CN1886467A - Trisazo compound, ink composition, and colored object - Google Patents
Trisazo compound, ink composition, and colored object Download PDFInfo
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- CN1886467A CN1886467A CN 200480035579 CN200480035579A CN1886467A CN 1886467 A CN1886467 A CN 1886467A CN 200480035579 CN200480035579 CN 200480035579 CN 200480035579 A CN200480035579 A CN 200480035579A CN 1886467 A CN1886467 A CN 1886467A
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Abstract
To provide: a black compound which is for use in ink-jet recording or writing utensils, is excellent in ozone resistance, light resistance, moisture resistance, and color rendering, and gives a recording fluid having satisfactory storage stability; and an ink composition containing the compound. The black compound is a trisazo compound represented by the following formula (1) or a salt thereof. (1) [In the formula (1), R<1> and R<2> each independently represents hydrogen, carboxy, sulfo, hydroxy, a C1-4 alkyl, C1-4 alkoxy, or sulfo group optionally substituted by C1-4 alkoxy, an optionally carboxylated C1-4 alkoxy group, etc.; and A represents phenyl or naphthyl (provided that the phenyl and naphthyl groups may be substituted by halogeno, carboxy, sulfo, sulfamonyl optionally substituted by alkyl or phenyl, nitro, etc.)].
Description
Technical field
The present invention relates to novel tris-azo compound or its salt, contain the ink composite and the consequent colouring agent of these materials.
Background technology
The recording method that is produced by the ink-jet printer of one of exemplary process in various colored writing-methods is to make it to produce the printing ink droplet, make it be recorded the method that material (paper, film, cloth etc.) writes down attached to various.This method is because record-header is little and quiet with the sound that the material that is recorded does not contact, sends, and in addition, because have the speciality of miniaturization, easy high speed, so popularize rapidly in recent years, big growth will from now on also wait in expectation.In the past, as the printing ink and the spray ink Printing recording ink of pen, plastic core pen etc., use the water color ink of dissolving water-soluble dye in aqueous medium, in these water-based inks, for the printing ink that prevents nib or inkjet nozzle stops up, generally add water-miscible organic solvent.Therefore, in these printing ink in the past, document image, nib or the nozzle that requirement provides full concentration do not stop up, be recorded that drying property on the material is good, infiltration less, excellent storage stability etc., in addition, special requirement are to the solubleness height of water, to being added to the solubleness height of the water-miscible organic solvent in the printing ink.The image stability of the image water tolerance that also require to form, photostabilization, anti-ozone gas, wet fastness etc.
So-called anti-ozone gas also simply is called ozone resistance or anti-gaseousness usually, be to the ozone gas that exists in the air with oxygenizement in recording paper with the dyestuff reaction, make the fade patience of phenomenon of the image variable color that is printed.As the oxidizing gas that also has this effect beyond the ozone gas, can enumerate NOx, SOx etc., but ozone gas is to promote the reason material that the image variable color of spray ink Printing record is faded more than these oxidizing gas.Particularly in the ink-receiver layer that photograph texture spray ink Printing dedicated paper surface is provided with, in order to accelerate ink setting, in addition, in order to reduce infiltration in high texture, use porous matter starting material mostly by generations such as white inorganic pigments, on such recording paper, can see significantly by the variable color of ozone gas generation and fading.The variable color that produces by this oxidizing gas fade phenomenon on ink jet print image because be distinctive phenomenon, so, improve anti-ozone gas and become one of most important problem.
From now on, should enlarge the use field of the printing process of using printing ink, ink-vapor recording with in operable ink composite and the colouring agent that is colored therefrom, require raising water tolerance, photostabilization, wet fastness, anti-ozone gas more consumingly.
The printing ink of various color and lusters is prepared from various dyestuffs, and wherein, black ink is the important printing ink that all is used in monochromatic and full-colour image.Dyestuff as these black inks are used proposes much until today, but does not also provide the goods that fully satisfy market demands.The many pigments that propose are two diazonium pigments, the tone of these pigments shallow excessively (becoming) with red black, have that colour rendering is poor, water tolerance and poor, the anti-ozone gas of wet fastness are insufficient etc. problem.In addition, when similarly proposing most azos and containing aurochrome, have contain metal ion, to the security of human body and the problem insufficient etc. to insufficient, the anti-ozone gas of the consideration of environment.In order to add shade, about prolonging the quadruple nitrogen pigment of conjugate class, the problem that poor, the anti-ozone gas of storage stability of low, water-soluble low, the aqueous solution of residual tone concentration and printing ink is insufficient etc.
About becoming the anti-ozone gas of most important problem in recent years, with the black ink dye compound, can enumerate for example compound of patent documentation 1 record as the spray ink Printing that is modified.But the anti-ozone gas of these compounds can not satisfy market demands fully.In addition, as being similar to the compound of black ink of the present invention on the structure with dye compound, can be set forth in the patent documentation 2,3 compound of record, but can not satisfy market demands fully, particularly can not fully satisfy requirement about anti-ozone gas.
Patent documentation 1: the spy opens the 2003-183545 communique
Patent documentation 2: the spy opens clear 62-109872 communique
Patent documentation 3: the spy opens the 2003-201412 communique
Summary of the invention
Even the object of the present invention is to provide when preserving high density aqueous dye solutions and printing ink for a long time also stable for the solvability height that with water is the medium of main component, provide the black recording image of fastness, particularly anti-ozone gas excellence of concentration height, the print image of print image, in addition, synthesize easy and cheap black ink pigment and ink composite thereof.
The result that the above-mentioned problem that the inventor etc. just should solve is furtherd investigate repeatedly, so that finished the present invention.That is, the present invention relates to
(1) tris-azo compound or its salt of representing with following formula (1)
(in the formula (1), R
1With R
2Represent independently respectively hydrogen atom, halogen atom, cyano group, carboxyl, sulfo group, sulfamyl, N-alkyl amino sulfonyl, N-phenyl amino alkylsulfonyl, phosphate, nitro, acyl group, urea groups, can be with hydroxyl or (C
1～C
4) (the C that replaces of alkoxyl group
1～C
4) alkyl, can be with hydroxyl, (C
1～C
4) (the C of alkoxyl group, sulfo group or carboxyl substituted
1～C
4) alkoxyl group or amide group, A represent phenyl or naphthyl (wherein, these phenyl and naphthyl also can with halogen atom, cyano group, carboxyl, sulfo group, the sulfamyl that can replace with alkyl or phenyl, phosphate, nitro, acyl group, urea groups, can be with hydroxyl or (C
1～C
4) (the C that replaces of alkoxyl group
1～C
4) alkyl, can be with hydroxyl, (C
1～C
4) (the C of alkoxyl group, sulfo group or carboxyl substituted
1～C
4) alkoxyl group or acyl amino replacement).)
(2) as tris-azo compound or its salt of (1) record, formula (1) is represented with following formula (2)
(in the formula (2), R
1Expression carboxyl, sulfo group or (C
1～C
4) alkoxyl group, R
2Expression hydrogen atom or sulfo group, R
3Expression carboxyl, sulfo group or (C
1～C
4) alkoxyl group, R
4Expression hydrogen atom, halogen atom, carboxyl, sulfo group, nitro, (C
1～C
4) alkoxyl group, sulfamyl or N-(C
1～C
4) alkyl amino sulfonyl, R
5Expression hydrogen atom, carboxyl or sulfo group).
(3) tris-azo compound or its salt of putting down in writing as (2), in formula (2), R
1Relatively azo-group is connected 2, nitro and is connected 4, R
2Be connected 5, R
3Azo-group is connected 2, R relatively
4Be connected 4, R
5Be connected 5 or 6.
(4) tris-azo compound or its salt of putting down in writing as (3), in formula (2), R
3Be carboxyl or sulfo group, R
4Be carboxyl, sulfo group, sulfamyl, N-(C
1～C
4) alkyl amino sulfonyl, nitro, (C
1～C
4) alkoxyl group, R
5Be hydrogen atom or carboxyl, R
3Azo-group is connected 2, R relatively
4Be connected 4, R
5Be connected 5.
(5) as tris-azo compound or its salt of (1) record, formula (1) is represented with following formula (2 ').
(in the formula (2 '), R
1Expression carboxyl or sulfo group, R
2The expression hydrogen atom, R
6Expression sulfo group or nitro, R
7Expression hydrogen atom or sulfo group.)
(6) tris-azo compound or its salt of putting down in writing as (5), the R in the formula (2 ')
1Relatively the nitro that is connected on 2, phenyl of azo-group is connected 4, with R
6With R
7In the naphthyl that replaces, azo-group is 1 or 2 of naphthyl, R
6At 5 or 6, R
7At 7 or 8.
(7) tris-azo compound or its salt of representing with following formula (2-1)
(8) with the salt of the tris-azo compound of any record of (1)～(7), salt is lithium salts, sodium salt, sylvite, ammonium salt or with the ammonium salt of general formula (3) expression,
(in the formula (3), Z
1, Z
2, Z
3, Z
4Represent hydrogen atom, alkyl, hydroxyalkyl or hydroxy alkoxy alkyl respectively independently).
(9) a kind of ink composite is characterized in that having tris-azo compound or its salt of any record of at least a (1)～(8).
(10) a kind of ink-jet printer, filling contains the container of the ink composite of record in (9).
(11) ink composite of putting down in writing is used in a kind of spray ink Printing recording method in (9).
(12) a kind of spray ink Printing recording method, the material that is recorded in (11) in the inkjet printing methods of record is an information transmission sheet.
