combine and form 5-or 6-unit ring.R 41And R 42Have and the identical implication of formula (B1).
In the azoic dyestuff of (B1-A), more preferably following formula (B1-B1) or (B1-B2) those:
In formula (B1-B1) with (B1-B2), R 47And R 48Have and the middle R of formula (B1-A) 41Identical implication.A 41, R 45, R 46, B 41, B 42And G 4Have and the identical implication of formula (B1-A).
Formula (B1-A) and (B1-B) term (substituting group) of (following (B1-B) comprise simultaneously formula (B1-B1) with (B1-B2)) middle use are described below in its more specifically notion of description formula (B1) level.These are common in following formula that provides (B1-C) and description (B1-D).
Halogen atom comprises fluorine, chlorine and bromine atoms.
Aliphatic group is meant and comprises alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl and substituted aralkyl.Aliphatic group can maybe can be a cyclic by branching.The aliphatic group contains 1 to 20 carbon atom, more preferably contains 1 to 16 carbon atom.The aryl moiety of aralkyl and substituted aralkyl is preferably phenyl or naphthyl, more preferably phenyl.The instance of aliphatic group comprises methyl, ethyl, butyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxy ethyl, cyano ethyl, trifluoromethyl, 3-sulfo group propyl group, 4-sulfo group butyl, cyclohexyl, benzyl, 2-styroyl, vinyl, and allyl group.
The monovalence aromatic group is meant and comprises aryl and substituted aryl.Preferred aryl groups is phenyl or naphthyl, is more preferably phenyl.Preferred monovalence aromatic group contains 6 to 20 carbon atoms, more preferably contains 6 to 16 carbon atoms.The instance of monovalence aromatic group be phenyl, right-tolyl, right-p-methoxy-phenyl, neighbour-chloro-phenyl-and-(3-sulfo group propyl group is amino) phenyl.Divalent aromatic radical still is that with monovalence aromatic group difference it is a divalent group corresponding to the monovalence aromatic group.Its instance be phenylene, right-tolylene, right-the methoxyl group phenylene, neighbour-chlorine phenylene ,-(3-sulfo group propyl group is amino) phenylene and naphthylidene.
Heterocyclic group is meant and comprises substituted heterocyclic group and unsubstituted heterocyclic group.Heterocyclic group can be any heterocyclic fused with aliphatic series ring, aromatics or other.Preferred heterocyclic group is 5-or 6-unit ring heterocyclic group.Form the heterocyclic heteroatoms and comprise N, O and S.The substituent instance of substituted heterocyclic group is aliphatic group, halogen atom, alkyl sulphonyl, aryl sulfonyl, acyl group, amido, sulfamyl, formamyl and ionic hydrophilic radical.The instance of monovalence heterocyclic group is 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-[4-morpholinodithio base, 2-benzoxazolyl and 2-furyl.Divalent heterocyclic group is derived from the monovalence heterocyclic group, through having free linkage from wherein removing a Wasserstoffatoms.
Formamyl is meant and comprises substituted formamyl and unsubstituted formamyl.A substituent instance of substituted formamyl is an alkyl.The instance of formamyl is methylamino formyl radical and formyl-dimethylamino.
Carbalkoxy is meant and comprises substituted carbalkoxy and unsubstituted carbalkoxy.Carbalkoxy is preferably and contains 2 to 20 carbon atoms.A substituent instance of substituted carbalkoxy is ionic hydrophilic radical.The instance of carbalkoxy comprises methoxycarbonyl and ethoxycarbonyl.
Aryloxy carbonyl is meant and comprises substituted aryloxy carbonyl and unsubstituted aryloxy carbonyl.Aryloxy carbonyl is preferably and contains 7 to 20 carbon atoms.A substituent instance of substituted aryloxy carbonyl is ionic hydrophilic radical.The instance of aryloxy carbonyl is a carbobenzoxy.
Heterocycle oxygen carbonyl is meant and comprises substituted heterocycle oxygen carbonyl and unsubstituted heterocycle oxygen carbonyl.Heterocycle oxygen carbonyl is preferably and contains 2 to 20 carbon atoms.A substituent instance of substituted heterocycle oxygen carbonyl is ionic hydrophilic radical.The instance of heterocycle oxygen carbonyl is a 2-pyridyl oxygen base carbonyl.
Acyl group is meant and comprises substituted acyl group and unsubstituted acyl.Acyl group is preferably and contains 1 to 20 carbon atom.A substituent instance of substituted acyl group is ionic hydrophilic radical.The instance of acyl group comprises ethanoyl and benzoyl-.
Alkoxyl group is meant and comprises substituted alkoxyl group and unsubstituted alkoxyl group.Alkoxyl group is preferably and contains 1 to 20 carbon atom.The substituent instance of substituted alkoxyl group is alkoxyl group, hydroxyl and ionic hydrophilic radical.The instance of alkoxyl group is methoxyl group, oxyethyl group, isopropoxy, methoxy ethoxy, hydroxyl-oxethyl and 3-carboxyl propoxy-.
Aryloxy is meant and comprises substituted aryloxy and unsubstituted aryloxy.Aryloxy is preferably and contains 6 to 20 carbon atoms.The substituent instance of substituted aryloxy is alkoxyl group and ionic hydrophilic radical.The instance of aryloxy comprises phenoxy, right-methoxyl group phenoxy and neighbour-methoxyl group phenoxy.
Heterocyclic oxy group is meant and comprises substituted heterocyclic oxy group and unsubstituted heterocyclic oxy group.Heterocyclic oxy group is preferably the heterocyclic oxy group that contains 2 to 20 carbon atoms.The substituent instance of substituted radical is an alkyl, alkoxyl group and ionic hydrophilic radical.The instance 3-pyridyl oxygen base of heterocyclic oxy group and 3-thienyl oxygen base.
Silyloxy is preferably contained the aliphatic series and/or the substituted silyloxy of aromatic group of 1 to 20 carbon atom.The instance of silyloxy is trimethylammonium silyloxy and diphenyl methyl silyloxy.
Acyloxy is meant and comprises substituted acyloxy and unsubstituted acyloxy.Acyloxy preferably contains the acyloxy of 1 to 20 carbon atom.A substituent instance of substituted acyloxy is ionic hydrophilic radical.The instance of acyloxy comprises acetoxyl group and benzoyloxy.
Formamyl oxygen base is meant and comprises substituted formamyl oxygen base and unsubstituted formamyl oxygen base.A substituent instance of substituted formamyl oxygen base is an alkyl.The instance of formamyl oxygen base is a N-methylamino formyl radical oxygen base.
Alkoxycarbonyloxy is meant and comprises substituted alkoxycarbonyloxy and unsubstituted alkoxycarbonyloxy.Alkoxycarbonyloxy preferably contains 2 to 20 carbon atoms.The instance of alkoxycarbonyloxy comprises methoxycarbonyl oxygen base and the different third oxygen ketonic oxygen base.
Aryloxy carbonyl oxygen base is meant and comprises substituted aryloxy carbonyl oxygen base and unsubstituted aryloxy carbonyl oxygen base.Aryloxy carbonyl oxygen base preferably contains 7 to 20 carbon atoms.An instance of aryloxy carbonyl oxygen base is a carbobenzoxy oxygen base.
Amino is meant and comprises unsubstituted amino and by the arbitrary substituted amino of alkyl, aryl or heterocyclic group.Substituting group, alkyl, aryl and heterocyclic group can further be substituted.Alkylamino preferably contains 1 to 20 carbon atom.A substituent instance of substituted radical is ionic hydrophilic radical.The instance of alkylamino comprises methylamino and diethylamino.
Arylamino is meant and comprises substituted arylamino and unsubstituted arylamino.Arylamino preferably contains 6 to 20 carbon atoms.The substituent instance of substituted arylamino is halogen atom and ionic hydrophilic radical.The instance of arylamino is that anilino and 2-chloro-phenyl-are amino.
Heterocyclic radical amino is meant and comprises that substituted heterocyclic radical is amino and unsubstituted heterocyclic is amino.Heterocyclic radical amino preferably contains 2 to 20 carbon atoms.The substituent instance of substituted radical is alkyl, halogen atom and ionic hydrophilic radical.
Amido is meant and comprises substituted amido and unsubstituted amido.Amido preferably contains 2 to 20 carbon atoms.A substituent instance of substituted amido is ionic hydrophilic radical.The instance of amido is a kharophen, propionamido, benzamido-, N-phenyl kharophen and 3,5-disulfobenzene formamido group.
Urea groups is meant and comprises substituted urea groups and unsubstituted urea groups.Urea groups preferably contains 1 to 20 carbon atom.The substituent instance of substituted urea groups is alkyl and aryl.The instance of urea groups is a 3-methyl urea groups, 3,3-dimethyl-urea groups and 3-phenyl urea groups.
Sulfamyl amino is meant and comprises that the amino and unsubstituted sulfamyl of substituted sulfamyl is amino.The amino substituent instance of substituted sulfamyl is an alkyl.An amino instance of sulfamyl is N, and N-dipropyl sulfamyl is amino.
Alkoxycarbonyl amido is meant and comprises substituted alkoxycarbonyl amido and unsubstituted alkoxycarbonyl amido.Alkoxycarbonyl amido preferably contains 2 to 20 carbon atoms.A substituent instance of substituted alkoxycarbonyl amido is ionic hydrophilic radical.An instance of alkoxycarbonyl amido is that ethoxycarbonyl is amino.
Aryloxy carbonyl amino is meant and comprises that the amino and unsubstituted aryloxy carbonyl of substituted aryloxy carbonyl is amino.Aryloxy carbonyl amino preferably contains 7 to 20 carbon atoms.A substituent instance of substituted radical is ionic hydrophilic radical.An amino instance of aryloxy carbonyl is that carbobenzoxy is amino.
Alkyl sulfonyl-amino and arlysulfonylamino are meant and comprise substituted alkyl sulfonyl-amino and arlysulfonylamino and unsubstituted alkyl sulfuryl amino and arlysulfonylamino.Sulfuryl amino is preferably and contains 1 to 20 carbon atom.A substituent instance of substituted radical is ionic hydrophilic radical.The instance of sulfuryl amino is that methyl sulphonyl is amino, and N-phenyl-methyl sulphonyl is amino, phenyl sulfonyl amino and 3-carboxyl phenyl sulfuryl amino.
The heterocycle sulfuryl amino is meant and comprises substituted heterocycle sulfuryl amino and unsubstituted heterocycle sulfuryl amino.The heterocycle sulfuryl amino preferably contains 1 to 12 carbon atom.A substituent instance of substituted radical is ionic hydrophilic radical.The instance of heterocycle sulfuryl amino is that 2-thienyl sulphonyl base is amino and the 3-pyridyl sulfonyl is amino.
The heterocycle alkylsulfonyl is meant and comprises substituted heterocycle alkylsulfonyl and unsubstituted heterocycle alkylsulfonyl.The heterocycle alkylsulfonyl preferably contains 1 to 20 carbon atom.A substituent instance of substituted radical is ionic hydrophilic radical.The instance of heterocycle alkylsulfonyl is 2-thienyl sulphonyl base and 3-pyridyl sulfonyl.
The heterocycle sulfinyl is meant and comprises substituted heterocycle sulfinyl and unsubstituted heterocycle sulfinyl.The heterocycle sulfinyl preferably contains 1 to 20 carbon atom.A substituent instance of substituted radical is ionic hydrophilic radical.An instance of heterocycle sulfinyl is a 4-pyridine sulfinyl.
Alkylthio, arylthio and heterocycle sulfenyl comprise substituted alkylthio, arylthio and heterocycle sulfenyl and unsubstituted alkylthio, arylthio and heterocycle sulfenyl.Alkylthio, arylthio and heterocycle sulfenyl are preferably and contain 1-20 carbon atom.A substituent instance of substituted radical is ionic hydrophilic radical.Alkylthio, the instance of arylthio and heterocycle sulfenyl is a methylthio group, thiophenyl and 2-pyridylthio base.
Alkyl sulphonyl and aryl sulfonyl are meant and comprise substituted alkyl sulphonyl and aryl sulfonyl and unsubstituted alkyl alkylsulfonyl and aryl sulfonyl.The instance of alkyl sulphonyl and aryl sulfonyl is methylsulfonyl and benzenesulfonyl.
Alkyl sulphinyl and aryl sulfonyl kia are meant and comprise substituted alkyl sulphinyl and aryl sulfonyl kia and unsubstituted alkyl sulfinyl and aryl sulfonyl kia.The instance of alkyl sulphinyl and aryl sulfonyl kia is methylsulfinyl and phenyl sulfinyl.
Sulfamyl is meant and comprises substituted sulfamyl and unsubstituted sulfamyl.A substituent instance of substituted sulfamyl is an alkyl.The instance of sulfamyl comprises dimethylamino alkylsulfonyl and two-(2-hydroxyethyl) sulfamyl.
Further describe formula (B1), (B1-A) and (B1-B).
In the following description, above-described those should apply to described group and substituting group.
In formula (B1), A 41, A 42And A 43The optional substituted aromatic group (A of independent separately expression 41And A 43The monovalence of respectively doing for oneself aromatic group is aryl for example; A 42Be for example arylidene of divalent aromatic radical) or optional substituted heterocyclic group (A 41And A 43The monovalence of respectively doing for oneself aromatic group example; A 42Be divalent aromatic radical).The instance of aromatic ring is benzene and naphthalene nucleus; Comprise N, O and S with formation heterocyclic heterocyclic atom.Heterocycle can with aliphatic series ring, aromatic ring or any other be heterocyclic fused.
Substituting group can be arylazo base or heterocycle azo base.Therefore, the dyestuff of formula (B1) comprises trisazo dye and Tetrakisazo dyes.
Preferably, A 41, A 42And A 43In at least two be heterocyclic group.
Preferably, be used for A 43Heterocyclic group be aromatics, nitrogenous 6-unit heterocyclic group.More preferably, A 43Be the aromatics of following formula (B1-C), nitrogenous 6-unit heterocyclic group.In this case, formula (B1) is corresponding to (B1-A).
In formula (B1-C), B 41And B 42Expression=CR separately 41-with-CR 42=, or any is nitrogen-atoms and another is=CR in them 41-or-CR 42=.Preferably, their expression=CR 41-with-CR 42=.
R 45And R 46Represent Wasserstoffatoms, aliphatic group, aromatic group, heterocyclic group, acyl group, carbalkoxy, aryloxy carbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl independently of one another.These groups can further be substituted.Preferably, R 45And R 46Respectively do for oneself Wasserstoffatoms, aliphatic group, aromatic group, heterocyclic group, acyl group, alkyl sulphonyl or aryl sulfonyl.More preferably, they are any in Wasserstoffatoms, aromatic group, heterocyclic group, acyl group, alkyl sulphonyl or the aryl sulfonyl; Most preferably, be any in Wasserstoffatoms, aryl or the heterocyclic group.These groups can further be substituted.
G 4, R 41And R 42Independent separately expression Wasserstoffatoms, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyanic acid, carboxyl, formamyl, carbalkoxy, aryloxy carbonyl, heterocycle oxygen carbonyl, acyl group, hydroxyl, alkoxyl group, aryloxy, heterocyclic oxy group, siloxy-, acyloxy, formamyl oxygen base, alkoxycarbonyloxy, aryloxy carbonyl oxygen base, amino (comprising alkylamino, arylamino, heterocyclic radical amino), amido, urea groups, sulfamyl amino, alkoxycarbonyl amido, aryloxy carbonyl amino, alkyl sulfonyl-amino, arlysulfonylamino, heterocycle sulfuryl amino, nitro, alkylthio, arylthio, heterocycle sulfenyl, alkyl sulphonyl, aryl sulfonyl, heterocycle alkylsulfonyl, alkyl sulphinyl, aryl sulfonyl kia, heterocycle sulfinyl, sulfamyl or sulfo group, and each group can further be substituted.
G 4Substituting group be preferably Wasserstoffatoms, halogen atom, aliphatic group, aromatic group, hydroxyl, alkoxyl group, aryloxy, acyloxy, heterocyclic oxy group, amino (comprising that alkylamino, arylamino, heterocyclic radical are amino), amido, urea groups, sulfamyl amino, alkoxycarbonyl amido, aryloxy carbonyl amino, alkylthio, arylthio or heterocycle sulfenyl; More preferably Wasserstoffatoms, halogen atom, alkyl, hydroxyl, alkoxyl group, aryloxy, acyloxy, amino (comprising that alkylamino, arylamino, heterocyclic radical are amino) or amido; Most preferably Wasserstoffatoms, arylamino or amido.These groups can further be substituted.
Preferred R 41And R 42Substituting group be Wasserstoffatoms, alkyl, aryl, heterocyclic group, halogen atom, carbalkoxy, carboxyl, formamyl, hydroxyl, alkoxyl group or cyanic acid.These groups can further be substituted.R 41And R 45, or R 45And R 46Can mutually combine and form 5-unit or 6-unit ring.For R 41, R 42, R 45, R 46And G 4The substituting group of substituted radical, refer to for G 4, R 41And R 42Above-mentioned those that mention.Preferably, dyestuff R therein 41, R 42, R 45, R 46And G 4Any arbitrary position contain ionic hydrophilic radical.
Substituting group, ionic hydrophilic radical comprise for example sulfo group, carboxyl, phosphono and quaternary ammonium group etc.Preferred ion property hydrophilic radical is carboxyl, phosphono or sulfo group, more preferably carboxyl or sulfo group.Carboxyl, phosphono and sulfo group can form salt.The instance that forms the counter ion of this salt is an ammonium ion, alkalimetal ion (for example lithium ion, sodium ion, and potassium ion) and organic cation (for example tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl phosphonium ion).
R 42Preferred heterocycle be thiophene, thiazole, imidazoles, benzoglyoxaline and thieno-thiazole ring.These heterocyclic groups can further be substituted.Especially, particularly preferably be thiophene, thiazole, imidazoles, benzoglyoxaline and thieno-thiazole ring in the following formula (h) to (1).Work as A 42Be thiphene ring (h) and work as A 43When having the structure of formula (B1-C), formula (B1) is corresponding to formula (B1-B1) so.Work as A 43Be thiazole ring (i) and work as A 43When having the structure of formula (B1-C), formula (B1) is corresponding to formula (B1-B2) so.
Figure G2008101757780D00441
Figure G2008101757780D00451
In formula (h) in (1), A 409To A 417Have with formula (B1-C) in G 4, R 41And R 42In the identical implication of substituting group.
For being used for the present invention, more preferably has the dyestuff of following formula (B1-D1) or structure (4-D2).(formula (B1-D) common name expression (B1-D1) simultaneously and (4-D2).)
Figure G2008101757780D00452
In formula (B1-D1), Z4 representes that Hammett (Hammett) substituent constant σ p is at least 0.20 electron-withdrawing group.Z 4Preferably σ p is at least 0.30 electron-withdrawing group, is more preferably σ p and is at least 0.45, more preferably is at least 0.60 again, but is no more than 1.0 electron-withdrawing group.
Particularly, to be at least the instance of 0.60 electron-withdrawing group be cyanic acid, nitro and alkyl sulphonyl (for example, methane sulfonyl, aryl sulfonyl for example benzenesulfonyl) to Hammett substituent constant σ p.
The instance that Hammett substituent constant σ p is at least 0.45 electron-withdrawing group except above-mentioned group be acyl group (like ethanoyl), carbalkoxy (like dodecyl oxygen carbonyl), aryloxy carbonyl (as-chlorobenzene oxygen carbonyl), alkyl sulphinyl (like the n-propyl sulfinyl), aryl sulfonyl kia (like the phenyl sulfinyl), sulfamyl (like N-ethyl sulfamyl, N, N-dimethylamino alkylsulfonyl), and haloalkyl (like trifluoromethyl).
Hammett substituent constant σ p is that the instance of at least 0.30 electron-withdrawing group is except above-mentioned group; Be that acyloxy (like acetoxyl group), formamyl are (like N-ethylamino formyl radical, N; N-dibutylamino formyl radical), halogenated alkoxy (like trifluoromethoxy), halo aryloxy (like penta fluoro benzene oxygen base), alkylsulfonyl oxygen base (like methylsulfonyl oxygen base), halogenated alkylthio (like the difluoro methylthio group), the quilt substituted aryl of electron-withdrawing group of at least two (each σ p is at least 0.15) are (as 2; 4-dinitrophenyl, five chlorophenyl), and heterocyclic group (like 2-benzoxazolyl, 2-[4-morpholinodithio base, 1-phenyl-2-benzimidazolyl-).
Hammett substituent constant σ p be the specific examples of at least 0.20 electron-withdrawing group except above-mentioned group, be halogen atom.
Especially, preferred Z 4Any in following: contain 2 to 20 carbon atoms acyl group, contain 2 to 20 carbon atoms alkyl oxygen carbonyl, nitro, cyanic acid, contain 1 to 20 carbon atom alkyl sulphonyl, contain 6 to 20 carbon atoms aryl sulfonyl, contain the formamyl of 1 to 20 carbon atom or contain the haloalkyl of 1 to 20 carbon atom; Any in more preferably following: cyanic acid, contain the alkyl sulphonyl of 1 to 20 carbon atom or contain the aryl sulfonyl of 6 to 20 carbon atoms, most preferably cyanic acid.
The detailed content of wherein alleged Hammett substituent constant σ p for example is described in JP-A2003-306622 (0059) to (0060) section.
R 41, R 42, R 45, R 46And R 47Have with formula (B1-B) in identical implication.R 43And R 44Independent separately expression Wasserstoffatoms, aliphatic group, aromatic group, heterocyclic group, acyl group, carbalkoxy, aryloxy carbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl or sulfamyl; Preferred Wasserstoffatoms, aromatic group, heterocyclic group, acyl group, alkyl sulphonyl or aryl sulfonyl; More preferably Wasserstoffatoms, aromatic group or heterocyclic group.
Group in the formula (B1-D) can further be substituted.For substituting group, refer in the above in the formula (B1-A) for group G 4, R 45And R 46Described those and ionic hydrophilic radical.
A 41Can be any in aromatic group or the heterocyclic group; But be preferably phenyl ring, naphthalene nucleus, pyridine ring, imidazole ring, pyrazoles ring, thiazole ring, isothiazole ring, thiadiazoles ring, benzothiazole ring or benzisothiazole ring; More preferably phenyl ring, naphthalene nucleus, pyridine ring, pyrazine ring, imidazole ring, isothiazole ring or benzothiazole ring, most preferably phenyl ring or naphthalene nucleus.