(13), it is characterized in that the information transmission contains porousness white inorganics with sheet as the spray ink Printing recording method of record in (12).
(14) a kind of colouring agent, painted by tris-azo compound or its salt of any record of (1)～(8).
The invention effect
Because the water-soluble excellence of tris-azo compound of the present invention is so good by the filterableness of utilizing membrane filter in the ink composite manufacturing processed, the stability when record liquid is preserved and the stability that spues are also excellent.In addition, the ink composite of the present invention that contains this tris-azo compound does not have that the crystallization after long-time the preservation is separated out yet, rerum natura variation, colour-change etc., and stability in storage is good.In addition, the ink composite that contains tris-azo compound of the present invention, can be used as spray ink Printing record usefulness, Writing utensil equipped usefulness, the gradation of drop-out colour height of the document image when common paper and spray ink Printing dedicated paper record, various fastness, particularly anti-ozone gas excellence.By shared, can carry out the panchromatic spray ink Printing record of various fastness excellences with scarlet, blue-greenish colour and yellow dyes.Like this, ink composite of the present invention is exceedingly useful with black ink as the spray ink Printing record.
Embodiment
Below, explain the present invention.
R in general formula (1) and general formula (2)
1～R
5In the substituting group that can replace on the phenyl or naphthyl of A,, can enumerate ethanoyl, propionyl, butyryl radicals, isobutyryl, benzoyl, naphthoyl etc. as the example of acyl group.
R in general formula (1) and general formula (2)
1～R
5On the phenyl or naphthyl of A; in the substituting group that can replace; example as the sulfamyl that can replace with alkyl or phenyl; can enumerate sulfamyl, N-methyl sulfamyl, N-ethyl sulfamyl, N-(normal-butyl) sulfamyl, N; N-dimethylamino alkylsulfonyl, N, N-two (n-propyl) sulfamyl, N-phenyl sulfamoyl base etc.
R in general formula (1) and general formula (2)
1～R
5On the phenyl or naphthyl of A, in the substituting group that can replace, as can be with hydroxyl or (C
1～C
4) (the C that replaces of alkoxyl group
1～C
4) example of alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, methoxy ethyl, 2-ethoxyethyl group, positive propoxy ethyl, isopropoxy ethyl, n-butoxy ethyl, methoxy-propyl, ethoxycarbonyl propyl, positive propoxy propyl group, isopropoxy butyl, positive propoxy butyl etc.
R in general formula (1) and general formula (2)
1～R
5On the phenyl or naphthyl of A, in the substituting group that can replace, as can be with hydroxyl, (C
1～C
4) (the C of alkoxyl group, sulfo group or carboxyl substituted
1～C
4) example of alkoxyl group, can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, the 2-hydroxyl-oxethyl, 2-hydroxyl propoxy-, 3-hydroxyl propoxy-, methoxy ethoxy, ethoxy ethoxy, the positive propoxy oxyethyl group, the isopropoxy oxyethyl group, the n-butoxy oxyethyl group, methoxy propoxy, the oxyethyl group propoxy-, the positive propoxy propoxy-, the isopropoxy butoxy, the positive propoxy butoxy, 2-'-hydroxyethoxy base oxethyl, the carboxyl methoxyl group, 2-carboxyl oxyethyl group, 3-carboxyl propoxy-, 3-sulfo group propoxy-, 4-sulfo group butoxy etc.
R in general formula (1) and general formula (2)
1～R
5On the phenyl or naphthyl of A, in the substituting group that can replace,, can enumerate acetamido, propionamido-, amide-based small, isobutyl amide, benzoylamino, naphthoyl amido etc. as the example of amide group.
Preferred R in general formula (1)
1With R
2It is hydrogen atom; the chlorine atom; bromine atoms; cyano group; carboxyl; sulfo group; sulfamyl; N-methyl sulfamyl; N-ethyl sulfamyl; phosphate; nitro; ethanoyl; benzoyl; urea groups; methyl; methoxyl group; ethyl; oxyethyl group; propyl group; propoxy-; the 2-hydroxyl-oxethyl; the 2-methoxy ethoxy; the 2-ethoxy ethoxy; 3-sulfo group propoxy-; 4-sulfo group butoxy; the carboxyl methoxyl group; 2-carboxyl oxyethyl group; acetamido; benzoylamino etc.; more preferably hydrogen atom; the chlorine atom; cyano group; sulfamyl; ethanoyl; nitro; carboxyl; sulfo group; phosphate, preferred especially hydrogen atom; carboxyl; sulfo group.
The preferred substituted that can replace on the phenyl or naphthyl of the A in general formula (1) is a hydrogen atom; the chlorine atom; bromine atoms; cyano group; carboxyl; sulfo group; sulfamyl; N-methyl sulfamyl; N-ethyl sulfamyl; phosphate; nitro; ethanoyl; benzoyl; urea groups; methyl; methoxyl group; ethyl; oxyethyl group; propyl group; propoxy-; the 2-hydroxyl-oxethyl; the 2-methoxy ethoxy; the 2-ethoxy ethoxy; 3-sulfo group propoxy-; 4-sulfo group butoxy; the carboxyl methoxyl group; 2-carboxyl oxyethyl group; acetamido; benzoylamino etc.; more preferably hydrogen atom; cyano group; methyl; methoxyl group; sulfamyl; ethanoyl; nitro; carboxyl; sulfo group; N-methyl sulfamyl, preferred especially hydrogen atom; methoxyl group; sulfamyl; nitro; carboxyl; sulfo group; N-methyl sulfamyl.
Preferred R in general formula (2)
3～R
5It is hydrogen atom; the chlorine atom; bromine atoms; cyano group; carboxyl; sulfo group; sulfamyl; N-methyl sulfamyl; N-ethyl sulfamyl; phosphate; nitro; ethanoyl; benzoyl; urea groups; methyl; methoxyl group; ethyl; oxyethyl group; propyl group; propoxy-; the 2-hydroxyl-oxethyl; the 2-methoxy ethoxy; the 2-ethoxy ethoxy; 3-sulfo group propoxy-; 4-sulfo group butoxy; the carboxyl methoxyl group; 2-carboxyl oxyethyl group; acetamido; benzoylamino etc.; more preferably hydrogen atom; cyano group; methyl; methoxyl group; sulfamyl; N-methyl sulfamyl; ethanoyl; nitro; carboxyl; sulfo group, preferred especially hydrogen atom; methoxyl group; sulfamyl; nitro; carboxyl; sulfo group; N-methyl sulfamyl.
With the salt of above-mentioned general formula (1), be inorganic or organic cationic salts with the compound of (2) expression.Wherein, as the object lesson of inorganic salt, can enumerate an alkali metal salt, alkali earth metal salt and ammonium salt, preferred inorganic salt are the salt and the ammonium salt of lithium, sodium, potassium, in addition, as organic cation salt, for example can enumerate with the salt of the compound of above-mentioned formula (3) expression but be not limited to these.
As the Z in the general formula (3)
1, Z
2, Z
3, Z
4In the example of alkyl, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl etc., as the example of hydroxyalkyl, can enumerate the hydroxyl-(C of methylol, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxyl butyl, 3-hydroxyl butyl, 2-hydroxyl butyl etc.
1～C
4) alkyl, as the example of hydroxy alkoxy alkyl, can enumerate hydroxyl (C such as '-hydroxyethoxy ylmethyl, 2-hydroxyl ethoxy ethyl, 3-hydroxyl-oxethyl propyl group, 2-hydroxyl-oxethyl propyl group, 4-hydroxyl-oxethyl butyl, 3-hydroxyl-oxethyl butyl, 2-hydroxyl-oxethyl butyl
1～C
4) alkoxyl group-(C
1～C
4) alkyl, wherein, preferred hydroxyl-oxethyl-(C
1～C
4) alkyl.As particularly preferred, can enumerate hydrogen atom; Methyl; Methylol; Hydroxyethyl; Hydroxyl-(the C of 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxyl butyl, 3-hydroxyl butyl, 2-hydroxyl butyl etc.
1～C
4) alkyl; Hydroxyl-oxethyl-(the C of '-hydroxyethoxy ylmethyl, 2-hydroxyl ethoxy ethyl, 3-hydroxyl-oxethyl propyl group, 2-hydroxyl-oxethyl propyl group, 4-hydroxyl-oxethyl butyl, 3-hydroxyl-oxethyl butyl, 2-hydroxyl-oxethyl butyl etc.
1～C
4) alkyl.
In table 1, represent the Z in the general formula (3)
1, Z
2, Z
3, Z
4Object lesson.
Table 1
| Compound N o. | Z 1 | Z 2 | Z 3 | Z 4 |
| 1-1 | H | -C 2H 4OH | -C 2H 4OH | -C 2H 4OH |
| 1-2 | CH 3 | -C 2H 4OH | -C 2H 4OH | -C 2H 4OH |
| 1-3 | H | -CH 2CH(OH)CH 3 | -CH 2CH(OH)CH 3 | -CH 2CH(OH)CH 3 |
| 1-4 | CH 3 | -CH 2CH(OH)CH 3 | -CH 2CH(OH)CH 3 | -CH 2CH(OH)CH 3 |
| 1-5 | H | -C 2H 4OH | H | -C 2H 4OH |
| 1-6 | CH 3 | -C 2H 4OH | H | -C 2H 4OH |
| 1-7 | H | -CH 2CH(OH)CH 3 | H | -CH 2CH(OH)CH 3 |
| 1-8 | CH 3 | -CH 2CH(OH)CH 3 | H | -CH 2CH(OH)CH 3 |
| 1-9 | CH 3 | -C 2H 4OH | CH 3 | -C 2H 4OH |
| 1-10 | CH 3 | -CH 2CH(OH)CH 3 | CH 3 | -CH 2CH(OH)CH 3 |
With the of the present invention tris-azo compound of general formula (1) with (2) expression, can be synthetic with for example following method.Here, enumerate example with the tris-azo compound of expression in general formula (2), but also can be synthetic with same method to the tris-azo compound with general formula (1) expression.In addition, the structural formula of compound in each operation is represented with the form of free acid.That is, in the presence of alkali, by 2-amino-5-naphthols-1, the reaction of 7-disulfonic acid and Tosyl chloride can obtain the compound by formula (4) expression,
Will be by usual method with the compound diazotization of formula (4) expression with formula (5)
The compound of expression carries out coupled reaction, generates the compound with formula (6) expression,
Make the compound of formula (6) expression, with usual method and with formula (7)
(in the formula, R
1With R
2Has an identical meaning with above-mentioned)
The diazotization thing of the compound of expression carries out coupled reaction, obtains the compound of formula (8) expression,
(in the formula, R
1With R
2Has an identical meaning with above-mentioned)
Compound hydrolysis under alkaline condition of formula (8) expression obtains with formula (9)
(in the formula, R
1With R
2Has an identical meaning with above-mentioned)
The compound of expression.Wherein, make with usual method formula (10)
(in the formula, R
4With R
5Has an identical meaning with above-mentioned)
The diazotization thing coupling of the compound of expression can obtain the tris-azo compound of the present invention with general formula (2) expression.
Do not limited especially as suitable example, but can be enumerated the material of following structural formula particularly at compound shown in the formula (1).
Table 2
Table 3
Table 4
Table 5
By 2-amino-5-naphthols-1, synthesizing of the compound of the formula (4) that the reaction of 7-disulfonic acid and Tosyl chloride produces, with itself known method enforcement, for example in water-based or water-based organic medium, with for example 20～100 ℃, preferably be favourable with 30～80 ℃ temperature and neutral pH value to alkalescence.Preferably with weakly alkaline pH value, for example implement with pH8～11.The adjusting of this pH value is implemented by adding alkali.As alkali, can use for example lithium hydroxide, the such alkali metal hydroxide of sodium hydroxide, alkaline carbonate that Quilonum Retard, yellow soda ash, salt of wormwood are such etc.Relative 2-amino-5-naphthols-1, the 7-disulfonic acid, Tosyl chloride uses 1～1.5 times of mole.
The diazotization of the compound of formula (4) is implemented with itself known method, for example in inorganic acid medium, with for example-5～30 ℃, preferably with 5～15 ℃ temperature, use nitrite, the such nitrite alkali metal-salt of for example Sodium Nitrite to implement.The coupling of the compound of the diazotization thing of the compound of formula (4) and formula (5) is also with itself known condition enforcement.In water-based or water-based organic medium, with for example-5～30 ℃, preferably with 5～20 ℃ temperature and acid to neutral pH value be favourable.Acidification is bathed in coupling, but preferably with acidity to weakly acidic pH value, for example with pH1～4 enforcements.The adjusting of this pH value is implemented by adding alkali.As alkali, can use for example lithium hydroxide, the such alkali metal hydroxide of sodium hydroxide, Quilonum Retard, yellow soda ash, the such alkaline carbonate of salt of wormwood, the acetate that sodium-acetate is such, ammonium or organic amine etc.The compound of formula (4) and formula (5) almost uses stoichiometric quantity.
The diazotization of the compound of formula (7) is also implemented with itself known method, for example in inorganic acid medium, with for example-5～30 ℃, preferably with 0～15 ℃ temperature, for example use the such nitrite alkali metal-salt of Sodium Nitrite to implement.The azo of the compound of the diazotization thing of the compound of formula (7) and general formula (6) is also with itself known condition enforcement.In water-based or water-based organic medium, being favourable for example-5～30 ℃, preferably with 10～25 ℃ temperature and slightly acidic to the pH value of alkalescence.Preferably with slightly acidic to weakly alkaline pH value, for example implement with pH5～10, the adjusting of pH value is implemented by interpolation alkali.As alkali, can use for example lithium hydroxide, the such alkali metal hydroxide of sodium hydroxide, the alkaline carbonate that Quilonum Retard, yellow soda ash or salt of wormwood are such, the acetate that sodium-acetate is such, or ammonium or organic amine etc.The compound of formula (6) and formula (7) almost uses stoichiometric quantity.
The manufacturing of the compound of the general formula (9) that is produced by the compound hydrolysis of formula (8) is also implemented with itself known method.The method that in the water-based alkaline medium, heats advantageously, for example, after adding sodium hydroxide or potassium hydroxide in the solution of the compound that contains general formula (8), making pH become more than 9.5, for example 20～150 ℃ temperature, preferred 30～100 ℃ temperature are implemented by being heated to.At this moment, the pH value of reaction soln preferably maintains 9.5～11.5.The adjusting of this pH value is implemented by adding alkali.Alkali can use above-mentioned alkali.
The diazotization of the compound of general formula (10) is also implemented with itself known method, for example, in inorganic acid medium with for example-5～30 ℃, preferably with 0～15 ℃ temperature, for example use the such nitrite alkali metal-salt of Sodium Nitrite to implement.The coupling of the compound of the diazotization thing of the compound of general formula (10) and general formula (9) is also implemented with itself known method.In water-based or water-based organic medium, with for example 5～40 ℃, preferably be favourable with 10～25 ℃ temperature and slightly acidic to the pH value of alkalescence.Preferably with neutrality to the pH value of alkalescence, for example implement with pH5～10, the adjusting of pH value is implemented by interpolation alkali.As alkali, can use for example lithium hydroxide, the such alkali metal hydroxide of sodium hydroxide, the alkaline carbonate that Quilonum Retard, yellow soda ash or salt of wormwood are such, the acetate that sodium-acetate is such, or ammonium or organic amine etc.The compound of general formula (9) and general formula (10) almost uses stoichiometric quantity.
With the tris-azo compound of general formula of the present invention (1) expression or its salt (following otherwise statement in advance, the compound or its salt list is called compound), after coupled reaction, can separate separately with the form of free acid by adding mineral acid, after this, clean by water or sour water and can remove inorganic salt.Then, the acid type pigment that obtains like this with hyposaline rate, can be in aqueous medium by desirable inorganic or organic bases neutralization, become corresponding salts solution.Example as mineral alkali, can enumerate for example lithium hydroxide, sodium hydroxide, such alkali metal hydroxide, the ammonium hydroxide of potassium hydroxide, or Quilonum Retard, yellow soda ash, the such alkaline carbonate of salt of wormwood, example as organic bases, can enumerate organic amine, the aliphatics hydramine of diethanolamine, trolamine etc. for example, but be not limited to these.
Ink composite of the present invention is described.Contain waterborne compositions, can dye by the material that Mierocrystalline cellulose is formed with the tris-azo compound of above-mentioned general formula of the present invention (1) expression.In addition, on other has the material of carboxylic acid amide key, also can dye, can be widely used for the dyeing of leather, fabric, paper.On the other hand, as the representational using method of The compounds of this invention, can be set forth in dissolving in the liquid medium and the ink composite of composition.
Contain reaction solution, can in the manufacturing of ink composite, directly use with the tris-azo compound of the present invention of above-mentioned general formula (1) expression.But, also can at first be dried, for example make it spraying drying and separation separately, or saltout with the inorganic salts of sodium-chlor, Repone K, calcium chloride, sodium sulfate etc., or with the mineral acid acid out of hydrochloric acid, sulfuric acid, nitric acid etc., or, then be processed into ink composite to make up above-mentioned saltout and diazonium compound of the present invention is analysed, taken out to the hydrochlorate of acid out.
Ink composite of the present invention, with contain usually 0.1～20 quality %, preferably contain 1～10 quality %, more preferably contain 2～8 quality %, be the composition of main medium with the water of the tris-azo compound of the present invention of general formula (1) expression.In ink composite of the present invention, can also contain 0～30 quality % for example water-miscible organic solvent, contain for example ink formulations of 0～5 quality %.In addition, as the pH of ink composite, for improving storage stability, preferred pH5～11, more preferably pH7～10.In addition, as the surface tension of coloured composition, preferred 25～70mN/m, more preferably 25～60mN/m.As the viscosity of coloured composition, below the preferred 30mPas, more preferably below the 20mPas.
Ink composite of the present invention, be water or water-miscible organic solvent (organic solvent or contain can with the water of water blended organic solvent) in the above-mentioned tris-azo compound of dissolving with general formula (1) expression, add the composition of ink formulations as required.When the printing ink that this ink composite is used as ink-jet printer uses, preferably using the few compound of inorganic content of metallic cation muriate, vitriol etc., the standard substantially of its content as tris-azo compound is for example about 1 quality % following (pigment substance relatively).In making the few tris-azo compound of inorganics, can be for example to utilize the usual method of oppositely soaking into film or to carry out desalting treatment at the dry product of tris-azo compound of the present invention or the method that in the mixed solvent of the alcohol of methyl alcohol etc. and water, stirs wet cake, filtration, drying etc.
As the water-miscible organic solvent that in the preparation of above-mentioned ink composite, can use, can enumerate for example C of methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol etc.