To being used for the present invention's black dyes; In order to guarantee the stability in storage of dyestuff in the aqueous solution or ink; Preferably has azoic dyestuff as substituent aromatic group or aromatic heterocyclic group; It is so design, so that the quantity of the conjugated pi-electronics of direct and azo-group bonded aromatic ring wherein surpasses 12 generally.Direct and azo-group bonded aromatic group is meant and the whole aromatic groups of azo-group bonded; And directly and azo-group bonded aromatic ring be meant such aromatic ring; It does not directly combine with azo-group, but on chromophoric group, exists to constitute azoic dyestuff as substituting group.For example, when naphthalene nucleus directly combines with azo-group, not that with phenyl ring of azo-group bonded of naphthalene nucleus but therewith the whole naphthalene nucleus of bonded is direct and azo-group bonded aromatic group so.When xenyl combines with azo-group, be direct and azo-group bonded aromatic ring with azo-group bonded phenyl so, and another phenyl is direct and azo-group bonded aromatic ring.Aromatic ring not only comprises aryl but also comprises heteroaromatic rings.Preferably, the azoic dyestuff that is used for the present invention is so design, so that the conjugated pi-electron amount of direct and azo-group bonded aromatic ring wherein surpasses 12.For example, can count conjugated pi-electron amount as follows: in containing a phenyl ring and the azoic dyestuff of a naphthalene nucleus as not direct and this azo-group bonded aromatic ring wherein, conjugated pi-electron amount is 6+10=16.Conjugated pi-the electronics of aromatic ring is conjugated pi-electronics that aromatic ring (aromatic ring comprises heterocycle, and is not limited to 6-unit ring) contains.Contain this type aromatic ring as substituting group, these dyestuffs can be more can be associating and can improve their stability in storage.The replacement position of preferred aromatic ring is R 41, R 42, R 43, R 44, R 45, R 46And R 47In any one, R more preferably 43, R 44, R 45, R 46And R 47In any one.
The black ink of mentioning below of the present invention that is is with the substituent special preferably combination in the azoic dyestuff.Preferred R 45And R 46Be any in Wasserstoffatoms, alkyl, aryl, heterocyclic group, alkylsulfonyl or the acyl group; Any in Wasserstoffatoms, aryl, heterocyclic group or the alkylsulfonyl more preferably; Most preferably be any in Wasserstoffatoms, aryl or the heterocyclic group.But, R 45And R 46Must not Wasserstoffatoms simultaneously.
G 4Preferably Wasserstoffatoms, halogen atom, alkyl, hydroxyl, amino or amido are more preferably Wasserstoffatoms, halogen atom, amino or amido, most preferably are Wasserstoffatoms, amino or amido.
Preferred A 41Be phenyl ring, naphthalene nucleus, pyridine ring, imidazole ring or pyrazoles ring; Most preferably phenyl ring or naphthalene nucleus.
Also preferably, B 41And B 42Be respectively=CR 41-with-CB 42=; And preferred R 41And R 42Any in Wasserstoffatoms, alkyl, halogen atom, cyanic acid, formamyl, carboxyl, hydroxyl, alkoxyl group or the carbalkoxy, more preferably any in Wasserstoffatoms, alkyl, carboxyl, cyanic acid or the formamyl.
As for the substituent preferably combination of the compound of formula (B1), it is desirable at least one substituting group is above-mentioned preferred group.More preferably, more substituting group is a preferred group.Most preferably, all substituting groups are preferred group.
What mention below is the specific examples of the azoic dyestuff of formula (B1), and still, the present invention should not receive these restriction.In the instance below, carboxyl, phosphono and sulfo group can form salt.The instance that forms the counter ion of this salt comprises ammonium ion, alkalimetal ion (for example lithium ion, sodium ion, potassium ion) and organic cation (for example tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl phosphonium ion).In these, preferred ammonium ion, organic cation and lithium ion; And lithium ion most preferably.
A 41—N＝N—A 42-N＝N—A 43
A 41—N＝N—A 42—N＝N—A 43
Figure G2008101757780D00501
A 41—N＝N—A 42—N＝N—A 43
Figure G2008101757780D00511
A 41—N＝N—A 42—N＝N—A 43
Figure G2008101757780D00521
A 41—N＝N—A 42—N＝N—A 43
Figure G2008101757780D00531
A 41—N＝N—A 42—N＝N—A 43
Figure G2008101757780D00541
A 41—N＝N—A 42—N＝N—A 43
Figure G2008101757780D00551
A 41—N＝N—A 42—N＝N—A 43
Figure G2008101757780D00561
A 41—N＝N—A 42—N＝N—A 43
Figure G2008101757780D00571
A 41—N＝N—A 42—N＝N—A 43
A 41—N＝N—A 42—N＝N—A 43
Figure G2008101757780D00591
A 41—N＝N—A 42—N＝N—A 43
Figure G2008101757780D00601
The black dyes that can prepare formula (B1) through the linked reaction of two azo components and coupling component.For this reason, for example can be with reference to the method for describing among JP-A 2003-306623 and the Japanese patent application 2003-353498.
As for λ max is the dyestuff (S) of 350nm to 500nm, preferably above-mentioned yellow dyes and yellow ultramarine.Wherein n be 0 or y be that 0 the formula (B1) and the dyestuff of formula (B2) can be used for dyestuff (S).
Preferably, the content of the azoic dyestuff of ink Chinese style (B1) is 0.2 to 20 weight %, more preferably 0.5 to 15 weight %.
Below the compound of detailed description formula (B2).
(B2) P-(N＝N-Qx)y-N＝N-R
Wherein, P, Q and R represent optional substituted aromatic group (P and R respectively do for oneself for example aryl of monovalence aromatic group, Q is a for example arylidene of divalent aromatic radical) separately.Particularly, preferred Q is for example naphthalene nucleus of many ring aromatic nucleus.
X is 1 or bigger integer, and y is 1 or bigger integer.Preferably, x=y=1.
Can be Wasserstoffatoms at the substituting group in the formula (B2); Halogen atom; Aliphatic group; Aromatic group; Heterocyclic group; Cyanic acid; Carboxyl; Formamyl; Carbalkoxy; Aryloxy carbonyl; Heterocycle oxygen carbonyl; Acyl group; Hydroxyl; Alkoxyl group; Aryloxy; Heterocyclic oxy group; Siloxy-; Acyloxy; Formamyl oxygen base; Alkoxycarbonyloxy; Aryloxy carbonyl oxygen base; Amino (comprises alkylamino; Arylamino; Heterocyclic radical is amino); Amido; Urea groups; Sulfamyl is amino; Alkoxycarbonyl amido; Aryloxy carbonyl is amino; Alkyl sulfonyl-amino; Arlysulfonylamino; The heterocycle sulfuryl amino; Nitro; Alkylthio; Arylthio; The heterocycle sulfenyl; Alkyl sulphonyl; Aryl sulfonyl; The heterocycle alkylsulfonyl; Alkyl sulphinyl; Aryl sulfonyl kia; The heterocycle sulfinyl; Sulfamyl and sulfo group.These substituting groups can further be substituted.These substituent preferred embodiments can be with identical corresponding to those of the group of formula (B1).Substituting group can also be the arylazo base.
What mention below is the specific examples of the black dyes of the formula (B2) that can be used for the present invention, and still, the present invention should not receive these restriction.In the instance below, sulfo group can form salt.The instance that forms the counter ion of this salt comprises ammonium ion, alkalimetal ion (for example lithium ion, sodium ion, potassium ion) and organic cation (for example tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl phosphonium ion).As for counter ion, the preferred, lithium ion.
Figure G2008101757780D00621
Figure G2008101757780D00631
Magenta ink of the present invention comprises oxidizing potential greater than 1.0V, is preferably greater than 1.1V, most preferably greater than the dyestuff of 1.2V.Comprise this dyestuff of oxidizing potential greater than 1.0V, this ink is given the image favorable durability, those of particularly good ozone resistance.
Preferably, oxidizing potential greater than the dyestuff content of 1.0V (with respect to SCE) be in the ink all dyestuffs at least 40%.
For comprising the dyestuff of oxidizing potential greater than 1.0V, will have heterocycle therein the bonded azoic dyestuff be used for the present invention with at least two kinds of combinations that have in the magenta dyestuff of any other structure.Dyestuff with any other structure is a kind of dyestuff different with the azoic dyestuff with azo-group, and each end of described azo-group has heterocycle on skeleton point.Particularly, it be do not have heterocycle to combine with azo-group or heterocycle only with terminal bonded azoic dyestuff or any other dyestuff except that azoic dyestuff of azo-group.Other dyestuff except that azoic dyestuff is anthrapyridone (anthrapyridone) dyestuff for example.
The azoic dyestuff that each end that preferably contains azo-group, azo-group contains heterocyclic is the dyestuff of formula (M1), and the dyestuff that preferably has any other structure is Anthrapyridone dyes, more preferably the Anthrapyridone dyes of formula (2).
(magenta dyestuff)
The dyestuff of formula (M1) is described below.
Be preferably used as magenta dyestuff of the present invention in aqueous medium, in the spectral region of 500-580nm, having absorption peak, oxidizing potential azoic dyestuff greater than 1.0V (with respect to SCE).
First of preferred structure that is used as the azoic dyestuff of magenta dyestuff among the present invention is characterised in that they have by formula: the chromophoric group of (heterocycle A)-N=N-(heterocycle B) expression.In this case, heterocycle A and heterocycle B can have same structure.Particularly, heterocycle A and heterocycle B are 5-or 6-unit heterocycle, and for example are selected from: pyrazoles, imidazoles, triazole 、 oxazole, thiazole, selenazoles, pyridone, pyrazine, pyrimidine and pyridine.Particularly, heterocycle is described among JP-A-2001-279145,2002-309116 and the 2003-12650.
Second preferred feature of the preferred structure of azoic dyestuff is that the azo-group in them contains bonded aromatics direct with it, nitrogenous 6 yuan of heterocyclic coupling compositions on its at least one side.The specific examples of this type azoic dyestuff is described among the JP-A-2002-371214.
The 3rd preferred feature of the preferred structure of azoic dyestuff is that auxochromous group wherein has aromatics cyclic amino or the amino structure of heterocyclic radical.Particularly, auxochromous group is anilino or assorted amino (heterylamino).
The 4th preferred feature of the preferred structure of azoic dyestuff is that they have three-dimensional arrangement.The specific examples of this type dyestuff is described among the JP-A-2002-371214.
Have above-mentioned concrete structure, azoic dyestuff can have the oxidizing potential of raising and the ozone resistance of raising.In order to improve the oxidizing potential of azoic dyestuff, for example, from them, remove α-Wasserstoffatoms.Consider the oxidizing potential of its raising, preferably the azoic dyestuff with formula (M1) is used for the present invention.As for the raising method of azoic dyestuff oxidizing potential, specifically reference is the specification sheets of JP-A-2003-64275.
The λ max (absorption maximum wavelength) that preferred the present invention comprises the magenta ink with any azoic dyestuff of said structure characteristic is 500 to 580nm, because its tone is good.More preferably, less than 100nm, promptly absorption peak is sharp-pointed at the half breadth of long wavelength side and short wavelength side for maximum absorption wavelength.This has specific descriptions in JP-A-2002-309133.The sharp-pointed absorption peak of the dyestuff that in addition, the introducing of Alpha-Methyl realization obtains in the azoic dyestuff of formula (M1).
The magenta ink that preferably comprises azoic dyestuff is at most 5.0 * 10 to the pressure fading rate constant of ozone gas -2[hour -1], more preferably be at most 3.0 * 10 -2[hour -1], more preferably be at most 1.0 * 10 again -2[hour -1].
The following pressure fading rate constant of measuring magenta ink to ozone gas: separately magenta ink is printed on the reflection-type image receiver media; And the part painted areas of the image that will form is thus elected the initial density point particularly as; Described part painted areas has the color in the main spectral absorption zone of ink, and the reflection density of measuring through state A spectral filter is 0.90-1.10.This initial density is beginning density (=100%).Therein ozone concn if having time all be this image that fades in the fadeometer of 5mg/ liter.The 80% o'clock needed time that the density of the sample that fades is reached the initial density of primary sample is carried out timing, and obtain its inverse [hour -1].Supposing that fade density and the relation between the time follow the speed mode of first order reaction, is the color fading reaction velocity constant with this value defined.
The printing sheet that is used to test can be printing sheet, the Macbeth chart gradient color chips of any JIS flip-flop 2223 black square signs, or any gradient density that other can carry out area measure is printed sheet.
The reflection density of the reflected image of printing for test (gradient color chips) is that optical density instrumentation amount is measured through the light of state A spectral filter, and this photodensitometer meets international standard ISO5-4 (how much states of reflection density).
Be used for the testing laboratory of the pressure fading rate constant of ozone gas test usefulness is equipped with ozonizer; This ozonizer can inner ozone concn is maintained the 5mg/ liter effluve system of AC voltage (as be used for applying to the exsiccant air) in free, and the temperature of exposed sample is controlled at 25 ℃ in producer.
This pressure fading rate constant be sample in oxidative environment, the index of oxidizability in the environment in the gas that contains photo-chemical smog, vehicle exhaust, produces in from the organic steam of furniture coatingsurface and carpet and the framework in the daylight room for example.Particularly, ozone gas is the representative of these oxidizing atmospheres.
The dyestuff of formula (M1) is the typical azoic dyestuff that has in the present invention the above-mentioned characteristic of using, and following description they.
Figure G2008101757780D00661
In formula (M1), A 31Expression 5-unit heterocycle.
B 31And B 32Expression=CR separately 31-or-CR 32=, or B 31And B 32In any expression nitrogen-atoms, and another expression=CR 31-or-CR 32=.
R 35And R 36Represent Wasserstoffatoms or substituting group independently of one another.Substituting group comprises aliphatic group, aromatic group, heterocyclic group, acyl group, carbalkoxy, aryloxy carbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl and sulfamyl; And the Wasserstoffatoms in each group can be substituted.
G 3, R 31And R 32Represent Wasserstoffatoms or substituting group independently of one another.Substituting group comprises halogen atom; Aliphatic group; Aromatic group; Heterocyclic group; Cyanic acid; Carboxyl; Formamyl; Carbalkoxy; Aryloxy carbonyl; Heterocycle oxygen carbonyl; Acyl group; Hydroxyl; Alkoxyl group; Aryloxy; Heterocyclic oxy group; Siloxy-; Acyloxy; Formamyl oxygen base; Alkoxycarbonyloxy; Aryloxy carbonyl oxygen base; Amino; Amido; Urea groups; Sulfamyl is amino; Alkoxycarbonyl amido; Aryloxy carbonyl is amino; Alkyl sulfonyl-amino; Arlysulfonylamino; The heterocycle sulfuryl amino; Nitro; Alkylthio; Arylthio; The heterocycle sulfenyl; Alkyl sulphonyl; Aryl sulfonyl; The heterocycle alkylsulfonyl; Alkyl sulphinyl; Aryl sulfonyl kia; The heterocycle sulfinyl; Sulfamyl and sulfo group; And the Wasserstoffatoms in each group can be substituted.
R 31And R 35, or R 35And R 36Can be interconnected to form 5-or 6-unit ring.
In formula (M1), A 31Expression 5-unit heterocycle.The heteroatomic instance of heterocyclic is N, S and O.Preferably, heterocycle is the first heterocycle of nitrogenous 5-.Heterocycle can be any heterocyclic fused with aliphatic series ring, aromatic ring or other.Be used for A 31The heterocyclic preferred embodiment be pyrazoles, imidazoles, thiazole, isothiazole, thiadiazoles ring, benzothiazole or benzisothiazole ring.These heterocycles can further be substituted.Especially, pyrazoles, imidazoles, isothiazole, thiadiazoles and the benzothiazole of preferred following formula (a) to (g).
In formula (a) in (g), R 307To R 322Be used for G in expression and the formula (M1) 3, R 31And R 35Those identical substituting groups of describing.
In formula (a) in (g), preferably formula (a) and (b) in pyrazoles and isothiazole ring; And the pyrazoles ring of formula (a) most preferably.
Figure G2008101757780D00671
In formula (M1), B 31And B 32Expression=CR respectively 31-with-CR 32=, or any the expression nitrogen-atoms in them, and another expression=CR 31-or-CR 32=.Preferably, their expression=CR 31-with-CR 32=.
Preferred R 35And R 36Each is any in Wasserstoffatoms, aliphatic group, aromatic group, heterocyclic group, acyl group, alkyl sulphonyl or the aryl sulfonyl naturally; Any in Wasserstoffatoms, aromatic group, heterocyclic group, acyl group, alkyl sulphonyl or the aryl sulfonyl more preferably; Most preferably be any in Wasserstoffatoms, aryl or the heterocyclic group.Wasserstoffatoms in these groups can be substituted.But, R 35And R 36Not Wasserstoffatoms simultaneously.
G 3, R 31And R 32Represent Wasserstoffatoms independently of one another; Halogen atom; Aliphatic group; Aromatic group; Heterocyclic group; Cyanic acid; Carboxyl; Formamyl; Carbalkoxy; Aryloxy carbonyl; Heterocycle oxygen carbonyl; Acyl group; Hydroxyl; Alkoxyl group; Aryloxy; Heterocyclic oxy group; Siloxy-; Acyloxy; Formamyl oxygen base; Alkoxycarbonyloxy; Aryloxy carbonyl oxygen base; Amino (comprises anilino; Heterocyclic radical is amino); Amido; Urea groups; Sulfamyl is amino; Alkoxycarbonyl amido; Aryloxy carbonyl is amino; Alkyl sulfonyl-amino; Arlysulfonylamino; The heterocycle sulfuryl amino; Nitro; Alkylthio; Arylthio; The heterocycle sulfenyl; Alkyl sulphonyl; Aryl sulfonyl; The heterocycle alkylsulfonyl; Alkyl sulphinyl; Aryl sulfonyl kia; The heterocycle sulfinyl; Sulfamyl or sulfo group; And these groups can further be substituted.
Preferably, G 3Be any in Wasserstoffatoms, halogen atom, aliphatic group, aromatic group, hydroxyl, alkoxyl group, aryloxy, acyloxy, heterocyclic oxy group, amino (comprise anilino, heterocyclic radical amino), amido, urea groups, sulfamyl amino, alkoxycarbonyl amido, aryloxy carbonyl amino, alkylthio, arylthio, the heterocycle sulfenyl; Any in Wasserstoffatoms, halogen atom, alkyl, hydroxyl, alkoxyl group, aryloxy, acyloxy, amino (comprise anilino, heterocyclic radical amino) or the amido more preferably; Most preferably be any in Wasserstoffatoms, anilino or the amido.Wasserstoffatoms in these groups can be substituted.
Also preferably, R 31And R 32Each is any in Wasserstoffatoms, alkyl, halogen atom, carbalkoxy, carboxyl, formamyl, hydroxyl, alkoxyl group or the cyanic acid naturally.Wasserstoffatoms in these groups can be substituted.
R 31And R 35, or R 35And R 36Can mutually combine and form 5-or 6-unit ring.
At A 31Be substituted or R 31, R 32, R 35, R 36And G 3In the further substituted situation of substituting group under, regard to G on so 3, R 31And R 32The substituting group of mentioning is meant the substituting group that is used to be substituted group.
Under the situation of dye soluble in water of formula (M1), it is desirable to A 31, R 31, R 32, R 35, R 36And G 3Contain other ionic hydrophilic radical substituting group.Be used for substituent ionic hydrophilic radical and comprise sulfo group, carboxyl, phosphono and quaternary ammonium group.For ionic hydrophilic radical, preferred carboxyl, phosphono and sulfo group; And more preferably carboxyl and sulfo group.Carboxyl, phosphono and sulfo group can be the form of salt.The instance of the salifiable counter ion of shape is ammonium ion, alkalimetal ion (for example lithium ion, potassium ion) and organic cation (for example tetramethyl ammonium, tetramethyl guanidine ion, tetramethyl phosphonium ion).
Substituent term in the indicating type (M1) is described below.These terms all are general to following formula of mentioning (M1) and formula (M1-A).
The instance of halogen atom comprises fluorine, chlorine and bromine atoms.
Aliphatic group is meant and comprises alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl and substituted aralkyl.The term " substituted " that is used for " substituted alkyl " etc. be meant Wasserstoffatoms that groups such as " alkyl " exists by on regard to G 3, R 31And R 32Any replacement in those substituting groups of mentioning.
Aliphatic group can maybe can be a cyclic by branching.Preferably, aliphatic group contains 1 to 20 carbon atom, more preferably 1 to 16 carbon atom.Aryl moiety in aralkyl and the substituted aralkyl is preferably phenyl or naphthyl, more preferably phenyl.The instance of aliphatic group is methyl, ethyl, butyl, sec.-propyl, the tertiary butyl, hydroxyethyl, methoxy ethyl, cyano ethyl, trifluoromethyl, 3-sulfo group propyl group, 4-sulfo group butyl, cyclohexyl, benzyl, 2-styroyl, vinyl and allyl group.
Aromatic group is meant and comprises aryl and substituted aryl.Aryl is preferably phenyl or naphthyl, more preferably phenyl.Preferred aromatic group contains 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms.
The instance of aromatic group be phenyl, right-tolyl, right-p-methoxy-phenyl, neighbour-chloro-phenyl-and-(3-sulfo group third amino) phenyl.
The instance of heterocyclic group is meant and comprises substituted heterocyclic group and unsubstituted heterocyclic group.Heterocycle can with aliphatic series ring, aromatics or any other be heterocyclic fused.Preferred heterocyclic group is 5-or 6-unit heterocycle.The substituent instance of substituted heterocyclic group is aliphatic group, halogen atom, alkyl sulphonyl, aryl sulfonyl, acyl group, amido, sulfamyl, formamyl and ionic hydrophilic radical.The instance of heterocyclic group is 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-[4-morpholinodithio base, 2-benzoxazolyl and 2-furyl.
Formamyl is meant and comprises substituted formamyl and unsubstituted formamyl.A substituent instance of substituted formamyl is an alkyl.The instance of formamyl is methylamino formyl radical and formyl-dimethylamino.
Carbalkoxy is meant and comprises substituted carbalkoxy and unsubstituted carbalkoxy.Carbalkoxy preferably contains 2 to 20 carbon atoms.A substituent instance of substituted radical is ionic hydrophilic radical.The instance of carbalkoxy is methoxycarbonyl and ethoxycarbonyl.
Aryloxy carbonyl is meant and comprises substituted aryloxy carbonyl and unsubstituted aryloxy carbonyl.Aryloxy carbonyl preferably contains 7 to 20 carbon atoms.A substituent instance of substituted radical is ionic hydrophilic radical.An instance of aryloxy carbonyl is a carbobenzoxy.
Heterocycle oxygen carbonyl is meant and comprises substituted heterocycle oxygen carbonyl and unsubstituted heterocycle oxygen carbonyl.As for the heterocyclic moiety of this group, refer to mentioned those of the heterocycle that regards to above-mentioned heterocyclic group.Heterocycle oxygen carbonyl preferably contains 2 to 20 carbon atoms.A substituent instance of substituted radical is ionic hydrophilic radical.An instance of heterocycle oxygen carbonyl is a 2-pyridyl oxygen base carbonyl.