1～C
4Alkanol, N, dinethylformamide or N, the carboxylic acid amide of N-N,N-DIMETHYLACETAMIDE etc., 2-Pyrrolidone, the lactan of N-methylpyrrolidin-2-ketone etc., 1,3-dimethyl-imidazo pyridin-2-ones or 1, the ring type urea class of 3-dimethyl hexahydroxy-pyrimid-2-one etc., acetone, methylethylketone, the ketone or the keto-alcohol of 2-methyl-2-hydroxyl pentane-4-ketone etc., the cyclic ethers of tetrahydrofuran (THF) diox etc., ethylene glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1, the 4-butyleneglycol, 1, the 6-hexylene glycol, diethylene glycol, triglycol, Tetraglycol 99, dipropylene glycol, polyoxyethylene glycol, polypropylene glycol, thiodiglycol, two thiodiglycols etc. have (a C
2～C
6) monomer, oligopolymer or the polyalkylene glycol of alkylidene group unit or thiodiglycol, glycerine, hexane-1,2, (the C of the polyvalent alcohol of the polyvalent alcohol of 6-triol etc. (triol), ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol list ether or triethylene glycol monomethyl ether or triglycol list ether etc.
1～C
4) alkyl oxide, butyrolactam or dimethyl sulfoxide (DMSO) etc.These organic solvents can use separately, also two or more kinds may be used.
As operable ink formulations in above-mentioned ink composite preparation, can enumerate for example sanitas, mould inhibitor, pH regulator agent, sequestrant, rust-preventive agent, water-soluble UV light absorber, water-soluble high-molecular compound, dyestuff solvating agent, antioxidant, tensio-active agent etc.To its object lesson explanation.
As above-mentioned mould inhibitor, can enumerate sodium dehydroacetate, Sodium Benzoate, sodium pyridine sulfo--1-oxide compound, ethyl p-hydroxybenzoate, 1,2-benzisothiazole-3-ketone and salt etc.These are preferred 0.02～1.00 quality % that uses in coloured composition.
As sanitas, can enumerate for example compound of organosulfur class, organonitrogen sulphur class, organic halogen class, halogenated allyl sulfonation class, iodine propargyl class, N-haloalkyl thio class, benzothiazoles, nitrile, pyridines, oxine class, benzothiazoles, isothiazoline class, dithiode class, pyridine oxide class, nitropropane class, organic tin, phenol, quaternary ammonium salt, triazines, thiazides, anilide class, adamantane, dithiocarbamate(s), bromination indane ketone, benzyl bromination acetate esters, inorganic salts etc.As organic halogen compounds, can enumerate for example sodium pentachlorophenate, as the pyridine oxide compounds, can enumerate for example 2-pyridine sulfo--1-oxide, sodium, as the inorganic salts compound, can enumerate for example sodium acetate, anhydrous, as the isothiazoline compounds, for example can enumerate 1,2-benzene isothiazoline-3-ketone, 2-n-hexyl-4-isothiazoline-3-ketone, 5-chloro-2-methyl-4-isothiazoline-3-ketone, 5-chloro-2-methyl-4-isothiazoline-3-ketone magnesium chloride, 5-chloro-2-methyl-4-isothiazoline-3-ketone calcium chloride, 2-methyl-4-isothiazoline-3-ketone calcium chloride etc.
As the pH regulator agent,, can use arbitrary substance if the printing ink that is conditioned is not brought bad influence, the pH of printing ink can be controlled at for example 5～11 scope.As its example, can enumerate the alkaline carbonate of alkali metal hydroxide, ammonium hydroxide (ammonia) or Quilonum Retard, yellow soda ash, sodium bicarbonate, the salt of wormwood etc. of the hydramine, lithium hydroxide, sodium hydroxide, potassium hydroxide etc. of for example diethanolamine, trolamine, N methyldiethanol amine etc., the mineral alkali of Potassium ethanoate, water glass, Sodium phosphate dibasic etc. etc.
As sequestrant, can enumerate for example sodium ethylene diamine tetracetate, sodium nitrilo triacetate, hydroxyethylethylene diamine tri-acetic acid sodium, diethylene triaminepentaacetic acid(DTPA) sodium, uridylic sodium diacelate etc.
As rust-preventive agent, can enumerate for example hydrosulphite, Sulfothiorine, ammonium mercaptoacetate, di-isopropyl ammonium nitride, four nitric acid tetramethylolmethanes, dicyclohexyl ammonium nitride etc.
As water-soluble UV light absorber, can enumerate for example sulfonated benzophenone compound, benzotriazole compound, salicylic acid compounds, cinnamic acid compound, compound in triazine class.
As water-soluble high-molecular compound, can enumerate polyvinyl alcohol, derivatived cellulose, polyamine, poly-imines etc.
As the dyestuff solvating agent, can enumerate for example ε-Ji Neixianan, NSC 11801, urea etc.
As antioxidant, can use fading of for example various organic classes and metal complex class to prevent agent.Prevent agent as fading of above-mentioned organic class, can enumerate hydroquinone type, alkoxyl group phenols, dialkoxy phenols, phenols, phenyl amines, amine, indane class, chroman class, alkoxy benzene amine, heterocyclic etc.
As tensio-active agent, can enumerate for example known tensio-active agents such as anionic species, cationic, nonionic class.As anion surfactant, can enumerate alkylsulphonic acid, alkyl carboxylate, alpha-olefin sulfonate, Voranol EP 2001 acetate, N-acylamino acid and salt thereof, N-acyl methyl taurine salt, resin acid soap, castor seeds oil sulfuric acid, lauryl alcohol sulfuric acid, alkylphenol type phosphoric acid ester, alkyl type phosphoric acid ester, alkylallyl sulfonate, diethyl sulfosuccinate, diethylhexyl sulfosuccinate, dioctyl sulfosuccinate etc.As cats product, 2-vinylpyridine piperidine derivatives, poly 4 vinyl pyridine derivative etc. are arranged.As amphoterics, lauryl dimethyl amine acetic acid trimethyl-glycine, 2-alkyl-N-carboxyl methyl-N-hydroxyethyl imidazole quinoline trimethyl-glycine, coco-nut oil fatty acid amido propyl dimethyl amine acetic acid trimethyl-glycine, poly-octyl group polyamine ethyl glycine and other imidazolidine derivatives etc. are arranged.As nonionogenic tenside, can enumerate polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, polyoxyethylene dodecyl phenolic ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, Voranol EP 2001, the ethers of polyoxy allyl group alkyl oxide etc., polyoxyethylene oleic acid, polyoxyethylene oleate, the polyoxyethylene SUNSOFT Q-182S, the sorbitan laurate, sorbitan monostearate, sorbitan monooleate, Span-83, the polyoxyethylene monoacetate, the ester class of polyoxyethylene stearic acid ester etc., 2,4,7,9-tetramethyl--5-decine-4, the 7-glycol, 3,6-dimethyl-4-methyl isooctenylamine-3, the 6-glycol, 3, (for example day is believed サ one Off イ ノ one Le 104 that chemical company produces to the acetylene glycols of 5-dimethyl-1-hexin-3-alcohol etc., 105,82,465, オ Le Off イ Application STG etc.) etc.These ink formulations can be used alone or as a mixture.
Ink composite of the present invention can mix, stir above-mentioned each composition in any order and obtain.The ink composite that obtains filters with membrane filter etc. in order to remove the impurity that is mingled with.In addition, in order to regulate the tone of black, also can mix other pigment with various tones.At this moment, beyond diazonium compound, can use the pigment of black with other tone and yellow, scarlet, blue-greenish colour, other color with general formula of the present invention (1) expression.
Ink composite of the present invention can use in various fields, but be fit at notes use printing ink, water-based printing ink, information recording ink etc., the spray ink Printing of forming as containing this ink composite uses with printing ink and is particularly suitable for, and is compatibly used in spray ink Printing recording method described later.
In the spray ink Printing recording method, ink composite of the present invention can and be used with Yellow ink composition, scarlet ink composite, blue-greenish colour ink composite.Versicolor ink composite is injected container separately respectively.
Ink-jet printer of the present invention is the ink-jet printer that is seated in definite stationkeeping (filling) at the container that will contain ink composite of the present invention.
In the spray ink Printing recording method that can be suitable for, use contains above-mentioned ink composite and the spray ink Printing formed is being subjected to the enterprising line item of picture material with printing ink, but the printing ink nozzle that uses at this moment etc. is had no particular limits, can suitably select according to purpose, can use known method, for example, can use and utilize electrostatic attraction, the electric charge control mode that printing ink is spued, utilize the formula that the oozes OLRT mode (pressure pulsation mode) of the vibration pressure of piezoelectric element, with converting electrical signal is sound beams, be radiated on the printing ink, utilize radiation to press the sound ink-jetting style that printing ink is spued, heating printing ink forms bubble, utilize thermal inkjet-printing (バ Block Le ジ エ Star ト (the registered trademark)) mode of the pressure that produces etc.In addition, in above-mentioned spray ink Printing recording mode, comprise in the most modes that penetrate the lower concentration printing ink of the printing ink that is referred to as to take a picture of small volume, use the different most printing ink of the concentration that comes down to same tone, improve the mode of picture quality and use the mode of water white transparency printing ink.
Colouring agent of the present invention is with above-mentioned compound of the present invention or contains the painted object of ink composite of this compound, preferredly is to use ink composite of the present invention, the painted object by ink-jet printer.As the object that can be colored, the information transmission that can enumerate for example paper, film etc. with sheet, fiber and cloth (Mierocrystalline cellulose, nylon, wool etc.), leather, colored filter with base material etc.As information transmission sheet, the sheet that the surface is processed preferably is provided with ink-receiver layer particularly on the base material of paper, synthetic paper, film etc.In ink-receiver layer, by for example impregnation or coating cationic polymkeric substance on above-mentioned base material, in addition, together be coated in the surface of above-mentioned base material by hydrophilic polymer and be provided with porous silica, the inorganic particles that can absorb pigment in the printing ink such as alumina sol and special ceramics and polyvinyl alcohol and polyvinylpyrrolidone etc.The material that is provided with such ink-receiver layer is commonly called spray ink Printing dedicated paper (film), glossy paper (film) etc., for example, as representational commercially available product, ピ Network ト リ コ (Asahi Glass (strain) production) is arranged, プ ロ Off エ Star シ ヨ Na Le Off オ ト ペ one パ one, ス one パ one Off オ ト ペ one パ one, マ Star ト Off オ ト ペ one パ one (all being that Canon's (strain) produces), PM photography paper (gloss), PM マ Star ト paper (all being Seiko one Ai Pusheng (strain) production), プ レ ミ ア system プ ラ ス Off オ ト paper, プ レ ミ ア system glossy film, Off オ ト is with paper (be Japanese ヒ ユ one レ Star ト パ Star カ one De (strain) produce), Off オ ト ラ イ Network QP (Konica (strain) produces) etc.In addition, can certainly utilize common paper.
The water-soluble excellence of tris-azo compound of the present invention contains the ink composite of the present invention of this tris-azo compound, also not the crystallization after long-time the preservation separate out, rerum natura variation, colour-change etc., stability in storage is good.In addition, the record black ink liquid that contains tris-azo compound of the present invention, can be used as spray ink Printing record usefulness, Writing utensil equipped usefulness, present the high black of gradation of drop-out colour, anti-ozone gas, photostabilization, wet fastness and colour rendering excellence when on common paper and spray ink Printing dedicated paper, writing down.
Embodiment
Below, more specifically describe the present invention by embodiment, but the present invention there is not any qualification by following embodiment.In addition, having " part " and " % " to locate herein, is quality criteria during not special the record.In addition, carboxyl, sulfo group are represented with the form of free acid.
Embodiment 1-1
Make 20.1 parts of 2-amino-5-naphthols-1,7-disulfonic acid and 12.6 parts of Tosyl chlorides are with pH8.0～8.5,70 ℃ reaction after 1 hour, to under acidity, saltout, filter the compound of the 28.4 parts of formulas (4) that obtain in 300 parts of water, the limit after pH6.0～8.0 preparation limits dissolving, adding 18.7 part of 35% hydrochloric acid, is 0～5 ℃ with yellow soda ash, add 10.7 part of 40% sodium nitrite in aqueous solution carries out diazotization.
In this diazotization suspension liquid, be added on outstanding turbid 19.1 parts of 4-amino-5-hydroxyl naphthalene-1 in 200 parts of water, behind the liquid of 7-disulfonic acid, remain on 2.4～2.8 limits 10～20 ℃ of pH values with the yellow soda ash limit and stirred 12 hours solution.After the stirring, with the pH value with yellow soda ash be adjusted to 7.0～8.5, dissolving, obtain containing the solution of the Monoazo compound of formula (6).
14.4 parts of 4-N-methyl-p-nitroaniline-2-sodium sulfonates of dissolving in 150 parts of water carry out diazotization with 18.8 part of 35% hydrochloric acid of 0～5 ℃ of interpolation, 10.6 part of 40% sodium nitrite in aqueous solution therein.In the solution of the Monoazo compound of the formula (6) that obtains in containing with above-mentioned reaction, keeping the pH value of solution at 10～20 ℃, limit with yellow soda ash is that 8.0～9.0 limits drip this diazonium suspension liquid.After drip finishing, stirred 2 hours, saltout, filter, obtain containing the wet cake of formula (1-8) compound by adding sodium-chlor with 15～30 ℃, pH8.0～9.0.
The above-mentioned wet cake that obtains of dissolving in 400 parts of water, be heated to 70 ℃ after, the limit keeps pH value 10.5～11.0 limits stirring 1 hour with sodium hydroxide.Behind the cool to room temperature, regulating pH by 35% hydrochloric acid is 7.0～8.0, adds sodium-chlor and saltouts, filters, and obtains containing the wet cake of formula (1-9) compound.
In 100 parts of water, make pH 5.0～7.0 dissolve 11.0 parts of 4-anisidine-2-sulfonic acid by adding sodium hydroxide, therein, with 0～5 ℃ add 15.8 part of 35% hydrochloric acid, 9.6 part of 40% sodium nitrite in aqueous solution carries out diazotization.The wet cake that in 300 parts of water, will contain the above-mentioned formula that obtains (1-9) compound, regulate pH with the sodium hydroxide limit and be 8.0～9.0, in the dissolved solution of limit, keeping the pH value of solution at 15～30 ℃, limit with yellow soda ash is that 8.0～9.0 limits drip this diazonium suspension liquid.After drip finishing, after stirring and coupled reaction was finished in 3 hours with 15～30 ℃, pH8.0～9.0, add sodium-chlor and saltout, filter.The wet cake that obtains of dissolving in 220 parts of water adds 300 parts of methyl alcohol and carries out crystallization and separate out, filter.Behind the wet cake that dissolving obtains in 150 parts of water, after adding 35% hydrochloric acid, being adjusted to the pH value below 0.5, dissolve again by adding lithium hydroxide.In this solution, undertaken by adding 200 parts of methyl alcohol and 50 parts of 2-propyl alcohol that crystallization is separated out, filtered, drying, obtain the compound (compound N in the table 2 is o.1) of 38.0 parts of formulas of the present invention (11).Maximum absorption wavelength (λ in the water of this compound
Max) be 595nm, the solubleness in the water is more than the 100g/l.
Embodiment 1-2
11.0 parts of 4-anisidine-2-sulfonic acid of embodiment 1-1 are changed to beyond 11.7 parts of 5-sulfo group anthranilic acids, to obtain the compound of 36.2 parts of formulas of the present invention (12) (compound N in the table 2 o.2) with the same method of embodiment 1-1.Maximum absorption wavelength is 591nm in the water of this compound, and the solubleness in the water is more than the 100g/l.
Embodiment 1-3
11.0 parts of 4-anisidine-2-sulfonic acid of embodiment 1-1 are changed to beyond the amino terephthalic acids of 9.8 parts of 2-, to obtain the compound of 30.4 parts of formulas of the present invention (13) (compound N in the table 2 o.3) with the same method of embodiment 1-1.Maximum absorption wavelength is 590nm in the water of this compound, and the solubleness in the water is more than the 100g/l.
Embodiment 1-4
11.0 parts of 4-anisidine-2-sulfonic acid of embodiment 1-1 are changed to beyond 11.7 parts of 5-sulphonamide anthranilic acids, to obtain the compound of 31.8 parts of formulas of the present invention (14) (compound N in the table 2 o.4) with the same method of embodiment 1-1.Maximum absorption wavelength is 591nm in the water of this compound, and the solubleness in the water is more than the 100g/l.
Embodiment 1-5
11.0 parts of 4-anisidine-2-sulfonic acid of embodiment 1-1 are changed to beyond 12.9 parts of 4-N-methyl-p-nitroaniline-2-sodium sulfonates, to obtain the compound of 37.8 parts of formulas of the present invention (15) (compound N in the table 2 o.5) with the same method of embodiment 1-1.Maximum absorption wavelength is 594nm in the water of this compound, and the solubleness in the water is more than the 100g/l.
Embodiment 1-6
11.0 parts of 4-anisidine-2-sulfonic acid of embodiment 1-1 are changed to beyond 12.4 parts of 5-(N-methyl sulfamyl) anthranilic acid, to obtain the compound of 32.3 parts of formulas of the present invention (16) (compound N in the table 2 o.9) with the same method of embodiment 1-1.Maximum absorption wavelength is 592nm in the water of this compound, and the solubleness in the water is more than the 100g/l.
Embodiment 1-7
11.0 parts of 4-anisidine-2-sulfonic acid of embodiment 1-1 are changed to 18.8 parts of 3-amino-7-nitro-naphthalenes-1, beyond the 5-sodium disulfonate, to obtain the compound of 30.9 parts of formulas of the present invention (17) (compound N in the table 2 o.20) with the same method of embodiment 1-1.Maximum absorption wavelength is 591nm in the water of this compound, and the solubleness in the water is more than the 100g/l.
Embodiment 1-8～1-12
(A) printing ink to manufacture
Mix following each composition, prepare ink composite of the present invention, then, filter, remove impurity by the membrane filter of 0.45 μ m.In addition, water uses ion exchanged water.Add water, lithium hydroxide, make the pH of ink composite become 8.0～10.0.
Table 6
| Each compound that obtains with the foregoing description | 5.0 part |
| Glycerine | 5.0 part |
| Urea | 5.0 part |
| The N-N-methyl-2-2-pyrrolidone N- | 4.0 part |
| Virahol | 3.0 part |
| Butylcarbitol | 2.0 part |
| Tensio-active agent (サ one Off イ ノ one Le 105, a day letter chemical company produce) | 0.1 part |
| Water+lithium hydroxide | 75.9 part |
| Add up to | 100.0 part |
In table 6, so-called each compound that obtains with the foregoing description represents that respectively embodiment 1-8 is that the compound of formula (11), the compound that embodiment 1-9 is formula (12), the compound that embodiment 1-10 is formula (13), compound, the embodiment 1-12 that embodiment 1-11 is formula (14) are the compounds of formula (15).PH during preparation printing ink is formulated as 8～10 with lithium hydroxide.This aqueous ink composition does not produce precipitate and separate when storing, in addition, even the variation that does not also produce rerum natura after long-time the preservation.