Acyl group is meant and comprises substituted acyl group and unsubstituted acyl.Acyl group preferably contains 1 to 20 carbon atom.A substituent instance of substituted acyl group is ionic hydrophilic radical.The instance of acyl group is ethanoyl and benzoyl-.
Alkoxyl group is meant and comprises substituted alkoxyl group and unsubstituted alkoxyl group.Alkoxyl group preferably contains 1 to 20 carbon atom.The substituent instance of substituted alkoxyl group is alkoxyl group, hydroxyl and ionic hydrophilic radical.The instance of alkoxyl group is methoxyl group, oxyethyl group, isopropoxy, methoxy ethoxy, hydroxyl-oxethyl and 3-carboxyl propoxy-.
Aryloxy is meant and comprises substituted aryloxy and unsubstituted aryloxy.Aryloxy preferably contains 6 to 20 carbon atoms.The substituent instance of substituted aryloxy is alkoxyl group and ionic hydrophilic radical.The instance of aryloxy is phenoxy, right-methoxyl group phenoxy and neighbour-methoxyl group phenoxy.
Heterocyclic oxy group is meant and comprises substituted heterocyclic oxy group and unsubstituted heterocyclic oxy group.As for the heterocyclic moiety of this group, refer to mentioned those of the heterocycle that regards to above-mentioned heterocyclic group.Heterocyclic oxy group preferably contains 2 to 20 carbon atoms.The substituent instance of substituted radical comprises alkyl, alkoxyl group and ionic hydrophilic radical.The instance of heterocyclic oxy group is 3-pyridyl oxygen base and 3-thienyl oxygen base.
Siloxy-is preferably the aliphatic series and/or the aromatic group that are contained 1 to 20 carbon atom and replaces.The instance of siloxy-is trimethylsiloxy and diphenyl methyl siloxy-.
Acyloxy is meant and comprises substituted acyloxy and unsubstituted acyloxy.Acyloxy preferably contains 1 to 20 carbon atom.A substituent instance of substituted acyloxy is ionic hydrophilic radical.The instance of acyloxy is acetoxyl group and benzoyloxy.
Formamyl oxygen base is meant and comprises substituted formamyl oxygen base and unsubstituted formamyl oxygen base.A substituent instance of substituted formamyl oxygen base is an alkyl.An instance of formamyl oxygen base is a N-methylamino formyl radical oxygen base.
Alkoxycarbonyloxy is meant and comprises substituted alkoxycarbonyloxy and unsubstituted alkoxycarbonyloxy.Alkoxycarbonyloxy preferably contains 2 to 20 carbon atoms.The instance of alkoxycarbonyloxy is methoxycarbonyl oxygen base and the different third oxygen ketonic oxygen base.
Aryloxy carbonyl oxygen base is meant and comprises substituted aryloxy carbonyl oxygen base and unsubstituted aryloxy carbonyl oxygen base.Aryloxy carbonyl oxygen base preferably contains 7 to 20 carbon atoms.An instance of aryloxy carbonyl oxygen base is a carbobenzoxy oxygen base.
Amino is meant and comprises substituted amino and the amino of not getting.The substituent instance of substituted-amino is alkyl, aryl and heterocyclic group.Alkyl, aryl and heterocyclic group can further be substituted.The instance of alkylamino comprises substituted alkylamino and unsubstituted alkyl amino.Alkylamino preferably contains 1 to 20 carbon atom.A substituent instance of substituted radical is ionic hydrophilic radical.The instance of alkylamino is methylamino and diethylamino.
Arylamino is meant and comprises substituted arylamino and unsubstituted arylamino.Arylamino preferably contains 6 to 20 carbon atoms.The amino substituent instance of substituted aryl is halogen atom and ionic hydrophilic radical.The instance of arylamino is that phenyl amino and 2-chloro-phenyl-are amino.
Heterocyclic radical amino is meant and comprises that substituted heterocyclic radical is amino and unsubstituted heterocyclic is amino.As for the heterocyclic moiety of this group, refer to the heterocycle that regards to above-mentioned heterocyclic group described those.Heterocyclic radical amino preferably contains 2 to 20 carbon atoms.The substituent instance of substituted radical is alkyl, halogen atom and ionic hydrophilic radical.
Amido is meant and comprises substituted amido and unsubstituted amido.Amido preferably contains 2 to 20 carbon atoms.A substituent instance of substituted amido is ionic hydrophilic radical.The instance of amido is kharophen, propionamido, benzamido-, N-phenyl kharophen and 3,5-disulfobenzene formamido group.
Urea groups is meant and comprises substituted urea groups and unsubstituted urea groups.Urea groups preferably contains 1 to 20 carbon atom.The substituent instance of substituted urea groups is alkyl and aryl.The instance of urea groups is a 3-methyl urea groups, 3,3-dimethyl-urea groups and 3-phenyl urea groups.
Sulfamyl amino is meant and comprises that the amino and unsubstituted sulfamyl of substituted sulfamyl is amino.The amino substituent instance of substituted sulfamyl is an alkyl.An amino instance of sulfamyl is N, and N-dipropyl sulfamyl is amino.
Alkoxycarbonyl amido is meant and comprises substituted alkoxycarbonyl amido and unsubstituted alkoxycarbonyl amido.Alkoxycarbonyl amido preferably contains 2 to 20 carbon atoms.A substituent instance of substituted alkoxycarbonyl amido is ionic hydrophilic radical.An instance of alkoxycarbonyl amido is that ethoxycarbonyl is amino.
Aryloxy carbonyl amino is meant and comprises that the amino and unsubstituted aryloxy carbonyl of substituted aryloxy carbonyl is amino.Aryloxy carbonyl amino preferably contains 7 to 20 carbon atoms.A substituent instance of substituted radical is ionic hydrophilic radical.An amino instance of aryloxy carbonyl is that carbobenzoxy is amino.
Alkyl sulfonyl-amino and arlysulfonylamino are meant and comprise substituted alkyl sulfonyl-amino and arlysulfonylamino and unsubstituted alkyl sulfuryl amino and arlysulfonylamino.Alkyl sulfonyl-amino and arlysulfonylamino preferably contain 1 to 20 carbon atom.A substituent instance of substituted radical is ionic hydrophilic radical.The instance of alkyl sulfonyl-amino and arlysulfonylamino is methyl sulphonyl amino, N-phenyl-methyl sulphonyl amino, phenyl sulfonyl amino and 3-carboxyl phenyl sulfuryl amino.
The instance of heterocycle sulfuryl amino is meant and comprises substituted heterocycle sulfuryl amino and unsubstituted heterocycle sulfuryl amino.As for the heterocyclic moiety of this group, refer to mentioned those of the heterocycle that regards to above-mentioned heterocyclic group.The heterocycle sulfuryl amino preferably contains 1 to 12 carbon atom.A substituent instance of substituted radical is ionic hydrophilic radical.The instance of heterocycle sulfuryl amino is that 2-thienyl sulphonyl base is amino and the 3-pyridyl sulfonyl is amino.
Alkylthio, arylthio and heterocycle sulfenyl are meant and comprise substituted alkylthio, arylthio and heterocycle sulfenyl and unsubstituted alkylthio, arylthio and heterocycle sulfenyl.As for the heterocyclic moiety of this group, refer to mentioned those of the heterocycle that regards to above-mentioned heterocyclic group.Alkylthio, arylthio and heterocycle sulfenyl preferably contain 1 to 20 carbon atom.A substituent instance of substituted radical is ionic hydrophilic radical.The instance of alkylthio, arylthio and heterocycle sulfenyl is methylthio group, thiophenyl and 2-pyridylthio base.
Alkyl sulphonyl and aryl sulfonyl are meant and comprise substituted alkyl sulphonyl and aryl sulfonyl and unsubstituted alkyl alkylsulfonyl and aryl sulfonyl.The instance of alkyl sulphonyl and aryl sulfonyl is methyl sulphonyl and phenyl sulfonyl.
The heterocycle alkylsulfonyl is meant and comprises substituted heterocycle alkylsulfonyl and unsubstituted heterocycle alkylsulfonyl.As for the heterocyclic moiety of this group, refer to mentioned those of the heterocycle that regards to above-mentioned heterocyclic group.The heterocycle alkylsulfonyl preferably contains 1 to 20 carbon atom.A substituent instance of substituted radical is ionic hydrophilic radical.The instance of heterocycle alkylsulfonyl comprises 2-thienyl sulphonyl base and 3-pyridyl sulfonyl.
Alkyl sulphinyl and aryl sulfonyl kia are meant and comprise substituted alkyl sulphinyl and aryl sulfonyl kia and unsubstituted alkyl sulfinyl and aryl sulfonyl kia.The instance of alkyl sulphinyl and aryl sulfonyl kia is methylsulfinyl and phenyl sulfinyl.
The heterocycle sulfinyl is meant and comprises substituted heterocycle sulfinyl and unsubstituted heterocycle sulfinyl.As for the heterocyclic moiety of this group, refer to mentioned those of the heterocycle that regards to above-mentioned heterocyclic group.The heterocycle sulfinyl preferably contains 1 to 20 carbon atom.A substituent instance of substituted radical is ionic hydrophilic radical.An instance of heterocycle sulfinyl is a 4-pyridyl sulfinyl.
Sulfamyl is meant and comprises substituted sulfamyl and unsubstituted sulfamyl.A substituent instance of substituted sulfamyl is an alkyl.The instance of sulfamyl is dimethylamino alkylsulfonyl and two-(2-hydroxyethyl) sulfamyl.
Dyestuff in formula (M1), more preferably those in the following formula (M1-A).
Figure G2008101757780D00731
In formula, R 31, R 32, R 35And R 35Have with formula (M1) in identical implication.
R 33And R 34Represent Wasserstoffatoms or substituting group independently of one another.Substituting group comprises aliphatic group, aromatic group, heterocyclic group, acyl group, carbalkoxy, aryloxy carbonyl, formamyl, alkyl sulphonyl, aryl sulfonyl and sulfamyl.In these, preferably Wasserstoffatoms, aromatic group, heterocyclic group, acyl group, alkyl sulphonyl and aryl sulfonyl; More preferably Wasserstoffatoms, aromatic group and heterocyclic group.
Z 31Expression Hammett substituent constant σ p is at least 0.20 electron-withdrawing group, preferred Z 31Be that σ p is at least 0.30, more preferably be at least 0.45, preferably be at least 0.60 again, but preferably be not more than 1.0 electron-withdrawing group.
Particularly; Hammett substituent constant σ p is at least 0.60 electron-withdrawing group and (for example comprises cyanic acid, nitro and alkyl sulphonyl; Methane sulfonyl) and aryl sulfonyl (for example; Phenyl sulfonyl) Hammett substituent constant σ p be at least the instance of 0.45 electron-withdrawing group except above-mentioned group be acyl group (like ethanoyl), carbalkoxy (like dodecyl oxygen carbonyl), aryloxy carbonyl (as-chlorobenzene oxygen carbonyl), alkyl sulphinyl (like the n-propyl sulfinyl), aryl sulfonyl kia (like the phenyl sulfinyl), sulfamyl (like N-ethyl sulfamyl, N, N-dimethylamino alkylsulfonyl) and haloalkyl (like trifluoromethyl).
The instance that Hammett substituent constant σ p is at least 0.30 electron-withdrawing group is that acyloxy (like acetoxyl group), formamyl are (like N-ethylamino formyl radical, N except above-mentioned group; N-diethylamino formyl radical), halogenated alkoxy (like trifluoromethoxy), halo aryloxy (like penta fluoro benzene oxygen base), alkylsulfonyl oxygen base (like methyl sulphonyl oxygen base), halogenated alkylthio (like the difluoro methylthio group), quilt at least two (the σ p of each is at least 0.15) substituted aryl of electron-withdrawing group (as 2,4-dinitrophenyl, pentafluorophenyl group) and heterocyclic group (like 2-benzoxazolyl, 2-[4-morpholinodithio base, 1-phenyl-2-benzimidazolyl-).
The specific examples that Hammett substituent constant σ p is at least 0.20 electron-withdrawing group is a halogen atom except above-mentioned group.
Especially, preferred Z 31Be any in following: contain the acyl group of 2 to 20 carbon atoms, the carbalkoxy that contains 2 to 20 carbon atoms, nitro, cyanic acid, contain 1 to 20 carbon atom alkyl sulphonyl, contain 6 to 20 carbon atoms alkyl sulphonyl, contain the sulfamyl of 1 to 20 carbon atom or contain the haloalkyl of 1 to 20 carbon atom; Any in more preferably following: cyanic acid, contain the alkyl sulphonyl of 1 to 20 carbon atom or contain the aryl sulfonyl of 6 to 20 carbon atoms; Cyanic acid most preferably.
Z 32Expression Wasserstoffatoms or substituting group.Substituting group comprises aliphatic group, aromatic group and heterocyclic group.Preferably, Z 32Be aliphatic group, more preferably contain the alkyl of 1 to 6 carbon atom.
Q representes Wasserstoffatoms or substituting group.Substituting group comprises aliphatic group, aromatic group and heterocyclic group.Especially, preferably Q is the group that comprises the non-metallic atom that forms 5-to 8-unit lottery of lotteries needs.5-to 8-unit ring can be substituted, and can be that saturated rings maybe can contain unsaturated link(age).Especially, more preferably it is aromatic group or heterocyclic group.The non-metallic atom of preferred its usefulness is nitrogen, oxygen, sulphur and carbon atom.The instance of ring texture is benzene, pentamethylene, hexanaphthene, suberane, cyclooctane, tetrahydrobenzene, pyridine, pyrimidine, pyrazine, pyridazine, triazine, imidazoles, benzoglyoxaline 、 oxazole, benzoxazole, thiazole, benzothiazole, oxyethane, tetramethylene sulfone and thian ring.
The Wasserstoffatoms of each group in formula (M1-A) can be substituted.For substituting group, refer to the group G in the formula of regarding to (M1) 3, R 31And R 32Mentioned those.
What mention below is the substituent special preferably combination of the azoic dyestuff of formula (M1).Preferred R 35And R 36Be any in Wasserstoffatoms, alkyl, aryl, heterocyclic group, alkylsulfonyl or the acyl group; Any in Wasserstoffatoms, aryl, heterocyclic group or the alkylsulfonyl more preferably; Most preferably be any in Wasserstoffatoms, aryl or the heterocyclic group.But, R 45And R 46Must not be Wasserstoffatoms simultaneously.
G 3Preferably Wasserstoffatoms, halogen atom, alkyl, hydroxyl, amino or amido are more preferably Wasserstoffatoms, halogen atom, amino or amido, most preferably are Wasserstoffatoms, amino or amido.
Preferred A 31Be pyrazoles ring, imidazole ring, isothiazole ring, thiadiazoles ring or benzothiazole ring, more preferably pyrazoles ring or isothiazole ring, optimum is the pyrazoles ring.
Also preferably, B 31And B 32Be respectively=CR 31-with-CB 32=; And preferred R 31And R 32Any in Wasserstoffatoms, alkyl, halogen atom, cyanic acid, formamyl, carboxyl, hydroxyl, alkoxyl group or the carbalkoxy, more preferably any in Wasserstoffatoms, alkyl, carboxyl, cyanic acid or the formamyl.
As for the substituent preferably combination of the compound of formula (M1), it is desirable at least one substituting group is above-mentioned preferred group.More preferably, more substituting group is a preferred group.Most preferably, all substituting groups are preferred group.
What mention below is the specific examples of the azoic dyestuff of formula (M1), and still, the present invention should not receive these restriction.
Figure G2008101757780D00761
Figure G2008101757780D00762
Figure G2008101757780D00771
Figure G2008101757780D00772
Figure G2008101757780D00782
Figure G2008101757780D00791
Figure G2008101757780D00792
Figure G2008101757780D00801
Figure G2008101757780D00811
Figure G2008101757780D00821
Figure G2008101757780D00831
Figure G2008101757780D00841
Figure G2008101757780D00851
Figure G2008101757780D00861
Figure G2008101757780D00871
Figure G2008101757780D00881
The content of azoic dyestuff in ink of preferred formula (M1) is 0.2 to 20 weight %, more preferably 0.5 to 15 weight %.Also the solubleness (or its dispersibility in stable condition) of preferred coloring agent in 20 ℃ water is at least 5 weight %, more preferably at least 10 weight %.
The dyestuff of formula (M2) is described below.
Figure G2008101757780D00891
Wherein R representes Wasserstoffatoms, alkyl, hydroxy lower alkyl, cyclohexyl, one or dialkyl aminoalkyl or cyanic acid-low alkyl group; Y representes the chlorine atom; Hydroxyl; Amino; One or dialkyl amido (choose wantonly on its moieties, to contain and be selected from sulfonic group; The substituting group of carboxyl and hydroxyl); Aryl alkyl amino; Cycloalkyl amino; Alkoxyl group; Phenoxy (is chosen wantonly on phenyl ring, to contain and is selected from sulfonic group; Carboxyl; Kharophen; The substituting group of amino and hydroxyl); Anilino (optional) with one or two substituting group replacement that is selected from sulfonic group and carboxyl; Naphthyl amino (wherein naphthyl can be replaced by sulfonic group); Or one or dialkyl aminoalkyl; X representes crosslinked group; Z representes Wasserstoffatoms, alkali metal, alkali earth metal, alkylamino, alkanol amino or ammonium.
In the present invention, preferably use the Anthrapyridone dyes of formula (M2).In formula; Preferred Z is alkali metal, alkali earth metal, alkylamino, alkanol amino or ammonium; For example sodium, potassium or lithium of alkali metal more preferably, alkanol amino is an alcohol amido, diethanolamino, triethanolamine base, amino, amino, three Virahol amino or the ammoniums of diisopropanol of a Virahol for example.
The compound of following formula (M3) is the representative instance of the dyestuff of formula (M2).
Figure G2008101757780D00901
The not special ground that limits, alleged here term " alkyl " is meant any and every kind of general alkyl that this area is so-called.Usually, only if specify that in addition preferred alkyl is to contain 1 to 10 carbon atom, the more preferably alkyl of 1 to 4 carbon atom.This should be applied to term equally, in alkoxyl group with the alkyl of aralkyl.
In formula of the present invention (M2) with (M3), the alkyl that is used for R is for example methyl, ethyl, n-propyl, a normal-butyl of C1-C4 alkyl for example.Be used for the hydroxy lower alkyl of R and the alkyl of cyanic acid-low alkyl group and comprise for example ethyl and propyl group, but preferred ethyl.The alkylamino that is used for Y be for example the C1-C8 alkylamino for example methylamino, ethylamino, butyl are amino, the 2-ethylhexyl is amino.Dialkyl amido be for example the C1-C8 dialkyl amido for example diethylamino, dibutylamino, dihexyl are amino.Alkyl aryl ammonium be for example phenyl (C1-C6) alkylamino for example benzylamino, styroyl are amino, hydrocinnamyl is amino.Cycloalkyl amino is for example to encircle (C5-C7) alkylamino for example cyclohexyl is amino, cyclopentyl is amino.Alkoxyl group is for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy, a butoxy of C1-C4 alkoxyl group for example.Moieties in the alkylamino that contains sulfonic acid or carboxyl is for example methyl, ethyl, n-propyl, a normal-butyl of C1-C4 alkyl for example.
The instance that is used for the phenoxy of Y, its substituting group that can be selected from sulfonic group, carboxyl, kharophen, amino and hydroxyl replaces, and is 4-sulfophenoxy, 4-carboxyl phenoxy, 4-kharophen phenoxy, 4-amino-benzene oxygen and 4-hydroxyphenoxy.
The instance that is used for the alkylamino of Y, it contains sulfonic group or carboxyl, is 2-sulfo group ethylamino, carboxyl methylamino, amino, the 1-carboxy ethyl amino, 1 of 2-carboxy ethyl, 2-dicarboxyl ethylamino and two (carboxyl methyl) amino.The instance of the alkylamino of hydroxyl is that hydroxyethylamino and dihydroxy ethyl are amino.
The instance that is used for the anilino of Y; Its one or two substituting group that can be selected from sulfonic group and carboxyl replaces; Be 2,5-disulfobenzene amido, 3-aniline sulfonic acid base, 2-aniline sulfonic acid base, 4-aniline sulfonic acid base, 2-carboxyl-4-aniline sulfonic acid base and 2-carboxyl-5-aniline sulfonic acid base.
Be used for the amino instance of naphthyl of Y, it can be replaced by sulfonic group, is 3,6,8-three sulfo groups-1-naphthyl amino, 4,6, and 8-three sulfo groups-2-naphthyl amino, 3,6,8-three sulfo groups-2-naphthyl amino and 4,8-disulfo-2-naphthyl is amino.
The crosslinked group that is used for X is for example to contain 1 to 20 carbon atom and the optional divalent group that comprises the arbitrary hydrocarbon residue of nitrogen, oxygen and sulphur atom, and it contains nitrogen or Sauerstoffatom and its at its two ends and contains two extensions from the nitrogen of its two ends or the key of Sauerstoffatom.Particularly, it can be expressed from the next:
-N (H) m (A-) nN (H) m-or-O-A-O-
Wherein A representes to contain 1 to 20 carbon atom and the optional divalent group that comprises the arbitrary hydrocarbon residue of nitrogen, oxygen and sulphur atom; N representes 1 or 2; M representes 1 or 0; And when n was 2, m was 0 so.
The divalent hydrocarbon residue base that contains 1 to 20 carbon atom that is used for A comprises that for example containing 1 to 15 carbon atom (for example comprises 1 or 2 heteroatoms with optional; Nitrogen, oxygen, sulphur) aliphatic group; Contain 3 to 10 carbon atoms; Preferred 5 to 19 carbon atoms and the optional divalent aromatic radical of 1 to 3 heteroatoms (for example, nitrogen, oxygen, sulphur) and the divalent group of aliphatic group and aromatic group combination of comprising.These groups can contain substituting group (sulfonic group, carboxyl, amino, and for aromatic group, low alkyl group).
Aliphatic group comprise for example contain 1 to 6 carbon atom with optional by low alkyl group substituted (gathering) methylene radical, for example methylene radical, dimethylene (ethylidene), trimethylene (propylidene), 2-methyl trimethylene (2-methyl propylidene), tetramethylene (butylidene), hexa-methylene; The ring alkylidene group that contains 5 to 7 carbon atoms is pentamethylene-1 for example, 2-or-1,3-two bases, cyclohexyl-1,2-,-1,3-or-1,4-two bases, pentamethylene-two base; Comprise low-grade alkylidene and the aliphatic group (optional replace) that contains the aliphatic series ring of 5 to 7 carbon atoms, methylene radical hexanaphthene-1 for example, 4-two own methylene radical (CH with low alkyl group 2-C 6H 10-CH 2-), methylene radical bicyclohexane-two base (C 6H 10-CH 2-C 6H 10-), methylene radical two (methylcyclohexane-two base) { C 6H 10(CH 3)-CH 2-C 6H 10(CH 3)-}, hexanaphthene-two bases-dimethylene (CH 2-C 6H 10-CH 2-); With contain 1 to 7 carbon atom and comprise heteroatomic aliphatic group, for example methylene radical oxygen methylene (CH 2-O-CH 2-), the amino (C of two (dimethylenes) 2H 4-NH-C 2H 4-), sulfonium methylide methylene (CH 2-S-CH 2-), oxygen base bicyclohexane-two base (C 6H 10-O-C 6H 10-).
Divalent aromatic radical is the aromatic group phenylene (C for example that for example contains 6 to 10 carbon atoms 6H 4-), naphthylidene (C 10H 6-).
The divalent group that forms through combination aliphatic group and aromatic group is xylylene (CH-C for example 6H 4-CH-).
More preferably, A is dimethylene, hexa-methylene, 1,3-xylylene, methylene radical bicyclohexane-4,1-two bases, methylene radical two (2-methylcyclohexane-4,1-two bases) or hexanaphthene-1,3-two bases-dimethylene.
Crosslinked group X for example comprises diamino-alkylidene group for example 1,2-diamino-ethylidene (NH-CH 2CH 2-NH-), 1,4-diamino-butylidene (NH-C 4H 8-NH-), 1,6-diamino-hexylidene (NH-C 6H 12-NH-); Diamino-phenylene for example 1,4-piperazine two base (NC 4H 8N-), 1,4-diamino-phenylene (NH-C 6H 4-P-NH-), 1,3-diamino-phenylene (NH-C 6H 4-m-NH-); Substituted diamino-phenylene is 4-sulfo group-1 for example, 3-diamino-phenylene { NH-C 6H 4(p-SO 3H)-and m-NH-}, 5-carboxyl-1, the 3-diamino-phenylene; 1,3-diamino-xylylene (NH-CH 2-C 6H 4-m-CH 2-NH-), 1,4-diamino-xylylene (NH-CH 2-C 6H 4-p-CH 2-NH-), 4,4 '-diamino--2-sulfo group-diphenyl amino (NH-C 6H 4(m-SO 3H)-NH-C 6H 4-p-NH-), 4,4 '-diamino-dicyclohexyl methane (NH-C 6H 10-4-CH 2-C 6H 10-4 '-NH-), 4,4 '-diamino--3,3 '-dimethyl-dicyclohexyl methyl hydride (NH-C 6H 10(3-CH 3)-4-CH 2-C 6H 10(3 '-CH 3)-4 '-NH-); 1,3-two (amino methyl) hexanaphthene (NH-CH 2-C 6H 10-3-CH-NH-); The substituted alkylidene group of dioxy base is dioxy base ethylidene (O-CH for example 2-CH 2-O-), 1,3-dioxy base butylidene (O-C 4H 8-O-), 2,2 '-dioxy benzyl ethyl ether (O-CH 2CH 2-O-CH 2CH 2-O-), 1,4-dioxy base phenylene (O-C 6H 4-p-O-), 1,3-dioxy base phenylene (O-C 6H 4-m-O-), 4,4 '-dioxy base diphenyl ether (O-C 6H 4-p-O-C 6H 4-p-O-), 4,4 '-dioxy phenylene-thioether (O-C 6H 4-p-S-C 6H 4-p-O-), 2,5-and 2,6-norbornane diamino-, 1,4-dioxy ylmethyl cyclohexylidene (O-CH-C 6H 10-4-CH 2-O-).Wherein n be 2 with m be that (A-) instance of the group of nN (H) m-is 1,4-piperazine two base (NC for formula-N (H) m of 0 4H 8N-).
The preferably combination of R, Y and X is following: for example, R is Wasserstoffatoms or methyl; Y is chlorine atom, hydroxyl or amino; And X is a diamino-ethylidene, 1,4-piperazine two bases, 1,3-diamino-xylylene, 4,4 '-diamino-dicyclohexyl methane, 4,4 '-diamino--3,3 '-dimethyl-dicyclohexyl methyl hydride or 1,3-two (amino methyl) hexanaphthene.
The specific examples of the Anthrapyridone compounds of formula (M3) is mentioned in following table.In table, the diamino-ethylidene is meant 1,2-diamino-ethylidene (NH-CH 2CH 2-NH-).Ph is meant phenyl.For example, PhO is a phenoxy, and NHPh is an anilino, and should be applicable to other equally.NHPh (p-SO 3H) be meant 4-aniline sulfonic acid base (p-SO wherein 3H is meant that sulfonic acid is in the contraposition of phenyl).NHPh (COOH) 2(3,5) are meant 3,5-dicarboxyl anilino (Ph (COOH) wherein 2(3,5) are meant that carboxyl replaces on the 3-of phenyl and 5-position).This is equally applicable to other." naphthyl " is naphthyl; " NH-2 naphthyl (SO 3H) 3 (3,6,8) " be 3,6,8-three sulfo groups-2-naphthyl is amino; And NH (cyclohexyl) is that cyclohexyl is amino.
Table 1
Sequence number R X Y
1 CH 3 The diamino-ethylidene OH
2 CH 3 The diamino-ethylidene Cl
3 CH 3 The diamino-ethylidene NH 2
4 CH 3 1,4-piperazine two bases Cl
5 CH 3 1,4-piperazine two bases NH 2
6 CH 3 1,3-diamino-xylylene Cl
7 CH 3 1,3-diamino-xylylene NH 2
8 CH 3 1,4-diamino-xylylene NH 2
9 CH 3 Two (3-aminopropyl) ether NH 2
10 CH 3 3,3 '-imino-(propyl group amine) NH 2
11 CH 3 2,2 '-imino-(ethylamine) NH 2
12 CH 3 1,4-diamino-butylidene NH 2
13 CH 3 1,4-diamino-hexylidene NH 2
14 CH 3 1, the 4-diamino-phenylene NH 2
15 CH 3 1, the 3-diamino-phenylene NH 2
16 CH 3 1,3-diamino--4-sulfo group phenylene NH 2
17 CH 3 1,3-diamino--5-carboxyl phenylene NH 2
18 CH 3 4,4 '-diamino--2-diphenylsulfone base amine NH 2
19 CH 3 4,4 '-diamino--3,3 '-dimethyl--dicyclohexyl methyl hydride NH 2
20 CH 3 4,4 '-diamino--dicyclohexyl methyl hydride NH 2
21 CH 3 The diamino-ethylidene NH(CH 2COOH)
22 CH 3 The diamino-ethylidene NH(CH 2CH 2COOH)
23 CH 3 The diamino-ethylidene NH(CH 2(COOH)CH 2COOH)
24 CH 3 The diamino-ethylidene NH(CH 2(COOH)CH 2CH 2COOH)
25 CH 3 The diamino-ethylidene CH 3O
26 CH 3 The diamino-ethylidene C 6H 5O
27 CH 3 The diamino-ethylidene NH(CH 2CH 2SO 3H)
28 CH 3 The diamino-ethylidene NHC 6H 5
29 CH 3 The diamino-ethylidene NHPh(p-SO 3H)
30 CH 3 The diamino-ethylidene NHPh(COOH) 2(3，5)
31 CH 3 The diamino-ethylidene NHPh(COOH) 2(3，5)
32 CH 3 The diamino-ethylidene NHPh(o-SO 3H)
33 CH 3 The diamino-ethylidene NHPh(m-SO 3H)
Table 2
Sequence number R X Y
34 CH 3 The diamino-ethylidene NHPh(SO 3H) 2(2，5)
35 CH 3 The diamino-ethylidene NH(CH 2CH 2CH 2N(C 2H 5) 2)
36 CH 3 The diamino-ethylidene NH(CH 2CH 2CH 2N(CH 3) 2)
37 CH 3 The diamino-ethylidene NH-2 naphthyl (SO 3H) 3(3，6，8)
38 CH 3 The diamino-ethylidene NH-2 naphthyl (SO 3H) 3(4，6，8)
39 CH 3 The diamino-ethylidene NH-2 naphthyl (SO 3H) 2(4，8)
40 CH 3 The diamino-ethylidene NH (positive C 4H 9)
41 CH 3 The diamino-ethylidene NH (cyclohexyl)
42 CH 3 The diamino-ethylidene NH(CH 2CH 2OH)
43 CH 3 The diamino-ethylidene N(CH 2CH 2OH) 2
44 CH 3 The diamino-ethylidene NHCH 2Ph
45 H The diamino-ethylidene NH 2
46 H 1,3-diamino-xylylene NH 2
47 H 1,4-piperazine two bases NH 2
48 C 2H 5 1,3-diamino-xylylene NH 2
49 C 4H 9 1,3-diamino-xylylene NH 2
50 Different-C 3H 7 1,3-diamino-xylylene NH 2
51 Cyclohexyl 1,3-diamino-xylylene NH 2
52 C 3H 6N(C 2H 5) 1,3-diamino-xylylene NH 2
53 CH 3 1,4-dioxy base phenylene NH 2
54 CH 3 4,4 '-dioxy base diphenyl ether NH 2
55 CH 3 4,4 '-dioxy base diphenylsulfide NH 2
56 CH 3 4,4 '-dioxy base sulfobenzide NH 2
57 CH 3 4,4 '-dioxy base ditan NH 2
58 CH 3 2,5-and 2,6-norbornane diamino- NH 2
59 CH 3 1,4-dioxy methyl cyclohexylidene NH 2
60 CH 3 2,5-dimethyl--1,4-piperazine two bases NH 2
Can for example obtain the compound of formula (M3) as follows; Wherein crosslinked group X contains amino at its two ends: 2 of the compound of 2 moles following formula (M4) and 2 to 2.4 moles; 4; 6-three chloro-S-triazines (cyanuryl chloride) are reaction 8 hours in 3 to 7 and 5 to 35 ℃ the water at pH, and first condenses that will obtain, and the diamino compounds of the compound of following formula (M5) and 1 mole following formula (M6) is to react 10 minutes to 5 hours for 4 to 10 and 5 to 90 ℃ times at pH; Obtain compound second condenses of following formula (M7), wherein Y is that two ends of chlorine atom and crosslinked group X are amino.
Figure G2008101757780D00961
(M6)
HN(H)m-(-A-)nN(H)mH
Wherein A representes linking group, and is the divalent hydrocarbon residue base that for example contains 1 to 20 carbon atom, and this can contain nitrogen-atoms, Sauerstoffatom or sulphur atom; N is 1 or 2; M is 1 or 0; When n was 1, m was 1 so, and when n was 2, m was 0 so.Preferred A is C1-C6 (a gathering) methylene radical, or optional substituted methylene radical, xylylene, methylene radical bicyclohexane-two base, methylene radical two (methylcyclohexane-two base) or hexanaphthene-two bases-dimethylene; More preferably dimethylene, hexa-methylene, 1,3-xylylene, methylene radical bicyclohexane-4,1-two bases, methylene radical two (2-methylcyclohexane)-4,1-two bases or hexanaphthene-1,3-two bases-dimethylene.
Figure G2008101757780D00971
But, when the compound (M6) that uses in the method be-NH (A) 2-NH (in formula (6), n=2, compound m=0) for example during piperidines, obtain the compound of formula (M7) so, wherein-and NH-A-NH-quilt-N is (A) 2-N-replaces.Then; Compound (M7) is 9 to 12 and 70 to 90 ℃ of following hydrolysis 1 to 5 hour at pH; Or with ammonia or corresponding amine, or with phenol, naphthols or alcohol for example methyl alcohol be 8 to 10 and 90 to 100 ℃ of down reactions 3 to 8 hours at pH, obtain the 3rd condenses so; The compound of following formula (M8), wherein Y is not the chlorine atom.
When the NH that uses formula (M6) in the method (A) 2During the compound of NH, the compound usefulness-N of the formula that obtains so (M8) (A) 2-N replacement-NH-A-NH-.The order of condensation reaction can suitably be confirmed according to the reactivity of question response compound in the method.Do not receive above-mentioned any restriction.
Chemical compound lot in the formula (M8) is the compound of above-mentioned table 1 and table 2.The preferred embodiment of the compound of formula (M8) is as follows, comprises those of table 1 and table 2.
Table 3
Sequence number R X Y
1 CH 3 Methylene radical bicyclohexane-4,1-two bases NH 2
2 CH 3 Methylene radical bicyclohexane-4,1-two bases Ethylamino
3 CH 3 Methylene radical bicyclohexane-4,1-two bases Propyl group is amino
4 CH 3 Methylene radical bicyclohexane-4,1-two bases Propyl group is amino
5 CH 3 Methylene radical bicyclohexane-4,1-two bases Butyl is amino
6 CH 3 Methylene radical bicyclohexane-4,1-two bases The 2-ethylhexyl is amino
7 CH 3 Methylene radical bicyclohexane-4,1-two bases Benzyl
8 CH 3 Methylene radical two (2-methylcyclohexane-4,1-two bases) NH 2
9 CH 3 Hexanaphthene-1,3-two bases-dimethylene NH 2
10 CH 3 Hexanaphthene-1,3-two bases-dimethylene Ethylamino
11 CH 3 Hexanaphthene-1,3-two bases-dimethylene Butyl is amino
12 CH 3 Hexanaphthene-1,3-two bases-dimethylene Dibutylamino
13 CH 3 Hexanaphthene-1,3-two bases-dimethylene The 2-ethylhexyl is amino
14 CH 3 Methylene radical bicyclohexane-4,1-two bases Benzyl
15 CH 3 Methylene radical bicyclohexane-4,1-two bases Cyclohexyl is amino
16 CH 3 Methylene radical bicyclohexane-4,1-two bases Cyclopentyl is amino
17 CH 3 Methylene radical bicyclohexane-4,1-two bases The diethylamino propyl group is amino
18 CH 3 Methylene radical bicyclohexane-4,1-two bases The dibutylamino propyl group is amino
When the glycol compound that uses formula HO-A-OH (wherein A have with above identical implication) replacement formula (M6) diamino compounds and when it being carried out condensation with common mode; Obtain the compound of formula (M7) so, wherein crosslinked group-NH-A-NH-is replaced by O-A-O.This can the mode identical with aforesaid method can process, and obtains the compound of formula (M8), and wherein crosslinked group-NH-A-NH-is replaced by O-A-O.
The compound that obtains with top mode thus can be any form of free acid and their salt.Therefore, can be with these compounds with free acid and the for example form use of an alkali metal salt, alkaline earth salt, alkylamino salt, alkanol amine salt or ammonium salt of their salt.Preferably, their form is for example sodium salt, sylvite, a lithium salts of an alkali metal salt; Alkanol amine salt is Monoethanolamine MEA BASF salt, diethanolamine salt, triethanolamine salt, a Virahol amine salt, diisopropanol amine salt, tri-isopropanolamine salt for example; And ammonium salt.(ink group)
For the formation or the tone control of full-colour image, ink group of the present invention can comprise any other dyestuff with above-mentioned dyestuff.The instance of the other dyestuff that can use in the present invention is following.
Yellow dyes is for example aryl or heteroaryl (heteryl) azoic dyestuff, and it contains phenol, naphthols, and aniline, pyrazolone, pyridone, or the open chain activity methene compound is as its coupling composition; Azomethine dyes, it contains the open chain activity methene compound as its coupling composition; Methine dyes such as Ben Yajiaji dyestuff, one methine-oxonol dye; Quinone dyestuff such as naphthoquinone dyestuff, anthraquinone dye.Except that other dyestuff kind these is quinophthalones (quinophthalone) dyestuff, nitro-nitroso-dyestuff, acridine dye and a dihydroketoacridine dyestuff.These dyestuffs can only just manifest yellow after its chromophoric part is by disassociation.In this case, counter cation can be inorganic cation such as basic metal or ammonium ion, or organic cation such as pyridine or quaternary ammonium salt cationic, maybe can also be to contain these polymer cations as its part-structure.
Magenta dyestuff is for example aryl or heteroaryl azoic dyestuff, and it contains phenol, naphthols, and aniline is as its coupling composition; Azomethine dyes, it contains pyrazolone or Pyrazolotriazole as its coupling composition; Methine dyes such as arylidene dyestuff, styryl dye, merocyanine dyes, oxonol dye; Carbonium dye such as diphenyl methane dye, triphenylmethane dye, xanthene dye; Quinone dyestuff such as naphthoquinone dyestuff, anthraquinone dye, Anthrapyridone dyes; Condensation polycyclic dyestuff such as dioxazine dyestuff.These dyestuffs can only just manifest carmetta after its chromophoric part is by disassociation.In this case, counter cation can be inorganic cation such as basic metal or ammonium ion, or organic cation such as pyridine or quaternary ammonium salt cationic, maybe can also be to contain these polymer cations as its part-structure.
Cyan dye is for example azomethine dyes such as indoaniline dyes, indophenol dye; Polymethin dye such as cyanine dyes, oxonol dye, merocyanine dyes; Carbonium dye is as like diphenyl methane dye, triphenylmethane dye, xanthene dye; Phthalocyanine pigment; Anthraquinone dye; Aryl or heteroaryl azoic dyestuff, it contains phenol, naphthols, or aniline is as its coupling composition; With indigo and thioindigo(id)dyes.These dyestuffs can only just manifest cyan after its chromophoric part is by disassociation.In this case, counter cation can be inorganic cation such as basic metal or ammonium ion, or organic cation such as pyridine or quaternary ammonium salt cationic, maybe can also be to contain these polymer cations as its part-structure.
In addition, also can use black dyes such as polyazo dye.
In addition, can also use water-soluble dye for example substantive dyestuff, matching stain, food dye, basic dyestuff and reactive dyestuffs here.Especially, particularly preferably be following dyestuff:
C.I. directly red 2,4,9,23,26,31,39,62,63,72,75,76,79,80,81,83,84,89,92,95,111,173,184,207,211,212,214,218,21,223,224,225,226,227,232,233,240,241,242,243,247;
C.I. direct purple 7,9,47,48,51,66,90,93,94,95,98,100,101;
C.I. direct yellow 8,9,11,12,27,28,29,33,35,39,41,44,50,53,58,59,68,86,87,93,95,96,98,100,106,108,109,110,130,132,142,144,161,163;
C.I. sun blue 1,10,15,22,25,55,67,68,71,76,77,78,80,84,86,87,90,98,106,108,109,151,156,158,159,160,168,189,192,193,194,199,200,201,202,203,207,211,213,214,218,225,229,236,237,244,248,249,251,252,264,270,280,288,289,291;
C.I. directly deceive 9,17,19,22,32,51,56,62,69,77,80,91,94,97,108,112,113,114,117,118,121,122,125,132,146,154,166,168,173,199;
C.I. acid red 35,42,52,57,62,80,82,111,114,118,119,127,128,131,143,151,154,158,249,254,257,261,263,266,289,299,301,305,336,337,361,396,397;
C.I. acid violet 5,34,43,47,48,90,103,126;
C.I. turmeric yellow 17,19,23,25,39,40,42,44,49,50,61,64,76,79,110,127,135,143,151,159,169,174,190,195,196,197,199,218,219,222,227;
C.I. acid blue 9,25,40,41,62,72,76,78,80,82,92,106,112,113,120,127:1,129,138,143,175,181,205,207,220,221,230,232,247,258,260,264,271,277,278,279,280,288,290,326;
C.I. erie black 7,24,29,48,52:1,172;
C.I. reactive red 3,13,17,19,21,22,23,24,29,35,37,40,41,43,45,49,55;
C.I. REACTIVE VIOLET 1,3,4,5,6,7,8,9,16,17,22,23,24,26,27,33,34;
C.I. reactive yellow 2,3,13,14,15,17,18,23,24,25,26,27,29,35,37,41,42;
C.I. Reactive blue 2,3,5,8,10,13,14,15,17,18,19,21,25,26,27,28,29,38;
C.I. HFGR REACTIVE Black HFGR 4,5,8,14,21,23,26,31,32,34;
C.I. alkali red 1:1 2,13,14,15,18,22,23,24,25,27,29,35,36,38,39,45,46;
C.I. alkaline purple 1,2,3,7,10,15,16,20,21,25,27,28,35,37,39,40,48;
C.I. basic yellow 1,2,4,11,13,14,15,19,21,23,24,25,28,29,32,36,39,40;
C.I. reflex blue 1,3,5,7,9,22,26,41,45,46,47,54,57,60,62,65,66,69,71;
C.I. basic black 8.
Operable pigment is commercially available pigment and any other known dye of in various reference, describing in the ink of the present invention.Reference for example is, Color Index (The Societyof Dyers and Colorists); Revised New Version, Pigment Handbook (Nipponpigment Techology Association, 1989); Latest pigment Application Techology (CMC Publishing, 1986); Printing Ink Techology (CMC Publishing, 1984); W.Herbst and K.Hunger, Industrial Organic Pigments, (VCHVerlagsgesellschaft, 1993).Particularly; Pigment dyestuff is azo pigment (azo lake pigment, insoluble azo colour, condensed azo-pigment, chelating-azo pigment); Many ring pigment (phthalocyanine pigment, anthraquinone pigment 、 perylene He perylene ketone (perinone) pigment, indigo pigment, quinacridone pigment 、 triazine dioxin pigment, isoindolinone pigment, quinophthalones pigment, diketopyrrolo-pyrrole pigment); Dyeing pigment lake (pigment lake of acidity or basic dyestuff) and azine pigment; And mineral dye is yellow ultramarine such as C.I. pigment yellow 34,37,42,53; Red pigment such as C.I. Pigment red 101,108; Blue pigments such as C.I. pigment blue 27,29,17:1; Black pigment such as C.I. Pigment black 7, magnetite; With white pigment such as C.I. Pigment white 4,6,18,21.
The pigment that is preferred for forming coloured image is blueness or green pigment for example phthalocyanine pigment, anthraquinonyl indanthrone dyestuff (for example C.I. pigment blue 60) and dyeing pigment lake such as triaryl carbon pigment.Particularly preferably be phthalocyanine pigment, and their preferred embodiment is copper phthalocyanine such as C.I. pigment Blue 15: 1,15:2,15:3,15:4,15:6; One chlorine or low chlorine copper phthalocyanine, the aluminium phthalocyanine is like in EP860475 those; Nonmetal phthalocyanine, C.I. pigment blue 16; Phthalocyanine with central metal atom with Zn, Ni or Ti.C.I. pigment Blue 15 most preferably: 3,15:4 and aluminium phthalocyanine.
Redness to violet pigment is azo pigment (preferred C.I. pigment red 3,5,11,22,38,48:1,48:2,48:3,48:4,49:1,52:1,53:1,57:1,63:2,144,146,184; More preferably C.I. Pigment red 57:1,146,184); Quinacridone pigment (preferred C.I. pigment red 122,192,202,207,209, C.I. pigment violet 19,42; More preferably pigment red 122); Dyeing pigment lake such as triaryl carbon pigment (preferred xanthene class C.I. pigment red 81: 1, C.I. pigment violet 1,2,3,27,39); Triazine dioxin pigment (for example C.I. pigment Violet 23,37); Ketone pyrrolopyrrole pigment (for example the C.I. Pigment red 254); Perylene dye (for example the C.I. pigment violet 29); Anthraquinone pigment (for example C.I. pigment violet 5:1,31,33); Thioindigo color (for example the C.I. pigment red 38,88).