(B) spray ink Printing
Use the above-mentioned ink composite that obtains respectively, by ink-jet printer (trade(brand)name, Canon Inc.'s production, BJ-S630), carry out the spray ink Printing record of 3 kinds of paper of common paper (Canon Inc., LBP PAPER LS-500), special-purpose glossy paper A (Canon Inc.'s production, プ ロ Off エ Star シ ヨ Na Le Off オ ト ペ one パ one PR-101) and special-purpose glossy paper B (Seiko Epson Corporation's production, PM photography paper (gloss) KA420PSK).
During printing, reflection density if can access a few stage tones construction drawing picture pattern like that, and the black that obtains employed intermediate color is printed thing.During printing because using grey scale pattern, so, in this light-colored part, can not and be used in yellow, blue-greenish colour, the wine-colored liquid that respectively writes down beyond the black recording liquid.In the test method of following record, in the gradation of drop-out colour of the project of using the colour examining machine to estimate was estimated, when measuring the reflection density D value of printing thing, this D value was used the highest part.In addition, when the mensuration of the light fastness test of the project of similarly using the colour examining machine to estimate, ozone resistance test, the printing thing reflection density D value use before the test is partly measured near the tone of 1.0 values.
(C) evaluation of document image
The document image that produces about aqueous ink composition of the present invention is estimated 3 of the tonal variation after the concentration behind gradation of drop-out colour, the light fastness test and tonal variation, the anti-ozone gas test etc.In addition, anti-ozone gas test, anti-moisture test are only tested special-purpose glossy paper A, B.This result of expression in table 7.Test method is as follows.
In addition, a part of test film is not put into the evaluation test machine and take care of, then, the test film of " before the test " of usefulness is judged in test as an illustration.
(1) gradation of drop-out colour evaluation
The color-tone concentration of document image uses Gretag Macbeth SpectroEye (production of GRETAG company) to measure, and calculates gradation of drop-out colour D value.Below represent judgment standard.
Zero common paper: 1.2≤D glossy paper: 2.2≤D
△ common paper: 1.0≤D＜1.2 glossy papers: 1.9≤D＜2.2
* common paper: D＜1.0 glossy papers: D＜1.9
(2) light fastness test
Use xenon weather meter Ci4000 (production of ATLAS company), the illumination with 0.36W/ square metre on test film was shone 50 hours.After the off-test, use the aberration (△ E) of above-mentioned chromatic measuring system determination test front and back and the decrement of color-tone concentration.Judgement is carried out with following benchmark.
Zero △ E: less than 5, residual rate is more than 90%
△ △ E and residual rate have only any one can not satisfy zero condition
* △ E:5 is above, residual rate is less than 90%
(3) anti-ozone gas test
As the test film of anti-ozone gas test usefulness, each is prepared, and 2 tests in 3 hours are used and each printing sample of 6 hours test usefulness.Use ozone weather meter (production of ス ガ trier company), place printing sample down for 24 ℃ in 40ppm ozone concn, humidity 60%RH, temperature.In each printing sample, 1 place 3 hours, in addition 1 placed 6 hours.After the off-test, use the △ E (aberration) of said determination systems measurement test front and back and the decrement of color-tone concentration.Judgement is carried out with following benchmark.
Zero test period 3 hours, △ E are less than 10, and test period 6 hours, △ E are less than 20
△ test period 3 hours, △ E are more than 10, and perhaps, test period 6 hours, △ E are more than 20
* test period 3 hours, △ E are more than 10, and test period 6 hours, △ E are more than 20
Comparative example 1-1
Object as a comparison as the water-soluble ink-jet printing pigment, uses 1 the pigment (following formula (18)) of the table 1-1 of patent documentation 1, to form the ink composition that makes up oil with the same printing ink of embodiment 1-8.The result of the gradation of drop-out colour evaluation of the document image that table 7 expression obtains, photostabilization evaluation, anti-ozone gas evaluation.
Comparative example 1-2
Similarly, object as a comparison, as the water-soluble ink-jet printing pigment, the pigment AN-250 (following formula (19)) of embodiment 1 explanation of using at patent documentation 3 is to form the ink composition that makes up oil with the same printing ink of embodiment 1-8.The result of the gradation of drop-out colour evaluation of the document image that table 7 expression obtains, photostabilization evaluation, anti-ozone gas evaluation.
Table 7
| Gradation of drop-out colour | Photostabilization | Anti-ozone gas | ||
| Embodiment 1-8 (formula (11)) | Common paper | ○ | ○ | |
| Special-purpose glossy paper A | ○ | ○ | ○ | |
| Special-purpose glossy paper B | ○ | ○ | ○ | |
| Embodiment 1-9 (formula (12)) | Common paper | ○ | ○ | - |
| Special-purpose glossy paper A | ○ | ○ | ○ | |
| Special-purpose glossy paper B | ○ | ○ | ○ | |
| Embodiment 1-10 (formula (13)) | Common paper | ○ | ○ | - |
| Special-purpose glossy paper A | ○ | ○ | △ | |
| Special-purpose glossy paper B | ○ | ○ | ○ | |
| Embodiment 1-11 (formula (14)) | Common paper | ○ | ○ | - |
| Special-purpose glossy paper A | ○ | ○ | ○ | |
| Special-purpose glossy paper B | ○ | ○ | ○ | |
| Embodiment 1-12 (formula (15)) | Common paper | ○ | ○ | - |
| Special-purpose glossy paper A | ○ | ○ | ○ | |
| Special-purpose glossy paper B | ○ | ○ | ○ | |
| Comparative example 1-1 (formula (18)) | Common paper | ○ | ○ | - |
| Special-purpose glossy paper A | ○ | × | × | |
| Special-purpose glossy paper B | ○ | ○ | △ | |
| Comparative example 1-2 (formula (19)) | Common paper | ○ | ○ | - |
| Special-purpose glossy paper A | ○ | × | × | |
| Special-purpose glossy paper B | ○ | ○ | × | |
As shown in Table 7, contain the ink composite gradation of drop-out colour height of tris-azo compound of the present invention, compare anti-ozone gas, photostabilization excellence with black dyes (comparative example) in the past.
Embodiment 2-1
(1) makes 20.1 parts of 2-amino-5-naphthols-1,7-disulfonic acid and 12.6 parts of Tosyl chlorides are with pH8.0～8.5,70 ℃ reaction after 1 hour, to under acidity, saltout, filter the compound of the 28.4 parts of following formulas (4) that obtain in 300 parts of water, the limit after pH6.0～8.0 preparation limits dissolving, adding 18.7 part of 35% hydrochloric acid, is 0～5 ℃ with yellow soda ash, add 10.7 part of 40% sodium nitrite in aqueous solution carries out diazotization.
In this diazotization suspension liquid, be added on outstanding turbid 19.1 parts of 4-amino-5-hydroxyl naphthalene-1 in 200 parts of water, behind the liquid of 7-disulfonic acid, remain on 2.4～2.8 limits 10～20 ℃ of pH values with the yellow soda ash limit and stirred 12 hours solution.After the stirring pH value is adjusted to 7.0～8.5 dissolvings with yellow soda ash, obtains containing the solution of the Monoazo compound of following formula (6).
(2) 14.4 parts of 4-N-methyl-p-nitroaniline-2-sodium sulfonates of dissolving in 150 parts of water carry out diazotization with 18.8 part of 35% hydrochloric acid of 0～5 ℃ of interpolation, 10.6 part of 40% sodium nitrite in aqueous solution therein.In the solution of the Monoazo compound of the formula (5) that obtains in containing with above-mentioned reaction, keeping the pH value of solution at 10～20 ℃, limit with yellow soda ash is that 8.0～9.0 limits drip this diazonium suspension liquid.After drip finishing, stirred 2 hours, saltout, filter, obtain containing the wet cake of formula (1-8) compound by adding sodium-chlor with 15～30 ℃, pH8.0～9.0.
The above-mentioned wet cake that obtains of dissolving in 400 parts of water, be heated to 70 ℃ after, the limit keeps pH value 10.5～11.0 limits stirring 1 hour with sodium hydroxide.Behind the cool to room temperature, regulating pH by 35% hydrochloric acid is 7.0～8.0, adds sodium-chlor and saltouts, filters, and obtains containing the wet cake of following formula (1-9) compound.
(3) in 70 parts of water, make pH 5.0～7.0 dissolve 12.2 parts of 2-amino-benzenes-1 by adding sodium hydroxide, the 4-disulfonate sodium, therein with 0～5 ℃ add 12.7 part of 35% hydrochloric acid, 8.0 part of 40% sodium nitrite in aqueous solution carries out diazotization.The wet cake that in 300 parts of water, will contain the above-mentioned formula that obtains (1-9) compound, regulating pH with the sodium hydroxide limit is in 8.0～9.0 limit dissolved solution, keeping the pH value of solution at 15～30 ℃, limit with yellow soda ash is that 8.0～9.0 limits drip this diazonium suspension liquid.After drip finishing, after stirring and coupled reaction was finished in 3 hours with 15～30 ℃, pH8.0～9.0, add sodium-chlor and saltout, filter.The wet cake that dissolving obtains in 200 parts of water carries out crystallization by 150 parts of methyl alcohol of interpolation and 350 parts of 2-propyl alcohol and separates out, filters.Repeating 2 times should operation, the filter cake that drying obtains, obtains the compound of 45.0 parts of formulas of the present invention (2-10).Maximum absorption wavelength (λ in the water of this compound
Max) be 592nm, in addition, be more than the 120g/l to the solubleness of water (ammonium alkalescence).