Yellow dyes is an azo pigment (preferred monoazo pigment C.I. Pigment Yellow 73 1,3,74,98; Two azo pigment, like the C.I. pigment Yellow 12,13,14,16,17,83; General azo pigment is like C.I. Pigment Yellow 73 93,94,95,128,155; Benzimidazolone pigment is like C.I. pigment Yellow 12 0,151,154,156,180; More preferably do not use benzidine compound as those of their feedstock production); Isoindoline or isoindolinone pigment (preferred C.I. Pigment Yellow 73 109,110,137,139); Quinophthalones pigment (preferred C.I. pigment yellow 13 8); Flavanthrone pigment (for example the C.I. Pigment Yellow 73 24).
Black pigment is mineral dye (preferred carbon black and magnetite) and nigrosine.In addition, can also use orange pigments (for example, C.I. pigment Orange 13,16) and veridian (for example C.I. pigment Green 7) in here.
Operable pigment can be that above-mentioned naked pigment maybe can be surface-treated pigment in the ink of the present invention.For their surface treatment; Can maybe can be to the pigment application tensio-active agent with resin or wax coating pigment; The active substance radical of silane coupling agent, epoxy compounds, polymeric polyisocyanate, diazonium salt (for example, from) is combined with surface of pigments.These for example are described in the following reference and patent publications:
<1>Properties?and?Applications?of?Metal?Soap(Miyuki?Publishing)
<2>Printing?Ink(CMC?Publishing，1984)
<3>Latestpigment?Application?Techology(CMC?Publishing，1986)；
<4>USP5,554,739、5,571，311
<5>JP-A9-151342、10-140065、10-292143、11-166145。
Particularly; As in the USP of top < 4>through making disperseing pigment certainly and being effectively of diazonium salt and carbon black prepared in reaction according to the capsule pigment of the method in the Japanese Patent publication of top < 5>preparation because they can stably be dispersed in the ink without any need for too much dispersion agent.
In the present invention, pigment can disperse through using dispersion agent.According to used pigment, can use various known dispersion agents.For example, can use the low dispersal agent molecule of surfactant types or the dispersion agent of polymer type.The case description of spendable dispersion agent is in for example JP-A3-69949 and European patent 549486 here.When using dispersion agent, can also be to wherein adding the pigment derivative that is called synergistic agent, to promote the absorption of pigment to dispersion agent.
Consider the size of discrete particles, the particle size that can be used for the pigment of ink of the present invention is preferably 0.01-10 μ m, more preferably 0.05-1 μ m.
For the dispersed color method, operable is any known technology that in ink preparation or toning agent preparation, uses usually.Disperseing machine can be any horizontal or vertical oscillating mill, attritor, colloid mill, ball mill, three-roll mill, ball mill, super grinding machine, impeller, dispersion machine, KD grinding machine, dynatron (dynatron), the pressure kneader.They are described in detail among the Latest pigment Application Techology (CMC Publishing, 1986).
Ink for inkjet of the present invention can comprise tensio-active agent, and tensio-active agent is described below.
Tensio-active agent in the ink of the present invention improves the ejection stability of ink to the liquid property of control ink, improves the water-repellancy of the image that ink forms and prevents that ink oozing out on printed matter from being effective.
Tensio-active agent comprises AS, like sodium lauryl sulphate, and dodecyloxy sodium sulfonate and sodium alkyl benzene sulfonate; Cats product such as pyrisept, trimethylammonium cetyltrimethyl ammonium muriate and tetrabutylammonium chloride; And nonionogenic tenside, like the T 46155 nonylplenyl ether, T 46155 naphthyl ether and polyoxyethylene octyl phenyl ether.Particularly preferably be nonionogenic tenside.
The content of the tensio-active agent of ink is 0.001 to 20 weight %, is preferably 0.005 to 10 weight %, more preferably 0.01 to 5 weight %.
Can prepare ink for inkjet recording of the present invention in the aqueous medium through above-mentioned dyestuff preferably being dissolved with tensio-active agent and/or being dispersed in.Alleged here " aqueous medium " is meant water, or the mixture of water and less water compatibility organic solvent, optional additive such as wetting agent, stablizer and the sanitas of comprising.
In preparation ink of the present invention, under the situation in the ink water soluble, preferably at first be dissolved in the water so.Then, add all kinds of SOLVENTS and additive to it, dissolving and mixing are to prepare uniform composition for ink.
For dissolved constituent, for example, can use the whole bag of tricks of stirring, ultrasonic irradiation and vibration.Particularly preferably be the method that stirs component.When stirring component, can use various stirring known in the art.For example, they can be with fluidization, reverse stir, stir with the modes such as shearing force stirring of dissolver.What also preferably use is the magnetic agitation method here, wherein uses magnetic stirring apparatus, to utilize the shearing force of giving the container bottom face.
The instance that can be used for the present invention's water miscibility organic solvent is alcohol (for example methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, hexanol, hexalin, phenylcarbinol), a polyvalent alcohol (for example 1; 2-ethylidene glycol, glycol ether, triglycol, polyoxyethylene glycol, Ucar 35, dipropylene glycol, W 166, butyleneglycol, pinakon, pentanediol, glycerine, hexanetriol, thiodiglycol), diol, derivatives (for example ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triglycol list ether, ethyleneglycol monophenylether), amine be (like thanomin, diethylolamine, trolamine, N methyldiethanol amine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, 1; 2-quadrol, NSC 446, Triethylenetetramine (TETA), polymine, 4-methyl-diaminopropane), and other polar solvent (like methane amide, N; Dinethylformamide, N; N-N,N-DIMETHYLACETAMIDE, DMSO 99.8MIN., tetramethylene sulfone, 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, N-vinyl-2-Pyrrolidone, 2-oxazolidone, 1,3-dimethyl--2-imidazolone, acetonitrile, acetone).Two or more above-mentioned water miscibility organic solvents of use capable of being combined.
At above-mentioned dyestuff is under the situation of oil-soluble colourant, can they be dissolved in high boiling organic solvent so, and emulsification and being distributed in the aqueous medium then is to prepare ink of the present invention.
The boiling point that is used for the present invention's high boiling organic solvent is 150 ℃ or higher, is preferably 170 ℃ or higher.
For example, described solvent comprises phthalic ester (for example Witcizer 300, DOP, dicyclohexyl phthalate, two-2-ethylhexyl phthalic ester, phthalic acid ester in the last of the ten Heavenly stems, two (2, the 4-di-tert-pentyl-phenyl) isophthalic acid ester, two (1; 1-diethylammonium propyl group) phthalic ester), Phosphoric acid or phosphonic acid ester (phosphone esters) (for example diphenyl phosphate, triphenylphosphate, Tritolyl Phosphate, 2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphoric acid ester, thricyclohexyl SULPHOSUCCINIC ACID ESTER, three-ethylhexyl dihydrogen phosphate, tridecyl phosphate, two-2-ethylhexyl phenyl phosphate ester), benzoic ether (2-ethylhexyl benzoic ether, 2 for example; 4-dichlorobenzoic acid ester, phenylformic acid dodecyl ester, 2-ethylhexyl-right-hydroxybenzoate), acid amides (N for example, N-diethylammonium lauramide, N; The N-diethyl lauramide), alcohol or phenol (for example isooctadecanol, 2,4-di-tert-pentyl phenol); Aliphatic ester (for example succsinic acid dibutoxy ethyl ester, two-2-ethylhexyl succinate, 2-hexyl decyl tetradecanoate, tributyl citrate, ethyl azelaate, lactic acid isooctadecane ester and trioctyl lemon acid); Anils (N, N-dibutyl-2-butoxy-uncle's 5-octyl group aniline), clorafin (cl content is 10% to 80% paraffin); 1; 3,5-benzenetricarboxylic acid ester (for example 1,3; 5-benzenetricarboxylic acid tri-n-butyl); Dodecylbenzene, diisopropylnaphthalene, phenol (for example 2; 4-di-tert-pentyl phenol, 4-dodecyloxy phenol, 4-dodecyl oxygen carbonyl phenol, 4-(4-dodecyloxy phenyl sulfonyl) phenol); Carboxylic acid (2-(2,4-two tert-pentyl phenoxybutyhc and 2-oxyethyl group suffering-capric acid) for example, alkyl phosphate (for example two-2-(ethylhexyl) SULPHOSUCCINIC ACID ESTER and diphenyl phosphate).By the high boiling organic solvent that uses and the weight ratio of oil-soluble colourant, the amount of high boiling organic solvent is 0.01 to 3 times of amount of oil-soluble colourant, preferred 0.01 to 1.0 times.
High boiling organic solvent can use or make up use (for example, Tritolyl Phosphate and Witcizer 300 separately; Trioctyl phosphate and two (2-ethylhexyl) sebate; Witcizer 300 with gather (N tert butyl acrylamide)).
Except that above-mentioned, can be used for other instance of the compound of high boiling organic solvent of the present invention, and/or the method that is used to prepare these high boiling organic solvents for example is described in: USP2,322,027,2,533,514,2,772,163,2,835,579,3,594,171,3; 676,137,3,689,271,3,700,454,3,748,141,3,764,336,3,765,897,3; 912,515,3,936,303,4,004,928,4,080,209,4,127,413,4,193; 802,4,207,393,4,220,711,4,239,851,4,278,757,4,353,979,4; 363,837,4,430,421,4,430,422,4,464,464,4,483,918,4,540; 657,4,684,606,4,728,599,4,745,049,4,935,321,5,013,639; EP276,319A, 286,253A, 289,820A, 309,158A, 309,159A, 309,160A, 509,311A, 510,576A; Deutsches Wirtschafts Patent 147,009,157,147,159,573,225,240A; English Patent 2,091,124A; JP-A48-47335; 50-26530; 51-25133; 51-26036; 51-27921; 51-27922; 51-149028; 52-46816; 53-1520; 53-1521; 53-15127; 53-146622; 54-91325; 54-106228; 54-118246; 55-59464; 56-64333; 56-81836; 59-204041; 61-84641; 62-118345; 62-247364; 63-167357; 63-214744; 63-301941; 64-9452; 64-9454; 64-68745; 1-101543; 1-102454; 2-792; 2-4239; 2-43541; 4-29237; 4-30165; 4-232946; 4-346338.
By the weight ratio of the amount of high boiling organic solvent that uses and oil-soluble colourant, the amount of high boiling organic solvent is 0.01 to 3 times of amount of oil-soluble colourant, preferred 0.01 to 1.0 times.
Among the present invention, with oil-soluble colourant and high boiling organic solvent emulsification be dispersed in the aqueous medium.For they emulsification better, can use low boiling point organic solvent.The boiling point of low boiling point organic solvent under normal pressure is about 30 ℃ to 150 ℃.Its preferred embodiment is ester (for example ETHYLE ACETATE, butylacetate, ethyl propionate, β-ethoxyethyl acetic ester, a methylcellosolve acetate); Alcohol (for example Virahol, propyl carbinol, sec-butyl alcohol); Ketone (for example MIBK, methyl ethyl ketone, pimelinketone); Acid amides (for example N, N-Methyl pyrrolidone), ether (for example THF 、 diox), but this is not restrictive.
Emulsification disperses as follows: dyestuff is dissolved in the high boiling organic solvent separately, or in the mixed solvent of itself and low boiling point organic solvent, preparing oil phase, and with its be dispersed in wrap basically aqueous water-based mutually in, to form the trickle oil droplet of oil phase thus.In this method, if desired, can additive such as tensio-active agent, wetting agent, dye stabilizers, emulsion stabilizer, sanitas and antiseptic-germicide be added among any or two kinds in water and the oil phase.
For emulsification, usually oil phase is joined water.But, in contrast, can also in oil phase, drip water with the phase reversion emulsification method.This is preferred in the present invention.When the dyestuff that is used for the present invention is water miscible dyestuff and additive when being oil-soluble additive, can also adopt emulsification method so.
In emulsification, can use various tensio-active agents.For example; AS preferably is like soap, alkyl sulfuric ester salt, sulfonated alkylbenzene, sulfonated alkyl naphathalene, dialkyl sulfosuccinates, alkylphosphonic, napsylate-Superlysoform condenses, laureth sulfate; And nonionogenic tenside; Like Voranol EP 2001, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl amine, glycerol fatty acid ester, oxygen ethene-oxypropylene segmented copolymer.Ethynyl T 46155 oxide compound further preferably, Surfynols (Air Products & Chemicals).The amphoterics of amine oxide type further preferably, like N, N-dimethyl--N-alkyl amine oxide.In addition, can also use at JP-A 59-157636 here, the 37th to 38 page; With the promoting agent that comes to the surface described in the ResearchDisclosure No.308119 (1989).
In order after its preparation, to make emulsion stable immediately, can be with above-mentioned combinations-of surfactants to wherein adding water-soluble polymers.The preferred embodiment of water-soluble polymers is Z 150PH, Vinylpyrrolidone polymer, polyethylene oxide, ROHM, SEPIGEL 305 and their multipolymer.It is also preferred that what use is natural water-soluble copolymer such as polysaccharide, casein, gelatin.For the stabilizing dye dispersion-s; Also spendable is the polymkeric substance that is insoluble to the water-based medium basically, like the polyvinyl compound that obtains through polymerizations such as propenoate, methacrylic ester, vinyl ester, acrylic amide, USAF RH-1, alkene, vinylbenzene, vinyl ether, vinyl cyanide, urethane, polyester, polymeric amide, polyureas, polycarbonate etc.Preferably, these polymkeric substance contain-SO 3 -Or-COO -When using these polymkeric substance that are insoluble to the water-based medium basically here, their amount is preferably the 20 weight % at the most of high boiling organic solvent, more preferably 10 weight % at the most.
When emulsification and dispersed oil soluble dye and high boiling organic solvent during, it is especially important control dyestuff dispersed particles size with the preparation water-base ink.In order to improve the colour purity and the density of the image that forms with the ink-jet pattern, must be reduced in the mean particle size of the dye granule in the jetting ink.Preferred coloring agent particulate volume averaging particle size is for being at most 1 μ m, more preferably 5nm to 100nm.
Can easily measure the volume averaging particle size and the particle size dispersion of dispersive dye granule with any known method.For this reason, for example, adoptable is static light scattering method, dynamic light scattering method or centrifugal settling method and in Lecture of Experimental Chemistry, the 4th edition, the method for the 417th to 418 page of description.Particularly, use the distilled water diluting ink samples, use commercially available volume averaging particle size analyser (the for example Microtrack UPA of Nikkiso) analysis then, to confirm the particle size of dye granule so that dye granule concentration is 0.1-1 weight %.Especially preferably will be used for measuring based on the dynamic light scattering method of laser doppler, wherein in addition little particle also can measure.
The volume averaging particle size is the mean particle size of particle volume weighting, and this is to obtain divided by all particulate TVs through the summation that the particulate diameter that each is gathered multiply by the product that obtains of its volume.The volume averaging particle size is described in for example S.Muroi, and Chemistry ofPolymer Latex (Polymer Publishing) is in the 119th page.
Be apparent that coarse particles has remarkable influence to the print performance of ink.Particularly, coarse particles blocks printhead, and perhaps even without obstruction, they pollute printhead, the result, and ink can not eject or spray inhomogeneous fully.This effect thus, coarse particles has remarkable influence to the print performance of ink.In order to prevent this trouble, importantly 1 μ, 1 ink comprise at the most 10 particle sizes be 5 μ m or bigger particle and at the most 1000 particle sizes be 1 μ m or bigger particle.
In order to remove these coarse particless, for example, adoptable is any known centrifugal or secondary filter.Removing coarse grained processing can carry out after the emulsification dispersion-s of preparation ink immediately, or after with various additives such as adding emulsification dispersion-ss such as wetting agent, tensio-active agent and just, before print cartridge that the ink that obtains is packed into, carries out.
As reducing mean particle size effectively and removing coarse particles, adoptable is the machinery emulsification device.
Emulsor can be any known a kind of, comprises for example simple whisking appliance, impeller auxiliary agitator, axial agitator, grinding machine for example colloidal mill, ultrasonic agitation device.Especially, particularly preferably be high-pressure homogenizer.
The mechanism of high-pressure homogenizer is for example being described in detail among USP 4,533,254 and the JP-A 6-47264 etc.Gaulin homogenizer (A.P.V.Gaulin), miniature fluidized-bed (Microfluidex) and Altimizer (Sugino Machine) are commercially available.
Recently, developed as at USP 5,720, the high-pressure homogenizer in 551, it is equipped with pulverizing particulate mechanism in superhigh pressure water jet, and these are preferred for emulsification of the present invention and dispersion treatment.An instance with emulsor of superhigh pressure water jet mechanism is DeBEE2000 (Bee International).
Pressure in the high-pressure emulsification decollator during emulsification is at least 50MPa, preferably is at least 60MPa, more preferably is at least 180MPa.
Particularly preferably be at least two kinds of dissimilar emulsors of use among the present invention.For example, will constitute component at first is emulsification in the stirring and emulsifying device, further emulsification in high-pressure homogenizer then.Also preferable methods is a kind of like this method; This method comprises: in case emulsification constitutes component with dispersion in emulsor as above; So in the emulsion that obtains, add additive such as wetting agent, tensio-active agent etc., and before in box that ink is packed into, with its emulsification in high-pressure homogenizer.
Under the situation that as above high boiling organic solvent uses, it is desirable to from emulsion, remove this low boiling point solvent at low boiling point organic solvent, to guarantee stability, security and the health of emulsion.In order to remove low boiling point solvent, can be according to using various known method to remove solvent the solvent types of removing.For example, adoptable is evaporation, vacuum-evaporation or ultrafiltration.It is desirable to after the emulsion preparation, remove low boiling point organic solvent as far as possible immediately.
The method for preparing jetting ink for example is described in detail among JP-A 5-148436,5-295312,7-97541,7-82515, the 7-118584, and this description can be used for preparing ink for inkjet recording of the present invention.
In preparation ink for inkjet recording of the present invention, can dyestuff and additive be dissolved in ultrasound application ripple in the system in the medium.
Ultrasonic vibration in the ink preparation is used for removing bubble from ink.This is because when ink was accepted the pressure from the record printhead, it can produce bubble so.For preventing like this, can accept to impose on ink in advance so that remove bubble from the ultrasonic energy of the energy that writes down printhead with being equal to or greater than ink.
The frequency of ultrasonic vibration is usually at 20Khz at least, preferred 40kHz at least, more preferably 50Khz at least.Be generally at least 2 * 10 through ultrasonic vibration to the energy that ink applies 7J/m 3, be preferably at least 5 * 10 7J/m 3, more preferably at least 1 * 10 8J/m 3The time of ultrasonic vibration is generally about 10 minutes to 1 hour.
Whenever ultrasonic vibration can carrying out after dyestuff is put into medium effectively.After in a single day the finished product ink stored, it can be exposed to UW, and this also is effective.But better is with when the dyestuff dissolving and/or being dispersed in the medium, applies UW to dyestuff, because they are more obvious to the effect of removal bubble, and because their promote dyestuff dissolving and/or dispersion in medium.
Therefore, ultrasonication can with dyestuff dissolving and/or when being dispersed in the medium or any stage afterwards carry out.In other words, ultrasonication can carried out once behind the preparation ink and before processing commodity any time at least.
In a preferred embodiment of the invention, the dissolving and/or the method for dispersed dye are included in the part medium its step of dissolving and with the medium of remainder and the dye solution blended step that obtains in medium.Preferably, in any one in these steps at least, apply UW to this system.More preferably, in the part medium, apply UW to this system in the last step of dissolving dye.
Can carry out the medium of remainder and a back step of the dye solution blended step that obtains with a stage or a plurality of stage.
In preparation ink of the present invention, it is desirable under heating or decompression, system outgased.This is preferred for more effectively from ink, removing bubble.In the dye solution mixing step that step that heating or decompression are carried out system down preferably prepares with medium and front with remainder or carry out afterwards.
Through any known ultra-sonic generator, can produce the UW that in the system of ink preparation, applies.
In preparation ink for inkjet recording of the present invention, it is also important that the composition for ink that filters preparation is with from wherein removing impurity.In this processing, use strainer.The effective pore radius of strainer size is 1 μ m at the most, is preferably 0.05 μ m to 0.3 μ m, more preferably 0.25 μ m to 0.3 μ m.Can various materials be used to form strainer.Particularly for the ink of water-soluble dye, preferred filters is be in particular the aqueous solvent design the sort of.More preferably, strainer is formed by the polymer materials that can finely catch impurity.For filtration, the pattern that composition for ink can the liquids in general charging is passed through strainer.In addition, any other pattern of all right here applying pressure filtration or filtration under diminished pressure.
After the filtration, ink can suck air therein usually.Bubble from air possibly often cause disturbing the image in the ink-vapor recording.Therefore, it is desirable to as top, ink carried out the other degassing again.For with its degassing, for example, it is static for a moment that ink can keep after filtration, or it can use the device that is purchased to carry out the ultrasonic degas or the degassing under reduced pressure.Preferably, carried out ultrasonic degas 30 seconds to 2 hours, more preferably about 5 minutes to 1 hour.
In order to prevent that ink is preferably carried out these processing by contaminating impurity in such as the space of cleaning chamber and clean hatch during handling.Among the present invention, it is desirable to carry out these processing in 1000 grades the space at the most at cleanliness factor.The value that " cleanliness factor " expression is measured with konimeter.
Ink for inkjet recording of the present invention can comprise and be used to prevent that ink is dry and be used to prevent the drying retarder of spray nozzle clogging at inkjet nozzle mouth place; Be used for promoting the penetration enhancer of ink bleed to paper; With other various additives, like UV light absorber, inhibitor, viscosity activator, surface tension activator, dispersion agent, dispersion stabilizer, anti-mycotic agent, rust-preventive agent, pH control agent, skimmer, sequestrant.Ink of the present invention can comprise any in suitable these that select.
For drying retarder, preferably has the water-miscible organic solvent of the vp lower than water.Its specific examples is a polyvalent alcohol, for example typically, and 1; 2-ethylidene glycol, Ucar 35, glycol ether, polyoxyethylene glycol, thiodiglycol, two thiodiglycols, 2-methyl isophthalic acid; Ammediol, 1,2,6-hexanetriol, acetylenediol verivate, glycerine, TriMethylolPropane(TMP); Polyvalent alcohol lower alkyl ether, the for example basic ether of terepthaloyl moietie one first (or second), the basic ether of glycol ether one first (or second), the basic ether of triglycol one second (or fourth); Heterogeneous ring compound, for example 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, 1,3-dimethyl--2-imidazolone, N-ethylmorpholine; Sulfocompound, for example tetramethylene sulfone, methyl-sulphoxide and 3-cyclobufene sultone; Polyfunctional compound, for example Pyranton, diethylolamine; And urea derivatives.In these, more preferably polyvalent alcohol, for example glycerine and glycol ether.Can use or make up one or more that use these drying retarders separately.Preferably, the drying retarder content of ink is 10 to 50 weight %.