Embodiment 2-2
(A) printing ink to manufacture
Mix in the following table 8 record each composition, prepare ink composite of the present invention, filter, remove impurity by the membrane filter of 0.45 μ m.In addition, water uses ion exchanged water.Add water, ammonium hydroxide, make the pH of ink composite become 8.0～10.0.
Table 8
| The compound that obtains with the foregoing description 2-1 | 5.0 part |
| Glycerine | 5.0 part |
| Urea | 5.0 part |
| The N-N-methyl-2-2-pyrrolidone N- | 4.0 part |
| Virahol | 3.0 part |
| Butylcarbitol | 2.0 part |
| Tensio-active agent (サ one Off イ ノ one Le 105, a day letter chemical company produce) | 0.1 part |
| Water+ammonium hydroxide | 75.9 part |
| Add up to | 100.0 part |
This aqueous ink composition does not produce precipitate and separate when storing, in addition, even the variation that does not also produce rerum natura after long-time the preservation.
(B) spray ink Printing
Use the above-mentioned ink composite that obtains respectively, by ink-jet printer (trade(brand)name, Canon Inc.'s production, BJ-S630), carry out the spray ink Printing record of common paper (Canon Inc., LBP PAPER LS-500), special-purpose glossy paper PR (Canon Inc.'s production, プ ロ Off エ Star シ ヨ Na Le Off オ ト ペ one パ one PR-101) and 3 kinds of paper of special-purpose glossy paper PM (Seiko Epson Corporation's production, PM photography paper (gloss) KA420PSK).
During printing, reflection density if can access a few stage tones construction drawing picture pattern like that, and the black that obtains employed intermediate color is printed thing.During printing because using grey scale pattern, so, can not and with black recording liquid yellow, blue-greenish colour, the wine-colored liquid that respectively writes down in addition.In the test method of following record, in the gradation of drop-out colour of the project of using the colour examining machine to estimate was estimated, when measuring the reflection density D value of printing thing, this D value was used the highest part.In addition, when the mensuration of the light fastness test of the project of similarly using the colour examining machine to estimate, ozone resistance test, the printing thing reflection density D value use before the test is partly measured near the tone of 1.0 values.
Use this printing ink, every day, 1 month printing was implemented on each 10 common paper ground, can not produce ground such as the style of calligraphy characterized by hollow strokes and keep good printing.
(C) evaluation of document image
The document image that produces about aqueous ink composition of the present invention is estimated 3 of the tonal variation after the change in concentration behind gradation of drop-out colour, the light fastness test, the anti-ozone gas test etc.In addition, anti-ozone gas test is only tested special-purpose glossy paper PR, PM.This result of expression in table 9.Test method is as follows.In addition, a part of test film is not put into the evaluation test machine and keeping, then, the test film of " before the test " of usefulness is judged in test as an illustration.
(1) gradation of drop-out colour evaluation
The color-tone concentration of document image uses GRETAGSPM50 (production of GRETAG company) to measure, and calculates gradation of drop-out colour D value.Below represent judgment standard.
Zero common paper: 1.2≤D glossy paper: 2.0≤D
△ common paper: 1.0≤D＜1.2 glossy papers: 1.8≤D＜2.0
* common paper: D＜1.0 glossy papers: D＜1.8
(2) light fastness test
Use xenon weather meter Ci4000 (production of ATLAS company), the illumination with 0.36W/ square metre on printing sample was shone 50 hours.After the off-test, use the residual rate of the color-tone concentration of above-mentioned chromatic measuring system determination test front and back.Judgement is carried out with following benchmark.
Zero residual rate: more than 95%
△ residual rate: less than 95%, more than 90%
* residual rate: less than 90%
(3) anti-ozone gas test
Use ozone weather meter (productions of ス ガ trier company), under 24 ℃ of 40ppm ozone concns, humidity 60%RH, temperature with printing sample placement 6 hours.After the off-test, use the △ E (aberration) of said determination systems measurement test front and back.Judgement is carried out with following benchmark.
Zero test period 6 hours, △ E are less than 15
More than △ test period 6 hours, the △ E15, less than 30
* test period 6 hours, more than the △ E30
(D) solubleness
Take by weighing dyestuff, the aqueous solution of the various concentration of preparation 120,100,80,60g/l.Water uses ion exchanged water, utilizes ammoniacal liquor to regulate pH9～9.5.Its normal temperature in ultrasonic bath was handled 5 minutes.Dropping point on Japan filter paper No.131, solubleness is judged on the surface after seeing drying.Dropping point evenly, do not observe the dissolving that is judged as of insolubles.Dropping point is inhomogeneous, observe being judged as of insolubles does not dissolve.Table 9 ecbatic.
Comparative example 2-1
Object as a comparison as the water-soluble ink-jet printing pigment, uses 1 the pigment (following formula (18)) of the table 1-1 of patent documentation 1, to form the ink composition that makes up oil with the same printing ink of embodiment 2-2.The result of the gradation of drop-out colour evaluation of table 9 expression solubleness and the document image that obtains, photostabilization evaluation, anti-ozone gas evaluation.
Comparative example 2-2
Similarly, object as a comparison as the water-soluble ink-jet printing pigment, uses the pigment AN-250 (following formula (19)) of explanation in the embodiment 1 of patent documentation 3, to form the ink composition that makes up oil with the same printing ink of embodiment 2-2.The result of the gradation of drop-out colour evaluation of table 9 expression solubleness and the document image that obtains, photostabilization evaluation, anti-ozone gas evaluation.
Table 9
| Solubleness (g/l) | Gradation of drop-out colour | Photostabilization | Anti-ozone gas | ||
| Embodiment 2-2 (formula (2-10)) | 120 | ||||
| Common paper | ○ | ○ | - | ||
| Special-purpose glossy paper PR | ○ | ○ | △ | ||
| Special-purpose glossy paper PM | ○ | ○ | ○ | ||
| Comparative example 2-1 (formula (18)) | Below 60 | ||||
| Common paper | ○ | △ | - | ||
| Special-purpose glossy paper PR | ○ | △ | × | ||
| Special-purpose glossy paper PM | ○ | ○ | △ | ||
| Comparative example 2-2 (formula (19)) | 60 | ||||
| Common paper | ○ | △ | - | ||
| Special-purpose glossy paper PR | ○ | △ | × | ||
| Special-purpose glossy paper PM | ○ | ○ | × | ||
As shown in Table 9, contain the ink composite gradation of drop-out colour height of diazonium compound of the present invention, compare, photostabilization, anti-ozone gas excellence with comparative example 2-1, comparative example 2-2.In addition, the solubleness height of tris-azo compound of the present invention, high density printing ink that can design stability.
Embodiment 3-1
11.0 parts of 4-anisidine-2-sulfonic acid of embodiment 1-1 are changed to beyond the amino m-phthalic acids of 9.8 parts of 5-, to obtain the compound of 31.1 parts of formulas of the present invention (3-1) (the No.24 compound in the table 5) with the same method of embodiment 1-1.Maximum absorption wavelength is 591nm in the water of this compound, and the solubleness in the water is more than the 100g/l.
Embodiment 3-2
14.4 parts of 4-N-methyl-p-nitroaniline-2-sodium sulfonates of embodiment 1-1 are changed to 14.4 parts of 2-N-methyl-p-nitroaniline-4-sodium sulfonates and 11.0 parts of 4-anisidine-2-sulfonic acid are changed to beyond the amino m-phthalic acids of 9.8 parts of 5-, to obtain the compound of 29.0 parts of formulas of the present invention (3-2) (the No.26 compound in the table 5) with the same method of embodiment 1-1.Maximum absorption wavelength is 597nm in the water of this compound, and the solubleness in the water is more than the 100g/l.
Embodiment 3-3～3-4
(A) printing ink to manufacture
Mix in the following table 10 record each composition, prepare ink composite of the present invention, filter, remove impurity by the membrane filter of 0.45 μ m.In addition, water uses ion exchanged water.Add water, ammonium hydroxide, make the pH of ink composite become 8～9.
Table 10
| The compound that obtains with the foregoing description | 5.0 part |
| Glycerine | 5.0 part |
| Urea | 5.0 part |
| The N-N-methyl-2-2-pyrrolidone N- | 4.0 part |
| Virahol | 3.0 part |
| Butylcarbitol | 2.0 part |
| Tensio-active agent (サ one Off イ ノ one Le 105, a day letter chemical company produce) | 0.1 part |
| Water+ammonium hydroxide | 75.9 part |
| Add up to | 100.0 part |
In table 10, the so-called compound that obtains with the foregoing description represents that respectively embodiment 3-3 is that compound, the embodiment 3-4 of formula (3-1) is the compound of formula (3-2).This aqueous ink composition does not produce precipitate and separate when storing, in addition, even the variation that does not also produce rerum natura after long-time the preservation.
(B) spray ink Printing
Use the above-mentioned ink composite that obtains respectively, by ink-jet printer (trade(brand)name, Canon Inc.'s production, BJ-S630), carry out the ink-vapor recording of common paper (Canon Inc., LBP PAPER LS-500), special-purpose glossy paper PR (Canon Inc.'s production, プ ロ Off エ Star シ ヨ Na Le Off オ ト ペ one パ one PR-101) and 3 kinds of paper of special-purpose glossy paper PM (Seiko Epson Corporation's production, PM photography paper (gloss) KA420PSK).