As for penetration enhancer, for example, spendable here is alcohol, for example ethanol, Virahol, butanols, two (three) glycol monobutyl ethers, 1,2-pinakon; With nonionogenic tenside sodium lauryl sulphate for example; Sodium oleate.Generally speaking, when the amount of these penetration enhancers in ink was 10 to 30 weight %, it was enough.But the amount of preferred so control penetration enhancer is not oozed out or printthrough so that ink can not cause.
UV light absorber is the stability that is used for improving image.As for UV light absorber, spendable here is like the benzotriazole cpd in JP-A 58-185677,61-190537,2-782,5-197075,9-34057; Like the benzophenone cpd in JP-A 46-2784,5-194483 and USP 3,214,463; Like the cinnamate compound in JP-B 48-30492,56-21141 and 10-88106; Like the triaizine compounds in JP-A 4-298503,8-53427,8-239368,10-182621 and JP-T8-50129 (term " JP-T " that uses is meant the translator of Japanese of disclosed PCT patented claim) here; Like the compound in Research Disclosure No.24239; And can absorb ultraviolet ray other compound with emitting fluorescence, or be white dyes, for example be typically stilbene compound and benzoazole compounds.
Inhibitor is the stability that is used for improving image.As for it, operable here is various organic or metal compounding material type fade inhibitors.Organic fade inhibitor comprises hydroquinones, alcoxyl phenol, dialkoxy phenol, phenols, phenyl amines, amine, 1,2-indane class, chroman, alcoxyl phenyl amines and heterogeneous ring compound; And the metal complexes fade inhibitor comprises nickel complex and Zn complex.More specifically; Operable here is the compound described in the patent publications related in Research Disclosure No.17643, ItemsVII-I to J, No.15162, the 650th page of left hurdle of No.18716, the 527th page of No.36544, the 872nd page of No.307105 and No.15162, and falls within the compound in the scope of typical compound and compound embodiment of the general formula indication described in the JP-A 62-215272 127-137 page or leaf.
Anti-mycotic agent comprises Sodium dehydroacetate, Sodium Benzoate, pyrithione-1-oxide sodium salt, ethylparaben, 1,2-benzisothiazole-3-ketone and salt thereof.Its amount in ink is preferably 0.02 to 5.00 weight %.
Its details is described in for example Dictionary of Antibacterials and Antifungals (TheDictionary Section of the Antibacterial and Antifungal Societyof Japan) ＂.
Rust-preventive agent comprises for example acid accumulator sulfite, Sulfothiorine, mercaptoethanol acid ammonium, nitrous acid di-isopropyl ammonium, trinitrol, nitrous acid dicyclohexyl ammonium and benzotriazole.Preferably, its content in ink is 0.02 to 5.00 weight %.
Preferred pH control agent is used for pH control and is used for dispersion stable.Preferably, pH in the control ink is to fall between 8 and 11 at 25 ℃.If the pH value is lower than 8, colorant dissolubility will descend and nozzle will get clogged easily so.But if the pH value is higher than 11, the water tolerance of ink will be poor so.The pH control agent can be for example organic bases and a mineral alkali of basic cpd, or acidic cpd for example organic acid and mineral acid.
Basic cpd comprises for example sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus, sodium acetate, potassium acetate, sodium phosphate, Sodium phosphate, dibasic and other mineral compound and ammoniacal liquor, methylamine, ethamine, diethylamine, triethylamine, thanomin, diethylolamine, trolamine, 1, piperidines, diazabicyclo octane, diazabicyclo undecylene, pyridine, quinoline, picoline, lutidine, trimethylpyridine and other organic bases.
Acidic cpd comprises, for example mineral compound hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, sodium pyrosulfate, sal enixum, potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC; And organic cpds, for example acetate, tartrate, phenylformic acid, trifluoroacetic acid, methylsulfonic acid, ethyl sulfonic acid, methylsulfonic acid, Phenylsulfonic acid, right-toluenesulphonic acids, saccharinic acid, phthalic acid, VPP, quinolinic acid.
Ink electric conductivity of the present invention can fall within 0.01 and 10S/m between, more preferably between 0.05 to 5S/m.
Can use each Repone K of commercially available drink, measure electric conductivity according to electrode method.
Can control electric conductivity by the ionic concn of the aqueous solution basically.When its salt concn is high, can solution be carried out desalination through ultrafiltration.When adding salt etc., can lead to various organic salts or inorganic salt are used for this purpose with the electric conductivity of control solution.
Inorganic salt and organic salt for example are, mineral compound salt such as potassium halide, sodium halide, sodium sulfate, vitriolate of tartar, sodium pyrosulfate, sal enixum, SODIUMNITRATE, saltpetre, sodium hydrogencarbonate, saleratus, sodium phosphate, Sodium phosphate, dibasic, borate, sodium phosphate, potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC; With organic cpds for example sodium acetate, potassium acetate, soluble tartrate, sodium tartrate, Sodium Benzoate, potassium benzoate, paratoluenesulfonic acid sodium salt, saccharinic acid potassium, phthalic acid potassium, VPP sodium.
Can also be through the concrete electric conductivity of selecting other components of additives control ink.
Ink viscosity of the present invention in 25 ℃ can be for 1 to 20mPas, but be preferably 2 to 15mPas, more preferably 2 to 10mPas.If viscosity is higher than 20mPas, possibly postpones the fixing of document image and possibly descend with ink ejection strength.If viscosity is lower than 1mPas, document image maybe be contaminated, so its downgrade.
Can control viscosity with any suitable mode through the amount of control ink solvent.Ink solvent comprises for example glycerine, glycol ether, trolamine, 2-Pyrrolidone, diethylene glycol monobutyl ether and triglycol monobutyl ether.
If desired, can use the viscosity activator.The viscosity activator comprises for example Mierocrystalline cellulose, and water-soluble polymers is Z 150PH and nonionogenic tenside for example.Its details is described in for example Viscosity Control Technology (the Technology Information Association, 1999), Chap.9; Chemicals for InkJet Printers (98 [)-Investigation of Trendsand Views in Development of Materials (CMC, 1997), the 162-174 page or leaf.
The measuring method of liquid viscosity is described in detail among the JIS Z8803.In the present invention, ink viscosity can easily be measured with simple mode with commercially available viscometer.For example, the rotational viscosimeter of TokyoInstrument and B-type viscometer and E-type viscometer are known.In the present invention, with Yamaichi Electric vibration viscometer, the VM-100A-L type is used for measuring viscosity down at 25 ℃.The unit of viscosity is pascal second (Pas), but milli-pascal second (mPas) normally.
Preferably, by dynamic surface tension and static surface tension, surface tension of the present invention is 20 to 50mN/m in 25 ℃.More preferably, it is 20 to 40mN/m.If surface tension is greater than 50mN/m, the ejection stability of ink will be poor so.In addition, if like this, the printed product that forms through the polychrome double exposure blurs and a palpus, and print quality will sharply descend.On the other hand, if when its surface tension is lower than 20mN/m, ink maybe with the surface adhesion of printing tools to worsen print quality.
In order to control the surface tension of ink, can in ink, add various positively charged ion recited above, negatively charged ion or nonionogenic tenside.Preferably, the amount of tensio-active agent that can be in ink is 0.01 to 20 weight %, more preferably 0.1 to 10 weight.If desired, can two or more dissimilar combinations-of surfactants be used in ink.
Static surface tension for measuring ink is known that capillary rise method, descent method and pendant method.In the present invention, measure the static surface tension of ink according to the vertical panel method.
In brief, when vertically hanging the thin plate of glass or platinum when being immersed in its part in the liquid simultaneously, surface tension of liquid will act on downward direction along the part at liquid and plate contact liq so.The capillary power and the force balance of directive effect that makes progress, thus the surface tension of determining liquid is big or small.
For the dynamic surface tension of measuring ink; Be known that vibration jet method, meniscus drop method and maximum bubble method; For example at Lecture of New Experimental Chemistry; Vol 18, " Interface and Colloid " (Maruzen), in the 69-90 page or leaf (1977).Also known also just like the liquid film destroy method among the JP-A3-2064.In the present invention, measure dynamic surface tension according to the bubble pressure differential method.The principle and the mechanism of this measuring method are described below.
When the homogeneous solution of preparation bubbles through stirring it, produced new liquid-vapo(u)r interface so, and the surfactant molecule in this solution accumulates in around the surface of water with constant speed.Under the sort of condition, bubble speed (forming the speed of bubble) is changed.When bubble speed is slow, so the more surfactant molecular aggregates around the bubble surface that forms, and just before bubble eruption largest air bubbles pressure low.Detection is for the largest air bubbles pressure (surface tension) of bubble speed.A preferred embodiment measuring dynamic surface tension is following: use big probe and little probe to amount to two, and in ink, form bubble.At these two probes under the largest air bubbles pressure state, measure differences in pressure, and calculate the dynamic surface tension in Heisui River by it.
For the ejection stability that guarantees ink, guarantee the good print quality of image aspect the anti-jail property of its pattern, image resistance to soiling and the non-sticky at printed product, preferably, the non-volatile content of ink of the present invention is 10 to 70 weight %.For the ejection stability that more advantageously guarantees ink with guarantee it particularly in the good print quality aspect the pattern resistance to soiling of printed product, more preferably it is 20 to 60 weight %.
Non-volatile content is included in boiling point under the normal atmosphere and is not less than 150 ℃ liquid and solid ingredient and polymeric constituent.The non-volatilization component of ink for inkjet recording is dyestuff, high boiling solvent and other optional polymer latex, tensio-active agent, dye stabilizers, anti-mycotic agent and buffer reagent.Most of non-volatilization component except that dye stabilizers is lower than the dispersion stabilization of ink, and is retained on the printer paper, disturbs dyestuff on it to associate and stable, and the result worsens the anti-jail property of image thus, and under high humidity, often pollutes print image.
Ink of the present invention can comprise polymer compound.Polymer compound is meant that number-average molecular weight in the ink is at least any and every kind of polymer compound of 5000.It is soluble water-soluble polymeric compounds, water dispersible polymer compound for example polymer latex and polymkeric substance emulsion and as soluble alcohol soluble polymer compound in the polyvalent alcohol of secondary solvent basically that polymer compound is included in the aqueous medium.As long as they are uniform dissolution or be dispersed in the ink basically, any polymer compound can be in ink of the present invention.
The instance of water-soluble polymers is a Z 150PH, silanol modified polyethylene alcohol, CMC 99.5, Natvosol, Vinylpyrrolidone polymer, polyalkylene oxide for example polyethylene oxide, gather Trimetylene, polyalkylene oxide derivative and other water-soluble polymers; And natural water-soluble copolymer for example polysaccharide, starch, cationic starch, casein, gelatin; The water soluble acrylic acid resinoid is ROHM, polypropylene amine and their multipolymer for example; Aqueous alkide resin contains in molecule-SO with other 3 -Or-COO -Basically dissolve in the water-soluble polymeric compounds of water-based medium.
Polymer latex comprises for example styrene-butadiene latex, styrene-propene acyl group latex, polyurethane rubber latex.Polymkeric substance emulsion is acrylic acid or the like emulsion etc.
Can be used alone or in combination these water-soluble polymeric compounds.
For the viscosity of controlling ink guarantees that to fall into ink well sprays the suitable range of viscosities of strength, is used as aforesaid viscosity activator with the water-soluble polymeric compounds.But if the ink inclusion compound is too many, ink viscosity possibly improve so, and the ejection poor stability of ink.In addition, if like this, ink possibly form deposition when storing, therefore maybe stopped nozzles.
For viscosity controller, though depend on the molecular weight (amount of the compound that molecular weight is high more possibly lacked more) of compound, the amount of the polymer compound that can in ink, add can be 0 to 5 weight %.Preferably it is 0 to 3 weight %, more preferably 0 to 1 weight %.
Except above-mentioned tensio-active agent, can also use other various nonionics, positively charged ion or AS as the surface tension activator.For example, AS is soap, alkyl-sulphate, sulfonated alkylbenzene, sulfonated alkyl naphathalene, dialkyl sulfosuccinates, alkylphosphonic, naphthene sulfonic acid-Superlysoform condenses, laureth sulfate.Nonionogenic tenside is Voranol EP 2001, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan aliphatic ester, T 46155 sorbitan aliphatic ester, polyoxyethylene alkyl amine, glycerin fatty hydrochlorate, oxygen ethene-oxypropylene segmented copolymer.Ethynyl T 46155 oxide surface promoting agent further preferably, Surfynols (Air Products & Chemicals Inc.).Amine oxide type amphoterics N for example further preferably, N-dimethyl--N-alkyl amine oxide.In addition, can also use the 37th to 38 page of JP-A 59-157636 here; With the tensio-active agent described in the Research Disclosure No.308119 (1989).
Among the present invention, can be with various positively charged ions, negatively charged ion or nonionogenic tenside such as above-mentioned those as dispersion agent or dispersion stabilizer, and if desired, can with fluorochemicals, silicone compounds and and sequestrant such as EDTA as skimmer.
(image receiving material)
The image that the present invention uses receives material and comprises reflecting medium described below for example recording paper and recording film.
Recording paper and recording film used carrier can be by dissolving pulps, for example LBKP, NBKP; Mechanical pulp, for example GP, PGW, RMP, TMP, CTMP, CMP and CGP; Perhaps reclaim formation such as paper pulp such as DIP.If desired, can be to wherein adding any known additives for example pigment, tackiness agent, sizing agent, fixing agent, cationoid reagent and paper intensity reinforcing agent.For example fourdrinier machine and mould machine are used to prepare carrier can also to use various paper machines.Except these carriers, what can also use is synthetic paper and plastic film here.Preferably, the thickness of carrier is 10 to 250 μ m, and its unit mass is 10 to 250g/m 2
Can directly on carrier, coat the image receiving material that image receiving layer and back coating manufacturing are used for ink of the present invention.If desired, can adopt applying glue or tackify coatings such as starch, Z 150PH, coat image receiving layer and back coating then, be used for image receiving material of the present invention to become to carrier.In addition, if desired, can also carry out planarizing process to carrier with mechanical roller calender, TG roller calender and soft roller calender etc.
The carrier that uses for the present invention, more preferably on the two sides all lamination the paper or the plastic film of polyolefine (for example Vilaterm, PS, polybutylenes or their multipolymer) or polyethylene terephthalate.Also preferably, in polyolefine, add white pigment (for example titanium white, zinc oxide) or illuminating colour (for example cobalt blue, ultramarine, Neodymium trioxide).
The image receiving layer that is formed on the carrier comprises porous material and aqueous binder.Preferably, image receiving layer comprises pigment.For pigment, white pigment preferably.White pigment comprises inorganic white pigment, for example lime carbonate, kaolin, talcum, clay, zeyssatite, synthetic soft silica, pure aluminium silicate, Magnesium Silicate q-agent, Calucium Silicate powder, white lake, aluminum oxide, lithopone, zeolite, permanent white, calcium sulfate, titanium oxide, zinc sulphide, lead carbonate; With organic white pigment, for example styrenic pigment, acrylic acid or the like pigment, urea resin, melamine resin.Preferred especially porous, inorganic white pigment, and more preferably have the synthetic soft silica of big hole area.The synthetic soft silica can be any in the anhydrous silicon oxide down that obtains through dry method (vapor phase process) or the hydrated SiO 2 that obtains through wet method.
The instance that in its image receiving layer, comprises the recording paper of above-mentioned pigment is disclosed in JP-A10-81064,10-119423,10-157277,10-217601,10-348409,2001-138621,2000-43401,2000-211235,2000-309157,2001-96897,2001-138627,11-91242,8-2087,8-2090,8-2091,8-2093,8-174992,11-192777,2001-301314 particularly, and can use any of these here.
Aqueous binder in the image receiving layer comprises water-soluble polymers, for example Z 150PH, silanol modified polyethylene alcohol, starch, cationic starch, casein, gelatin, CMC 99.5, Natvosol, Vinylpyrrolidone polymer, polyalkylene oxide, polyalkylene oxide derivative; And aqueous dispersion polymers, for example styrene-butadiene latex, acrylic acid or the like emulsion.Can be used alone or in combination one or more of these aqueous binders here.In these, consider the adhesivity and the anti-separability of image receiving layer of they and pigment, particularly preferably be Z 150PH and silanol modified polyethylene alcohol.
Except wherein pigment and aqueous binder, image receiving layer can comprise any other additive for example mordant, water-resisting agent, the anti-firm property improvement agent of light, the property improvement of anti-steam agent, tensio-active agent and stiffening agent.
Preferably the mordant in image receiving layer is passivated.Particularly, preferred polymers mordant.
Polymer mordant is described for example in JP-A 48-28325,54-74430,54-124726,55-22766,55-142339,60-23850,60-23851,60-23852,60-23853,60-57836,60-60643,60-118834,60-122940,60-122941,60-122942,60-235134,1-161236; USP 2,484, and 430,2,548,564,3,148,061,3,309,690,4,115,124,4,124,386,4,193,800,4,273,853,4,282,305,4,450,224.Especially preferably will be used in the present invention's the image receiving material in polymer mordant described in the JP-A1-161236 212-215 page or leaf.The image that its acquisition has good quality and the anti-jail property of good light.
Water-resisting agent is effective for the image of preparation waterproof.For water-resisting agent, particularly preferably be resin cation(R.C.).Resin cation(R.C.) is for example polymeric amide polyamine Epicholorohydrin, polymine, polyamine sulfone, dimethyl diallyl ammonium chloride polymkeric substance, cationic polyacrylamide.The content of the resin cation(R.C.) of preferred ink receiving layer is 1 to 15 weight % of the total solids level of this layer, more preferably 3 to 10 weight %.
Anti-firm property improvement agent of light and the property improvement of anti-steam agent comprise for example phenolic compound; Hindered phenol compound; Sulfide compound; Thiourea compound; Rhodan-compound; Amine compound; Hindered amine compound; The TEMPO compound; Hydrazine compound; Hydrazide compound; Amidine compound; Contain vinyl compound; Ester cpds; Amide compound; Ether compound; Alkylol cpd; Sulfinic acid compound; Carbohydrate; Water miscible reducible compound; Organic acid; Mineral acid; The hydroxyl organic acid; Benzotriazole cpd; Benzophenone cpd; Triaizine compounds; Heterogeneous ring compound; Water-soluble metal salt; Organometallic compound; Metal complexes.
The specific examples of these compounds is described in JP-A 10-182621,2001-260519,2000-260519; JP-B 4-34953,4-34513,4-34512; JP-A 11-170686,60-67190,7-276808,2000-94829; JP-T 8-512258; JP-A 11-321090.
Tensio-active agent plays coatings additive(s), releases property improvement agent, smooth activator or static inhibitor.It is described in for example JP-A 62-173463,62-183457.
Can use organofluorine compound to come the substitution list surface-active agent.Preferably, organofluorine compound used herein is hydrophobic.The instance of organofluorine compound is fluorochemical surfactant, oiliness fluorochemicals (for example fluorocarbon oil) and solid fluorine-containing compound resin (for example tetrafluoroethylene resin).The organic fluoride-containing compound is described in JP-B 57-9053 (8 to 17 hurdle); JP-A 61-20994,62-135826.
For stiffening agent, can use at described in JP-A 1-161236 (222 pages), 9-263036,10-119423, the 2001-310547 those here.
Can other additive in image receiving layer be pigment dispersing agent, thickening material, skimmer, dyestuff, white dyes, sanitas, pH control agent, matting agent and stiffening agent.Image receiving material can have one or more layers ink receiving layer.
Recording paper and recording film can have back coating.This layer can comprise white pigment, aqueous binder and other component.
Can comprise by the white pigment in back coating for example inorganic white pigment such as light calcium carbonate, water-ground limestone, kaolin, talcum, calcium sulfate, permanent white, titanium oxide, zinc oxide, zinc sulphide, zinc carbonate, stain white, pure aluminium silicate, zeyssatite, Calucium Silicate powder, Magnesium Silicate q-agent, synthetic soft silica, colloid silica, colloidal alumina, pseudobochmite, white lake, aluminum oxide, lithopone, zeolite, hydro-halloysite, magnesiumcarbonate, Marinco H; And pigment dyestuff, for example styrene plastic pigment, acrylics pigment, Vilaterm microcapsule, urea resin and melamine resin.
Can comprise by the aqueous binder in back coating, for example water-soluble polymers such as vinylbenzene/maleate copolymer, styrene/acrylic salt copolymer, Z 150PH, silanol modified polyethylene alcohol, starch, cationic starch, casein, gelatin, CMC 99.5, Natvosol Vinylpyrrolidone polymer; And aqueous dispersion polymers, for example styrene-butadiene latex, acrylic acid or the like emulsion.Can other component in back coating be skimmer, foam preventer, dyestuff, white dyes, sanitas, water-resisting agent etc.
Can dispersion of polymer particles be added in the composition layer (comprising backing layer) of ink jet recording paper or film among the present invention.Dispersion of polymer particle is used to improve the physical properties of coating, the dimensional stability that for example is used to improve these layers be used to prevent that these from curling, adhesion and breaking.Dispersion of polymer particle is described in for example JP-A 62-245258,62-1316648,62-110066.When in the layer that contains mordant, adding the dispersion of polymer particles of lower glass transition temperatures (not in 40 ℃), this is effective for preventing that layer from breaking and curling.When in backing layer, adding the polymer fine particles dispersion-s of high glass-transition temperature, this also is effective for preventing that layer from curling.
(ink-vapor recording)
Inkspot volume on the recording materials among preferred the present invention is 0.1pl to 100pl, 0.5pl to 50pl more preferably, 2pl to 50pl more preferably again.
To the not special restriction of the ink-jet recording system among the present invention, can be used in known any system.What for example, can adopt is any in the following system: spray the also Electrostatic Control system of ink through electrostatic attraction; Utilize dropping as required (drop-on-demand) system (pressure pulse system) of the vibration pressure of piezoelectric element; Electrical signal is changed into acoustic beam, it is applied to ink, and under radiation pressure, spray the sound ink jet system of ink; Or heating ink produces hot ink-jet (bubble jet) system of the pressure of bubble and utilization generation.
Ink-jet recording system comprises: spray the system of drop of the lower concentration light ink of a large amount of small volumes, use with multiple basic identical color but the different ink of concentration improves the system of picture quality and the system of use water white transparency ink.Mainly be controlled at the some volume on the recording materials through printhead.
For example, in hot ink-jet system, can be according to the structure control point volume of printhead.Particularly, change ink chamber, heating region and jet size, can any ideal mode change a volume thus.A plurality of during when in hot ink-jet system, using at printheads different aspect heating region and the jet size, can obtain different big or small ink droplets so.
In the dropping system as required that uses piezo-electric device, with as top hot ink-jet system, also can be according to the structural modification point volume of printhead.But, described at this as below, can control the waveform of the actuate signal of piezo-electric device, and realize the ink droplet of different sizes thus through the printhead of same structure.
When a shape sprays ink of the present invention on recording materials, preferably spray frequency and be at least 1kHz.
In order to obtain high quality, must use little ink droplet to be used to reproduce clear and high quality graphic as photo shape image.For this reason, dot density must be at least 600dpi (point of per inch).
On the other hand, in printhead ejection ink that has a plurality of nozzles through each and register system that recording paper moves perpendicular to these printheads, the quantity of the printhead that wherein can drive simultaneously can be for tens of to about 200.Even in wire printing head (line-head) system of fixing a plurality of printheads, the quantity limitation of the printhead that also can drive simultaneously is hundreds of.This is because driving power is restricted, and therefore the heat of these printheads possibly can not drive more substantial print-head nozzle simultaneously to some influences of image generation that form.Therefore, when the dot density in document image improves, writing time possibly prolonged so.But,, possibly improve writing speed so if improve driving frequency.
In order to control the ink-jet frequency in the hot ink-jet system, can control the frequency of the printhead actuate signal that adds thermal printer head.
In piezoelectric system, can control the signal frequency of drive pressure electric installation.
The expulsion mechanism of piezoelectric printhead is described.In the stamping machine control area, be used for the images printed signal, and form the signal that drives printhead in control aspect a size, spot speed and the dot frequency.Guide the actuate signal that forms thus into printhead.Piezoelectric drive signal reference mark size, spot speed and dot frequency.Form and amplitude by driving ripple can be confirmed spot size and spot speed, and confirm frequency by the signal recirculation.
When dot frequency is set at 10kHz, under per 100 microseconds, drive printhead so, and a line item will be accomplished in 400 microseconds.When design record paper translational speed like this, so that recording paper can move 1/600 inch, or promptly, about 42 microns/400 microseconds can be printed one in so per 1.2 seconds.
As for the structure of the type printer that uses among the present invention and the structure of stamping machine, for example, preferably reference is like the embodiment among the JP-A 11-170527.For ink cartridge, for example, preferably at those of JP-A 5-229133 illustrated.The structure of the sucker mechanism when printing and cover the structure of the cap of printhead, for example, preferably reference is at those of JP-A 7-276671 illustrated.Also preferably, the for example strainer of the bubble removal in JP-A 9-277552 is being provided near the printhead.
Also preferably, for example, in JP-A-2002-292878, for water-repellancy working nozzle surface.For its application, can with stamping machine that computer is connected in use ink of the present invention, or can in the stamping machine that is in particular the photo design, use.
It is desirable in ink jet recording method of the present invention, ink is 2m/ at least second with equalization point speed, more preferably 5m/ sprays on recording materials second at least.
For reference mark speed, can control shape and amplitude that printhead drives ripple.
When in a stamping machine, optionally using multi-form a plurality of driving ripple,, can spray the inkspots of different sizes so through the same printhead in the stamping machine.
(ink-jet applications)
Ink for inkjet recording of the present invention can be used for using except ink-vapor recording those any other application.For example, it can be used for display image formation, the formation of upholstery image, the formation of exterior decoration image.
The application that display image forms is meant and (for example writes on or adhere to placard, wallpaper, sequin; Ornamental; Figure), flyer, wrapping paper, wrapping material, paper bag, polyethylene bag, lapping, billboard, transportation facilities (automobile for example; Motorbus, electric car) image on the side, and clothes with sign.When dyestuff of the present invention was used to form this display image, image not only comprised those of the literal narrow sense meaning so, and comprised can being all multi color patterns that the people discerns, for example abstract design, letter, geometric scheme etc.
Be used for house decorative material that image forms above that and be meant various article such as wallpaper, sequin (ornamental, figure), the design part of set lights, furniture parts, floor or top ceiling etc.When dyestuff of the present invention being used on this material, form image, image not only comprises those of the literal narrow sense meaning so, and comprises can being all multi color patterns that the people discerns, for example abstract design, letter, geometric scheme etc.
The material that is used for the exterior decoration that image forms above that is meant various article such as wall covering, roof cladding, billboard, gardening material, the outer ornamental (ornamental, figure) of cell and exterior lighting parts.When dyestuff of the present invention being used on this material, form image, image not only comprises those of the literal narrow sense meaning so, and comprises can being all multi color patterns that the people discerns, for example abstract design, letter, geometric scheme etc.
In above-mentioned application, the medium that forms pattern on it can comprise paper, fiber, fabric (comprising nonwoven fabric), plastics, metal, pottery and other various article.As for the dyeing pattern on them, can be used for the activity with reactive group is introduced wherein with any pattern of mordant dyeing, printing or chemical reaction with dye application and fixing on it.Among these forms, particularly preferably be the mordant dyeing pattern of fixed dye on medium.
Embodiment
Through describing the present invention with reference to following embodiment, still, the present invention is not limited by these.
(embodiment 1)
In component described below, add ultrapure water (resistance, 18M Ω at least) to process 1 liter, under 30 to 40 ℃ of heating, stirred 1 hour then.Then, be that the micro-filter of 0.25 μ m filters the mixture obtain under reduced pressure, with preparation yellow ink Y-101 through average cell size.
(prescription of yellow ink, Y-101)
(solid ingredient)
Yellow dyes (DYE-83) 50g/ liter
Proxel 5g/ liter
Urea 25g/ liter
(liquid ingredient)
Triglycol monobutyl ether (TGB) 100g/ liter
Glycerine (GR) 115g/ liter
Triglycol (TEG) 100g/ liter
2-Pyrrolidone 35g/ liter
Trolamine (TEA) 8g/ liter
Surfynol STG (SW) duty 10g/ liter
The yellow dyes that here uses (DYE-83) is 1.23V (with respect to SCE) in the cyclic voltammetry (CV) of analyzing the aqueous solution of dyestuff (1 mmole/liter) and the oxidizing potential of change disk electrode method measurement.
For relatively, use the yellow ink box, the FM-980 of Epson.
Same way as with preparation yellow ink Y-101 prepares other yellow ink described in the following table, still, uses yellow dyes C, DYE-51, YJ-3 or YJ-7 to replace dyestuff, DYE-83.
The oxidizing potential of the yellow dyes C that here uses as the oxidizing potential of 0.98V (with respect to SCE) and all dyestuffs except that it greater than 1.2V (with respect to SCE).
Yellow dyes C
Table 4
Sequence number Yellow dyes
PM-950C (comparison) -
Y-101 (comparison) DYE-83 (50g/ liter)
Y-102 (comparison) C (55g/ liter)
Y-103 (comparison) YJ-3 (60g/ liter)
Y-104 (comparison) DYE-51 (45g/ liter)
Y-105 (comparison) YJ-7 (50g/ liter)
Y-106 (comparison) DYE-83 (25g/ liter) C (28g/ liter)
Y-107 (the present invention) DYE-83 (20g/ liter) YJ-3 (36g/ liter)
Y-108 (the present invention) DYE-83 (40g/ liter) YJ-3 (12g/ liter)
Y-109 (the present invention) DYE-83 (35g/ liter) YJ-3 (18g/ liter)
Y-110 (the present invention) DYE-51 (30g/ liter) YJ-7 (18g/ liter)
Y-111 (the present invention) DYE-83 (40g/ liter) YJ-7 (10g/ liter)
These inks of in the yellow ink box that Epson ink-jet printer PM-980C uses, packing into; Wherein other color ink of PM-980C is in corresponding ink cartridge; Drive stamping machine with 6 look printing models, progressively change monochromatic yellows color image pattern and gray image pattern with print density thus.
The image-receiving sheet that here uses is the ink jetting paper of Fuji Photo Film, photograph glossy paper " Gasai ".The anti-jail property of picture quality, image of assessment printed sample and ink ejection stability.(evaluation test)
1) under the different condition of mentioning below, according to spraying stability test as follows with surrounding temperature and relative humidity change: in stamping machine, place print cartridge, and through respective nozzles ejection ink.
After this, the paper of under these all different conditions, printing 300 A4-sizes is having image above that, and these are all analyzed their picture quality.When duration of test uses ink, change print cartridge so and continue to print test.
(test conditions)
At 30 ℃ of 80% RH; 30 ℃ of 20% RH; 10 ℃ of 80% RH; 4 kinds of different conditions with 10 ℃ of 20% RH.
(evaluation criteria)
A: begin to finishing not find to print confusion from printing.
B: find that some printings are chaotic.
C: in whole printing, find to print chaotic.
2) the image storage property of assessment printed sample
(1) according to the anti-jail property of following assessment light: with X-Rite 310 measure print after immediately the image density Ci of fresh sample.Then, print image is carried out argon gas exposure (85,000 lux) 20 days, measure its image density Cf then from the aging machine of Atlas.From (Cf/Ci) * 100) and obtain the dyestuff conservation rate, and this representes the anti-jail property of light of printed sample.As for the dyestuff retentivity, analyze reflection density in each sample and be three points of 1,1.5 and 2.The dyestuff conservation rate of each point is at least 70% sample and is " A "; The dyestuff conservation rate of two points be lower than 70% those for " B "; With the dyestuff conservation rate of all three points be lower than 70% those be " C ".
(2) according to the hot anti-jail property of following assessment: kept printed sample 10 days in 80 ℃ with 70%RH, and measure them in stored position and density afterwards with X-Rite310.From these data, confirm the dyestuff conservation rate of every kind of sample, and the hot anti-jail property of this expression sample.As for the dyestuff conservation rate, the reflection density of analyzing each sample is three points of 1,1.5 and 2.The dyestuff conservation rate of each point is at least 90% sample and is " A "; The dyestuff conservation rate of two points be lower than 90% those for " B "; With the dyestuff conservation rate of all three points be lower than 90% those be " C ".
Under condition in the above, store the dyestuff conservation rate level of knowing each point and be 90% sample in the time of 1 day, and the density that stored afterwards them when 1 day rises to 5% or when higher, the evaluation grade of sample is " AX " then.
(3) according to the anti-jail property of following assessment ozone: in constant concentration of ozone gas is to place printed sample 3 days in the box of 5ppm.Before being exposed to ozone gas,, measure the image density of every kind of sample, and confirm the dyestuff conservation rate of every kind of sample with reflection densitometer (X-Rite310TR) with afterwards.As for the dyestuff conservation rate, the reflection density of analyzing each sample is three points of 1,1.5 and 2.Ozone concn in the box keeps constant with ozone gas monitor (the OZG-EM-01 type of Applics).
With the sample classification of test thus is three kinds of grades: the dyestuff conservation rate of each point be at least 80% those for " A "; The dyestuff conservation rate of one or two point be lower than 80% those for " B "; With the dyestuff conservation rate of all three points be lower than 70% those be " C ".
The result who obtains is shown in the following table.
Table 5
Sequence number Ejection stability The anti-jail property of light The anti-jail property of heat O 3Anti-jail property
PM-950C (comparison) A C B C
Y-101 (comparison) A A AX A
Y-102 (comparison) A C B C
Y-103 (comparison) A B A B
Y-104 (comparison) A A AX A
Y-105 (comparison) A B A B
Y-106 (comparison) A B A B
Y-107 (the present invention) A A A A
Y-108 (the present invention) A A A A
Y-109 (the present invention) A A A A
Y-110 (the present invention) A A A A
Y-111 (the present invention) A A A A
In heat-resisting anti-jail property assessment, find that density improves 3% in 1 day stores with Y-107.
Result in table proves that the system that uses ink of the present invention obtains having good anti-jail property and has the good images of good color stability of equilibrium.
(embodiment 2)
Add ultrapure water (resistance, 18M Ω at least) to process 1 liter in the component shown in following, under 30 to 40 ℃ of heating, stirred 1 hour then.Then, be that the micro-filter of 0.25 μ m filters the mixture obtain under reduced pressure, with preparation yellow ink Y-201 through mean pore size.
(prescription of yellow ink, Y-201)
(solid ingredient)
Yellow dyes of the present invention (DYE-83) 30g/ liter
Proxel 5g/ liter
Urea 20g/ liter
(liquid ingredient)
Triglycol monobutyl ether (TGB) 60g/ liter
Glycerine (GR) 100g/ liter
Triglycol (TEG) 40g/ liter
Virahol 40g/ liter
1,5-pentanediol 40g/ liter
Trolamine (TEA) 8g/ liter
Surfynol STG (SW) 10g/ liter
Same way as with preparation yellow ink Y-201 prepares other yellow ink described in the following table, and still, the dyestuff shown in use is following replaces dyestuff DYE-83.
Table 6
Sequence number Yellow dyes
PM-950C (comparison) -
Y-201 (comparison) DYE-83 (30g/ liter)
Y-202 (comparison) C (33g/ liter)
Y-203 (comparison) YJ-3 (36g/ liter)
Y-204 (comparison) DYE-51 (27g/ liter)
Y-205 (comparison) YJ-7 (30g/ liter)
Y-206 (comparison) DYE-83 (15g/ liter) C (17g/ liter)
Y-207 (the present invention) DYE-51 (11g/ liter) YJ-3 (21g/ liter)
Y-208 (the present invention) DYE-83 (24g/ liter) YJ-3 (7g/ liter)
Y-209 (the present invention) DYE-51 (19g/ liter) YJ-3 (11g/ liter)
Y-210 (the present invention) DYE-51 (18g/ liter) YJ-7 (10g/ liter)
Y-211 (the present invention) DYE-83 (24g/ liter) YJ-7 (6g/ liter)
These inks of in the yellow ink box that Canon ink-jet printer BJ-950 uses, packing into, wherein other color ink of BJ-950 and drives stamping machine, monochromatic yellows color image pattern that print density progressively changes and gray image pattern in corresponding ink cartridge.
The image-receiving sheet that here uses is ink jetting paper, the photograph glossy paper " Gasai " of Fuji PhotoFilm.With with embodiment 1 same way as, the anti-jail property of picture quality, image and the ink ejection stability of assessment printed sample.
Provide the result below.
Table 7
Sequence number Ejection stability The anti-jail property of light The anti-jail property of heat O 3Anti-jail property
PM-950C (comparison) A C B C
Y-201 (comparison) A A AX A
Y-202 (comparison) A C C C
Y-203 (comparison) A B B B
Y-204 (comparison) A A AX A
Y-205 (comparison) A B A B
Y-206 (comparison) A B A B
Y-207 (the present invention) A A A A
Y-208 (the present invention) A A A A
Y-209 (the present invention) A A A A
Y-210 (the present invention) A A A A
Y-211 (the present invention) A A A A
In heat-resisting anti-jail property assessment, find that density improves 3% in 1 day stores with Y-207.
The same with embodiment 1, the result in table proves that the system that uses ink of the present invention obtains having good anti-jail property and has the good images of good color stability of equilibrium.
(embodiment 3)
Add ultrapure water (resistance, 18M Ω at least) to process 1 liter in the component shown in following, under 30 to 40 ℃ of heating, stirred 1 hour then.Then, be that the micro-filter of 0.25 μ m filters the mixture obtain under reduced pressure through mean pore size.The ink for preparing different colours thus.
(prescription of pale cyan inks)
(solid ingredient)
Cyan dye (C-1) 20g/ liter
Urea (UR) 15g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Proxel XL2 (PXL) 3.5g/ liter
(liquid ingredient)
Triglycol (TEG) 110g/ liter
Glycerine (GR) 130g/ liter
Triglycol monobutyl ether (TGB) 110g/ liter
2-Pyrrolidone (PRD) 60g/ liter
Trolamine (TEA) 7g/ liter
Surfynol STG (SW) 10g/ liter
Cyan dye (C-1)
(prescription of cyan)
(solid ingredient)
Cyan dye (C-1) 60g/ liter
Urea (UR) 30g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Proxel XL2 (PXL) 3.5g/ liter
(liquid ingredient)
Triglycol (TEG) 110g/ liter
Glycerine (GR) 130g/ liter
Triglycol monobutyl ether (TGB) 130g/ liter
2-Pyrrolidone (PRD) the thousand zhang 60g/ liters that fall
Trolamine (TEA) 7g/ liter
Surfynol STG (SW) 10g/ liter
(prescription of shallow magenta ink)
(solid ingredient)
Magenta dyestuff (M-1) 7.5g/ liter
Urea (UR) 10g/ liter
Proxel 5g/ liter
(liquid ingredient)
Glycol ether (DEG) 90g/ liter
Glycerine (GR) 70g/ liter
Triglycol monobutyl ether (TGB) 70g/ liter
Trolamine (TEA) 6.9g/ liter
Surfynol STG (SW) 10g/ liter
Magenta dyestuff (M-1)
Figure G2008101757780D01331
(prescription of magenta ink)
(solid ingredient)
Magenta dyestuff (M-1) 23g/ liter
Urea (UR) 15g/ liter
Proxel 5g/ liter
(liquid ingredient)
Glycol ether 90g/ liter
Glycerine 70g/ liter
Triglycol monobutyl ether (TGB) 70g/ liter
Trolamine 6.9g/ liter
Surfynol STG 10g/ liter
(prescription of yellow ink)
(solid ingredient)
Yellow dyes (Y-1) 35g/ liter
Proxel 3.5g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Urea 10g/ liter
(liquid ingredient)
Triglycol monobutyl ether (TGB) 130g/ liter
Glycerine (GR) 115g/ liter
Glycol ether (DEG) 120g/ liter
2-Pyrrolidone 35g/ liter
Trolamine (TEA) 8g/ liter
Surfynol STG (SW) 10g/ liter
Yellow dyes (Y-1)
Figure G2008101757780D01341
(prescription of deep yellow ink)
(solid ingredient)
Yellow dyes (Y-1) 35g/ liter
Magenta dyestuff (M-1) 2g/ liter
Cyan dye (C-1) 2g/ liter
Proxel 5g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Urea 10g/ liter
(liquid ingredient)
Triglycol monobutyl ether (TGB) 140g/ liter
Glycerine (GR) 125g/ liter
Glycol ether (DEG) 120g/ liter
2-Pyrrolidone 35g/ liter
Trolamine (TEA) 8g/ liter
Surfynol STG (SW) 10g/ liter
(prescription of black ink)
(solid ingredient)
Black dyes (Bk-1) (λ max, 587nm; Half breadth, 105nm)
The 75g/ liter
Black dyes (Bk-2) ((λ max, 447nm) 30g/ liter
Proxel 5g/ liter
Urea 10g/ liter
Benzotriazole (BTZ) 3g/ liter
(liquid ingredient)
Triglycol monobutyl ether (DGB) 120g/ liter
Glycerine (GR) 125g/ liter
Glycol ether (DEG) 100g/ liter
2-Pyrrolidone 35g/ liter
Trolamine (TEA) 8g/ liter
Surfynol STG (SW) 10g/ liter
Black dyes (Bk-1)
Figure G2008101757780D01351
Black dyes (Bk-2)
Figure G2008101757780D01361
The ink group for preparing these inks, and this is IS-101.In addition, to prepare other ink group IS-102 to IS-108 with top same procedure, still, and wherein, with the partly according to the form below change of dyestuff of black ink.
The oxidizing potential (Eox) of all dyestuffs that here use is all greater than 1.2V (with respect to SCE).
Table 8
Additive
IS-101 (comparison) No
IS-102 (comparison) Half of Bk-1 among the IS-101 changed into dyestuff A
IS-103 (comparison) Half of Bk-1 among the IS-101 changed into dyestuff B
IS-104 (the present invention) Half of Bk-1 among the IS-101 changed into dyestuff C
IS-105 (the present invention) Half of Bk-1 among the IS-101 changed into dyestuff D
IS-106 (the present invention) 1/3 of Bk-1 among the IS-101 is changed into dyestuff C
IS-107 (the present invention) 1/3 of Bk-1 among the IS-101 is changed into dyestuff D
IS-108 (the present invention) Half of Bk-1 among the IS-101 changed into dyestuff E
Dyestuff A:C.I. directly deceives 38
Figure G2008101757780D01362
Dyestuff C:
Figure G2008101757780D01371
Dyestuff D:
Dyestuff E:
Figure G2008101757780D01373
These inks of in the ink cartridge of Epson ink-jet printer PM-980C, packing into, and the mode activated stamping machine that forms with monochrome image, the gray image pattern that progressively changes at the image-receiving sheet print density thus.
The image-receiving sheet that here uses is ink jetting paper, the photograph glossy paper " Gasai " of Fuji Photo Film.
(evaluation test)
1) uses photodensitometer X-Rite, measure the Dvis value of every kind of sample, and this representes maximum grey colour density.
2) assess the image storage property of gradient gray image as follows:
(1) according to the anti-jail property of following assessment light: with X-Rite 310 measure print after immediately the image density Ci of fresh sample.Then, print image is carried out argon gas exposure (85,000 lux) 20 days, measure its image density Cf then from the aging machine of Atlas.From (Cf/Ci) * 100) and obtain the dyestuff conservation rate, and this representes the anti-jail property of light of printed sample.As for the dyestuff retentivity, analyze reflection density in each sample and be three points of 1,1.5 and 2.The dyestuff conservation rate of each point is at least 80% sample and is " A "; The dyestuff conservation rate of two points be lower than 80% those for " B "; With the dyestuff conservation rate of all three points be lower than 80% those be " C ".
(2) according to the anti-jail property of following assessment ozone: in constant concentration of ozone gas is to place printed sample 7 days in the box of 5ppm.Before being exposed to ozone gas,, measure the image density of every kind of sample, and confirm the dyestuff conservation rate of every kind of sample with reflection densitometer (X-Rite310TR) with afterwards.As for the dyestuff conservation rate, the reflection density of analyzing each sample is three points of 1,1.5 and 2.Ozone concn in the box keeps constant with ozone gas monitor (the OZG-EM-01 type of Applics).
With the sample classification of test thus is three kinds of grades: the dyestuff conservation rate of each point be at least 80% those for " A "; The dyestuff conservation rate of one or two point be lower than 80% those for " B "; With the dyestuff conservation rate of all three points be lower than 80% those be " C ".
(3) according to the ejection of following assessment ink stability: under 30 ℃ of controlled conditions with 80%RH, print the big or small paper of 100 A4-with every group of ink group.Chaotic and the thin stain of the image of the black image that inspection is printed.Not having the sample of trouble is A; There are chaotic with other trouble those of some images to be B; And have many troubles those be C.
Table 9
Sequence number Maximum density The anti-jail property of light The anti-jail property of ozone Ink ejection stability
PM-980C (comparison) 2.43 C C A
IS-101 (comparison) 2.21 A A C
IS-102 (comparison) 2.31 B B C
IS-103 (comparison) 2.35 B B C
IS-104 (the present invention) 2.42 A A A
IS-105 (the present invention) 2.41 A A A
IS-106 (the present invention) 2.42 A A A
IS-107 (the present invention) 2.39 A A A
IS-108 (the present invention) 2.39 A A A
Above support effect of the present invention dry straightly.
(embodiment 4)
Add ultrapure water (resistance, 18M Ω at least) to process 1 liter in the component shown in following, under 30 to 40 ℃ of heating, stirred 1 hour then.Then, be that the micro-filter of 0.25 μ m filters the mixture obtain under reduced pressure through mean pore size.The ink for preparing different colours thus.
(prescription of photograph cyan)
(solid ingredient)
Cyan dye (C-1) 10g/ liter
Urea (UR) 15g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Proxel XL2 (PXL) 3.5g/ liter
(liquid ingredient)
Triglycol (TEG) 50g/ liter
Glycerine (GR) 100g/ liter
Triglycol monobutyl ether (TGB) 60g/ liter
1,5-pentanediol (PTD) 40g/ liter
Virahol (IPA) 20g/ liter
Trolamine (TEA) 7g/ liter
Surfynol STG (SW) 10g/ liter
(prescription of cyan)
(solid ingredient)
Cyan dye (C-1) 30g/ liter
Urea (UR) 40g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Proxel XL2 (PXL) 3.5g/ liter
(liquid ingredient)
Triglycol (TEG) 40g/ liter
Glycerine (GR) 100g/ liter
Triglycol monobutyl ether (TGB) 70g/ liter
1,5-pentanediol (PTD) 50g/ liter
Virahol (IPA) 20g/ liter
Trolamine (TEA) 7g/ liter
Surfynol STG (SW) 10g/ liter
(prescription of photograph magenta ink)
(solid ingredient)
Magenta dyestuff (M-1) 7.5g/ liter
Urea (UR) 10g/ liter
Proxel 5g/ liter
(liquid ingredient)
Triglycol (TEG) 40g/ liter
Glycerine (GR) 100g/ liter
Triglycol monobutyl ether (TGB) 60g/ liter
1,5-pentanediol (PTD) 40g/ liter
Virahol (IPA) 20g/ liter
Trolamine (TEA) 6.9g/ liter
Surfynol STG (SW) 10g/ liter
(prescription of magenta ink)
(solid ingredient)
Magenta dyestuff (M-1) 23g/ liter
Urea (UR) 15g/ liter
Proxel 5g/ liter
(liquid ingredient)
Triglycol (TEG) 50g/ liter
Glycerine (GR) 100g/ liter
Triglycol monobutyl ether (TGB) 50g/ liter
1,5-pentanediol (PTD) 40g/ liter
Virahol (IPA) 20g/ liter
Trolamine 6.9g/ liter
Surfynol STG 10g/ liter
(prescription of yellow ink)
(solid ingredient)
Yellow dyes (Y-1) 35g/ liter
Proxel 3.5g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Urea 10g/ liter
(liquid ingredient)
Triglycol (TEG) 40g/ liter
Glycerine (GR) 100g/ liter
Triglycol monobutyl ether (TGB) 70g/ liter
1,5-pentanediol (PTD) 60g/ liter
Virahol (IPA) 20g/ liter
Trolamine (TEA) 8g/ liter
Surfynol STG (SW) 10g/ liter
(prescription of black ink)
(solid ingredient)
Black dyes (Bk-1) 75g/ liter
Black dyes (Bk-2) 30g/ liter
Proxel 5g/ liter
Urea 10g/ liter
Benzotriazole (BTZ) 3g/ liter
(liquid ingredient)
Triglycol (TEG) 60g/ liter
Glycerine (GR) 100g/ liter
Triglycol monobutyl ether (TGB) 70g/ liter
1,5-pentanediol (PTD) 50g/ liter
Virahol (IPA) 20g/ liter
Trolamine (TEA) 8g/ liter
Surfynol STG (SW) 10g/ liter
The ink group and this that prepare these inks are IS-201.In addition, to prepare other ink IS-202 to IS-208 with top same procedure, still, the additive below wherein adding in the table.Among all dyestuff A to E that here use and the embodiment 3 those are identical.
Table 10
Additive
IS-201 (comparison) No
IS-202 (comparison) Half of Bk-1 among the IS-201 changed into dyestuff A
IS-203 (comparison) Half of Bk-1 among the IS-201 changed into dyestuff B
IS-204 (the present invention) Half of Bk-1 among the IS-201 changed into dyestuff C
IS-205 (the present invention) Half of Bk-1 among the IS-201 changed into dyestuff D
IS-206 (the present invention) 1/3 of Bk-1 among the IS-201 is changed into dyestuff C
IS-207 (the present invention) 1/3 of Bk-1 among the IS-201 is changed into dyestuff D
IS-208 (the present invention) Half of Bk-1 among the IS-201 changed into dyestuff E
These inks of in Canon ink-jet printer PIXUS950i, packing into, and drive stamping machine on image-receiving sheet, to print the picture pattern that 6 kinds of color C, M, Y, B, G and R and gray density progressively change.
The image-receiving sheet that here uses is to duplicate offset paper, and the ink jetting paper of Fuji Photo Film, photograph glossy paper " Gasai ".
With with embodiment 3 in identical mode assess images printed.
Provide the result below.
Table 11
Sequence number Maximum density The anti-jail property of light The anti-jail property of ozone Ink ejection stability
PIXUS950i (comparison) 2.33 C C A
IS-201 (comparison) 2.11 A A C
IS-202 (comparison) 2.11 B B C
IS-203 (comparison) 2.15 B B C
IS-204 (the present invention) 2.32 A A A
IS-205 (the present invention) 2.31 A A A
IS-206 (the present invention) 2.32 A A A
IS-207 (the present invention) 2.33 A A A
IS-208 (the present invention) 2.33 A A A
Above supported effect of the present invention dry straightly.
(embodiment 5)
Add ultrapure water (resistance, 18M Ω at least) to process 1 liter in the component shown in following, under 30 to 40 ℃ of heating, stirred 1 hour then.Then, be that the micro-filter of 0.25 μ m filters the mixture obtain under reduced pressure through mean pore size.The ink for preparing different colours thus.
According to the following formulation of mentioning shallow magenta ink of the present invention.
(prescription of shallow magenta ink)
(solid ingredient)
Magenta dyestuff (M-1) 8g/ liter
Urea (UR) 10g/ liter
Proxel 5g/ liter
(liquid ingredient)
Glycol ether (DEG) 90g/ liter
Glycerine (GR) 120g/ liter
Triglycol monobutyl ether (TGB) 110g/ liter
Trolamine (TEA) 8g/ liter
Surfynol STG (SW) 10g/ liter
According to the following prescription of mentioning, the preparation magenta ink, wherein magenta dyestuff (M-1) is brought up to 28g.
(prescription of magenta ink)
(solid ingredient)
Magenta dyestuff (M-1) 28g/ liter
Urea (UR) 15g/ liter
Proxel 5g/ liter
(liquid ingredient)
Glycol ether person 100g/ liter
Glycerine 130g/ liter
Triglycol monobutyl ether 110g/ liter
Trolamine 8g/ liter
Surfynol STG 10g/ liter
Magenta dyestuff (M-1)
Figure G2008101757780D01461
Form other ink of ink group of the present invention according to the following formulation of mentioning.
(prescription of pale cyan inks)
(solid ingredient)
Cyan dye (C-1) 20g/ liter
Urea (UR) 15g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Proxel XL2 (PXL) 3.5g/ liter
(liquid ingredient)
Triglycol (TEG) 110g/ liter
Glycerine (GR) 130g/ liter
Triglycol monobutyl ether (TGB) 110g/ liter
2-Pyrrolidone (PRD) 60g/ liter
Trolamine (TEA) 7g/ liter
Surfynol STG (SW) 10g/ liter
Cyan dye (C-1)
(prescription of cyan)
(solid ingredient)
Cyan dye (C-1) 60g/ liter
Urea (UR) 30g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Proxel XL2 (PXL) 3.5g/ liter
(liquid ingredient)
Triglycol (TEG) 110g/ liter
Glycerine (GR) 130g/ liter
Triglycol monobutyl ether (TGB) 130g/ liter
2-Pyrrolidone (PRD) 60g/ liter
Trolamine (TEA) 7g/ liter
Surfynol STG (SW) 10g/ liter
(prescription of yellow ink)
(solid ingredient)
Yellow dyes (Y-1) 35g/ liter
Proxel 3.5g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Urea 10g/ liter
(liquid ingredient)
Triglycol monobutyl ether (TGB) 130g/ liter
Glycerine (GR) 115g/ liter
Glycol ether (DEG) 120g/ liter
2-Pyrrolidone (PRD) 35g/ liter
Trolamine (TEA) 8g/ liter
Surfynol STG (SW) 10g/ liter
Yellow dyes (Y-1)
Figure G2008101757780D01481
(prescription of deep yellow ink)
(solid ingredient)
Yellow dyes (Y-1) 35g/ liter
Magenta dyestuff (M-1) 2g/ liter
Cyan dye (C-1) 2g/ liter
Proxel 5g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Urea 10g/ liter
(liquid ingredient)
Triglycol monobutyl ether (TGB) 140g/ liter
Glycerine (GR) 125g/ liter
Glycol ether (DEG) 120g/ liter
2-Pyrrolidone 35g/ liter
Trolamine (TEA) 8g/ liter
Surfynol STG (SW) 10g/ liter
(prescription of black ink)
(solid ingredient)
Black dyes (Bk-1) 75g/ liter
Black dyes (Bk-2) 30g/ liter
Proxel 5g/ liter
Urea 10g/ liter
Benzotriazole 3g/ liter
(liquid ingredient)
Diethylene glycol monobutyl ether (DGB) 120g/ liter
Glycerine (GR) 125g/ liter
Glycol ether (DEB) 100g/ liter
2-Pyrrolidone 35g/ liter
Trolamine (TEA) 8g/ liter
Surfynol STG (SW) 10g/ liter
Black dyes (Bk-1)
Figure G2008101757780D01491
Black dyes (Bk-2)
Figure G2008101757780D01501
The ink group for preparing these inks.This is IS-301.To prepare other ink group IS-302 to IS-308, still, wherein, change in the magenta ink and the magenta dyestuff of shallow magenta ink according to following table with top same procedure.
The oxidizing potential (Eox) of the dyestuff that here uses is all greater than 1.0V (with respect to SCE).
Table 12
Shallow magenta ink Magenta ink
IS-301 (comparison) M-1 8g/ liter M-1 28g/ liter
IS-302 (comparison) M-2 20g/ liter M-2 60g/ liter
IS-303 (comparison) M-3 9g/ liter M-3 30g/ liter
IS-304 (the present invention) M-2 20g/ liter M-2 20g/ rises M-3 20g/ liter
IS-305 (the present invention) M-2 20g/ liter M-1 7g/ rises M-2 15g/ and rises M-3 15g/ liter
IS-306 (the present invention) M-3 9g/ liter M-2 20g/ rises M-3 20g/ liter
IS-307 (the present invention) M-2 8g/ rises M-3 7.5g/ liter M-1 7g/ rises M-2 15g/ and rises M-3 15g/ liter
IS-308 (the present invention) M-2 13.5g/ rises M-3 6g/ liter M-2 20g/ rises M-3 20g/ liter
Figure G2008101757780D01511
These inks of in Epson ink-jet printer PM-980C, packing into, and drive stamping machine, on image-receiving sheet, to print the picture pattern that 6 kinds of color C, M, Y, B, G and R and gray density progressively change.
Using the hypograph Reiceiver sheet here is the ink jetting paper of Fuji Photo Film, photograph glossy paper " Gasai ".
(evaluation test)
In stamping machine, settle print cartridge, and spray ink through nozzle separately.Print the paper of 100 A4 sizes with its, and according to following criterion evaluation:
A: begin to finishing not find to print confusion from printing.
B: find that some printings are chaotic.
C: find to print chaotic in whole printing kind.
2) according to the image storage property of following assessment carmetta gradient image
(1) according to the anti-jail property of following assessment light: with X-Rite 310 measure print after immediately the image density Ci of fresh sample.Then, print image is carried out argon gas exposure (85,000 lux) 20 days, measure its image density Cf then from the aging machine of Atlas.From (Cf/Ci) * 100) and obtain the dyestuff conservation rate, and this representes the anti-jail property of light of printed sample.As for the dyestuff retentivity, analyze reflection density in each sample and be three points of 1,1.5 and 2.The dyestuff conservation rate of each point is at least 70% sample and is " A "; The dyestuff conservation rate of two points be lower than 70% those for " B "; With the dyestuff conservation rate of all three points be lower than 70% those be " C ".
(2) according to the anti-jail property of following assessment ozone: in constant concentration of ozone gas is to place printed sample 7 days in the box of 5ppm.Before being exposed to ozone gas,, measure the image density of every kind of sample, and confirm the dyestuff conservation rate of every kind of sample with reflection densitometer (X-Rite310TR) with afterwards.As for the dyestuff conservation rate, the reflection density of analyzing each sample is three points of 1,1.5 and 2.Ozone concn in the box keeps constant with ozone gas monitor (the OZG-EM-01 type of Applics).
With the sample classification of test thus is three kinds of grades: the dyestuff conservation rate of each point be at least 70% those for " A "; The dyestuff conservation rate of one or two point be lower than 70% those for " B "; With the dyestuff conservation rate of all three points be lower than 70% those be " C ".
(3) anti-exudative according to being evaluated at the high humidity hypograph as follows: as to use the distance between the white line each 4 carmetta square as 3cm * 3cm to be formed pattern, to form the print pattern in " field " as 1mm.Under 25 ℃ of conditions with 90%RH, kept image sample 72 hours, through state A spectral filter inspection the oozing out of magenta dyestuff in the white line distance.This be with the fresh sample of printing immediately in ooze out comparison.Carmetta density in storing back white line distance improves when being lower than 0.01, and sample is " A " so; When it was 0.01 to 0.05, sample was " B " so; When it surpassed 0.05, sample was " C " so.
Provide the result below.
Table 13
Ink group sequence number Ejection stability The anti-jail property of light The anti-jail property of ozone Ooze out
PM-980C (comparison) A C C B
IS-301 (comparison) A C C A
IS-302 (comparison) C B A A
IS-303 (comparison) A A A C
IS-304 (the present invention) A A A A
IS-305 (the present invention) A A A A
IS-306 (the present invention) A A A A
IS-307 (the present invention) A A A A
IS-308 (the present invention) A A A A
Above supported effect of the present invention dry straightly.
(embodiment 6)
Add ultrapure water (resistance, 18M Ω at least) to process 1 liter in the component shown in following, under 30 to 40 ℃ of heating, stirred 1 hour then.Then, be that the micro-filter of 0.25 μ m filters the mixture obtain under reduced pressure through mean pore size.The ink for preparing different colours thus.
(prescription of photograph magenta ink)
(solid ingredient)
Magenta dyestuff (M-1) 5g/ liter
Urea (UR) 10g/ liter
Proxel 5g/ liter
(liquid ingredient)
Triglycol (TEG) 40g/ liter
Glycerine (GR) 100g/ liter
Triglycol monobutyl ether (TGB) 60g/ liter
1,5-pentanediol (PTD) 40g/ liter
Virahol (IPA) 20g/ liter
Trolamine (TEA) 6.9g/ liter
Surfynol STG (SW) 10g/ liter
(prescription of magenta ink)
(solid ingredient)
Magenta dyestuff (M-1) 15g/ liter
Urea (UR) 15g/ liter
Proxel 5g/ liter
(liquid ingredient)
Triglycol (TEG) 50g/ liter
Glycerine 100g/ liter
Triglycol monobutyl ether (TGB) 50g/ liter
1,5-pentanediol (PTD) 40g/ liter
Virahol (IPA) 20g/ liter
Trolamine 6.9g/ liter
Surfynol STG 10g/ liter
(prescription of photograph cyan)
(solid ingredient)
Cyan dye (C-1) 10g/ liter
Urea (UR) 15g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Proxel XL2 (PXL) 3.5g/ liter
(liquid ingredient)
Triglycol (TEG) 50g/ liter
Glycerine (GR) 100g/ liter
Triglycol monobutyl ether (TGB) 60g/ liter
1,5-pentanediol (PTD) 40g/ liter
Virahol (IPA) 20g/ liter
Trolamine (TEA) 7g/ liter
Surfynol STG (SW) 10g/ liter
(prescription of cyan)
(solid ingredient)
Cyan dye (C-1) 30g/ liter
Urea (UR) 40g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Proxel XL2 (PXL) 3.5g/ liter
(liquid ingredient)
Triglycol (TEG) 40g/ liter
Glycerine (GR) 100g/ liter
Triglycol monobutyl ether (TGB) 70g/ liter
1,5-pentanediol (PTD) 50g/ liter
Virahol (IPA) 20g/ liter
Trolamine (TEA) 7g/ liter
Surfynol STG (SW) 10g/ liter
(prescription of yellow ink)
(solid ingredient)
Yellow dyes (Y-1) 35g/ liter
Proxel 3.5g/ liter
Benzotriazole (BTZ) 0.08g/ liter
Urea 10g/ liter
(liquid ingredient)
Triglycol (TEG) 40g/ liter
Glycerine (GR) 100g/ liter
Triglycol monobutyl ether (TGB) 70g/ liter
1,5-pentanediol (PTD) 60g/ liter
Virahol (IPA) 20g/ liter
Trolamine (TEA) 8g/ liter
Surfynol STG (SW) 10g/ liter
(prescription of black ink)
(solid ingredient)
Black dyes (Bk-1) 75g/ liter
Black dyes (Bk-2) 30g/ liter
Proxel 5g/ liter
Urea 10g/ liter
Benzotriazole (BTZ) 3g/ liter
(liquid ingredient)
Triglycol (TEG) 60g/ liter
Glycerine (GR) 100g/ liter
Triglycol monobutyl ether (TGB) 70g/ liter
1,5-pentanediol (PTD) 50g/ liter
Virahol (IPA) 20g/ liter
Trolamine (TEA) 8g/ liter
Surfynol STG (SW) 10g/ liter
The ink group for preparing these inks.This is IS-401.In addition, to prepare other ink group IS-402 to IS-408, still, wherein, the dyestuff according to the form below in magenta ink and the photograph magenta ink is changed with top same procedure.
Table 14
The photograph magenta ink Magenta ink
IS-401 (comparison) M-1 5g/ liter M-1 15g/ liter
IS-402 (comparison) M-2 15g/ liter M-2 45g/ liter
IS-403 (comparison) M-3 5g/ liter M-3 15g/ liter
IS-404 (the present invention) M-2 15g/ liter M-2 15g/ rises M-3 10g/ liter
IS-405 (the present invention) M-2 15g/ liter M-1 5g/ rises M-2 15g/ and rises M-3 5g/ liter
IS-406 (the present invention) M-3 5g/ liter M-2 15g/ rises M-3 10g/ liter
IS-407 (the present invention) M-2 5g/ rises M-3 4g/ liter M-1 7g/ rises M-2 15g/ and rises M-3 15g/ liter
IS-408 (the present invention) M-2 10g/ rises M-3 2g/ liter M-2 15g/ rises M-3 10g/ liter
These inks of in Canon ink-jet printer PIXUS950i, packing into drive stamping machine, on image-receiving sheet, to print the picture pattern that 6 kinds of color C, M, Y, B, G and R and gray density progressively change.
Using the hypograph Reiceiver sheet here is ink jetting paper, the photograph glossy paper " Gasai " of Fuji Photo Film.
With stable with embodiment anti-jail property of 5 same way as evaluate image and ink ejection.
Provide the result below.
Table 15
Ink group sequence number Ejection stability The anti-jail property of light The anti-jail property of ozone Ooze out
PIXU950i (comparison) A C C A
IS-401 (comparison) A C C A
IS-402 (comparison) C B A A
IS-403 (comparison) A A A C
IS-404 (the present invention) A A A A
IS-405 (the present invention) A A A A
IS-406 (the present invention) A A A A
IS-407 (the present invention) A A A A
IS-408 (the present invention) A A A A
Above supported effect of the present invention dry straightly.
Through with reference to concrete embodiment illustrated in detail the present invention, but be can be to what it will be apparent to those skilled in that in various modifications of adding and change in scope of the present invention and the spirit.
It all is Japanese patent application JP2003-363727, JP2003-363728 and the JP2003-363883 that submits on October 23rd, 2003 that the application is based on, and its content is combined in this by reference.
Industrial usability
Can apply the present invention to ink jet recording method and unqualified.What for example, can adopt is any in the following system: spray the also Electrostatic Control system of ink through electrostatic attraction; Utilize the dropping system as required (pressure pulse system) of the vibration pressure of piezoelectric element; Electrical signal is changed into acoustic beam, it is applied to ink, and under radiation pressure, spray the sound ink jet system of ink; Or heating ink produces hot ink-jet (bubble jet) system of the pressure of bubble and utilization generation.

Claims (5)

1. inkjet recording black ink, it comprises:
Aqueous medium; With
At least two kinds of dyestuffs, wherein said at least two kinds of dyestuffs have independently of one another: λ max is 500nm to 700nm; Half breadth in the absorption spectrum of diluting soln is 100nm or higher, and it is 1.0 that described absorption spectrum is made its absorbancy under λ max by stdn,
Wherein at least a dyestuff is the compound by formula (B1) expression:
A 41-N＝N-A 42-N＝N-A 43
Wherein, A 41, A 42And A 43Expression independently of one another replaces or unsubstituted aromatic group or heterocyclic group; A 41And A 43It is univalent perssad; A 42Be divalent group,
Wherein at least a dyestuff is the compound by formula (B2) expression:
P-(N＝N-Qx)y-N＝N-R
Wherein, P, Q, R represent to replace or unsubstituted aromatic group separately; X representes 1 or bigger integer; Y is 0 or bigger integer,
At least a oxidizing potential in wherein said at least two kinds of dyestuffs is higher than 1.0V with respect to SCE.
2. according to the inkjet recording black ink of claim 1, it also comprises the dyestuff that λ max is 350nm to 500nm.
3. according to the inkjet recording black ink of claim 1, the Q in its Chinese style (B2) is the polycyclic aromatic ring.
4. according to the inkjet recording black ink of claim 2, be that the dyestuff of 350nm to 500nm is the compound by formula (B1) expression wherein according to the λ max of claim 2.
5. ink for inkjet recording group, it comprises the black ink according to claim 1.
CN 200810175778 2003-10-23 2004-10-22 Ink and ink set for inkjet recording Expired - Fee Related CN101665637B (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP2003-363727 2003-10-23
JP2003363728 2003-10-23
JP2003363883 2003-10-23
JP2003363728 2003-10-23
JP2003-363883 2003-10-23
JP2003363883 2003-10-23
JP2003-363728 2003-10-23
JP2003363727 2003-10-23
JP2003363727 2003-10-23

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CN101665637B true CN101665637B (en) 2012-07-11

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CN100577751C (en) 2010-01-06

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