During printing, reflection density if can access a few stage tones construction drawing picture pattern like that, and the black that obtains employed intermediate color is printed thing.During printing because using grey scale pattern, so, in this light-colored part, can not and be used in yellow, blue-greenish colour, the wine-colored liquid that respectively writes down beyond the black recording liquid.In the test method of following record, in the gradation of drop-out colour of the project of using the colour examining machine to estimate was estimated, when measuring the reflection density D value of printing thing, this D value was used the highest part.In addition, when the mensuration of the light fastness test of the project of similarly using the colour examining machine to estimate, ozone resistance test, the printing thing reflection density D value use before the test is partly measured near the tone of 1.0 values.
(C) evaluation of document image
The document image that produces about aqueous ink composition of the present invention is estimated 3 of the tonal variation after the change in concentration behind gradation of drop-out colour, the light fastness test, the anti-ozone gas test etc.In addition, anti-ozone gas test is only tested special-purpose glossy paper PR, PM.This result of expression in table 11.Test method is as follows.In addition, a part of test film is not put into the evaluation test machine and keeping, then the test film of " before the test " of usefulness is judged in test as an illustration.
(1) gradation of drop-out colour evaluation
The color-tone concentration of document image uses GRETAGSPM50 (production of GRETAG company) to measure, and calculates gradation of drop-out colour D value.Below represent judgment standard.
Zero common paper: 1.2≤D glossy paper: 2.0≤D
△ common paper: 1.0≤D＜1.2 glossy papers: 1.8≤D＜2.0
* common paper: D＜1.0 glossy papers: D＜1.8
(2) light fastness test
Use xenon weather meter Ci4000 (production of ATLAS company), the illumination with 0.36W/ square metre on printing sample was shone 50 hours.After the off-test, use the residual rate of the color-tone concentration of above-mentioned chromatic measuring system determination test front and back.Judgement is carried out with following benchmark.
Zero residual rate: more than 95%
△ residual rate: less than 95%, more than 90%
* residual rate: less than 90%
(3) anti-ozone gas test
Use ozone weather meter (productions of ス ガ trier company), under 24 ℃ of 40ppm ozone concns, humidity 60%RH, temperature with printing sample placement 6 hours.After the off-test, use the △ E (aberration) of said determination systems measurement test front and back.Judgement is carried out with following benchmark.
Zero test period 6 hours, △ E are less than 15
More than △ test period 6 hours, the △ E15, less than 30
* test period 6 hours, more than the △ E30
Comparative example 3-1
Object as a comparison as the water-soluble ink-jet printing pigment, uses 1 the pigment (following formula (18)) of the table 1-1 of patent documentation 1, to form the ink composition that makes up oil with the same printing ink of embodiment 3-3.The result of the gradation of drop-out colour evaluation of the document image that table 11 expression obtains, photostabilization evaluation, anti-ozone gas evaluation.
Comparative example 3-2
Similarly, object as a comparison, as the water-soluble ink-jet printing pigment, the pigment AN-250 (following formula (19)) of embodiment 1 explanation of using at patent documentation 3 is to form the ink composition that makes up oil with the same printing ink of embodiment 3-3.The result of the gradation of drop-out colour evaluation of the document image that table 11 expression obtains, photostabilization evaluation, anti-ozone gas evaluation.
Table 11
| Gradation of drop-out colour | Photostabilization | Anti-ozone gas | ||
| Embodiment 3-3 (formula (3-1)) | Common paper | ○ | ○ | - |
| Special-purpose glossy paper PR | ○ | ○ | △ | |
| Special-purpose glossy paper PM | ○ | ○ | ○ | |
| Embodiment 3-4 (formula (3-1)) | Common paper | ○ | ○ | - |
| Special-purpose glossy paper PR | ○ | ○ | △ | |
| Special-purpose glossy paper PM | ○ | ○ | ○ | |
| Comparative example 3-1 (formula (18)) | Common paper | ○ | △ | - |
| Special-purpose glossy paper PR | ○ | △ | × | |
| Special-purpose glossy paper PM | ○ | ○ | △ | |
| Comparative example 3-2 (formula (19)) | Common paper | ○ | △ | - |
| Special-purpose glossy paper PR | ○ | △ | × | |
| Special-purpose glossy paper PM | ○ | ○ | × | |
As shown in Table 11, contain the ink composite gradation of drop-out colour height of tris-azo compound of the present invention, compare anti-ozone gas, photostabilization excellence with black dyes (comparative example) in the past.
Embodiment 4-1
In 100 parts of water, being become by interpolation sodium hydroxide is pH5.0～7.0,11.0 parts of 4-anisidine-2-sulfonic acid of dissolving, carries out diazotization with 15.8 part of 35% hydrochloric acid of 0～5 ℃ of interpolation, 9.6 part of 40% sodium nitrite in aqueous solution therein.The wet cake limit that to contain the compound of the formula (1-9) that the foregoing description 1-1 obtains in 300 parts of water is formulated as with sodium hydroxide in pH8.0～9.0, the limit dissolved solution, with 15～30 ℃, keep 8.0～9.0 limits to drip this diazonium suspension liquid on the pH value limit of solution with lithium hydroxide.After drip finishing, stirred 3 hours with 15～30 ℃, pH8.0～9.0, coupled reaction is finished after, saltout, filter by adding lithium chloride.The wet cake that dissolving obtains in 300 parts of water, crystallization is separated out, is filtered by adding 600 parts of 2-propyl alcohol.Again in 250 parts of water behind the wet cake that obtains of dissolving, by adding 600 parts of 2-propyl alcohol crystallization separate out, filter, drying, obtain the compound (compound N in the table 2 is o.1) of formula of the present invention (11).Maximum absorption wavelength (λ in the water of this compound
Max) be 595nm, the solubleness in the water is more than the 100g/l.
Industrial applicibility
The ink composite that contains trisazo compound of the present invention can be used as inkjet printing record with, the Writing utensil equipped dyeing, painted that is used for paper, cloth with black ink liquid.
Claims (14)
1. tris-azo compound or its salt with following formula (a 1) expression,
(in the formula (1), R
1With R
2Represent independently respectively hydrogen atom, halogen atom, cyano group, carboxyl, sulfo group, sulfamyl, N-alkyl amino sulfonyl, N-phenyl amino alkylsulfonyl, phosphate, nitro, acyl group, urea groups, can be with hydroxyl or (C
1～C
4) (C that replaces of alkoxyl group
1～C
4) alkyl, can be with hydroxyl, (C
1～C
4) (the C of alkoxyl group, sulfo group or carboxyl substituted
1～C
4) alkoxyl group or amide group, A represent phenyl or naphthyl (wherein, these phenyl and naphthyl also can with halogen atom, cyano group, carboxyl, sulfo group, the sulfamyl that can replace with alkyl or phenyl, phosphate, nitro, acyl group, urea groups, can be with hydroxyl or (C
1～C
4) (the C that replaces of alkoxyl group
1～C
4) alkyl, can be with hydroxyl, (C
1～C
4) (the C of alkoxyl group, sulfo group or carboxyl substituted
1～C
4) alkoxyl group or acyl amino replacement).)
2. tris-azo compound as claimed in claim 1 or its salt, formula (1) is with following formula (2) expression,
(in the formula (2), R
1Expression carboxyl, sulfo group or (C
1～C
4) alkoxyl group, R
2Expression hydrogen atom or sulfo group, R
3Expression carboxyl, sulfo group or (C
1～C
4) alkoxyl group, R
4Expression hydrogen atom, halogen atom, carboxyl, sulfo group, nitro, (C
1～C
4) alkoxyl group, sulfamyl or N-(C
1～C
4) alkyl amino sulfonyl, R
5Expression hydrogen atom, carboxyl or sulfo group).
3. tris-azo compound as claimed in claim 2 or its salt, in formula (2), R
1Relatively azo-group is connected 2, nitro and is connected 4, R
2Be connected 5, R
3Azo-group is connected 2, R relatively
4Be connected 4, R
5Be connected 5 or 6.
4. tris-azo compound as claimed in claim 3 or its salt, in formula (2), R
3Be carboxyl or sulfo group, R
4Be carboxyl, sulfo group, sulfamyl, N-(C
1～C
4) alkyl amino sulfonyl, nitro, (C
1～C
4) alkoxyl group, R
5Be hydrogen atom or carboxyl, R
3Azo-group is connected 2, R relatively
4Be connected 4, R
5Be connected 5.
5. tris-azo compound as claimed in claim 1 or its salt, formula (1) is with following formula (2 ') expression,
(in the formula (2 '), R
1Expression carboxyl or sulfo group, R
2The expression hydrogen atom, R
6Expression sulfo group or nitro, R
7Expression hydrogen atom or sulfo group).
6. tris-azo compound as claimed in claim 5 or its salt, the R in the formula (2 ')
1Relatively the nitro that is connected on 2, phenyl of azo-group is connected 4, with R
6With R
7In the naphthyl that replaces, azo-group is 1 or 2 of naphthyl, R
6At 5 or 6, R
7At 7 or 8.
7. tris-azo compound or its salt with following formula (2-1) expression.
8. as any described tris-azo compound or its salt of claim 1～7, salt is lithium salts, sodium salt, sylvite, ammonium salt or with the ammonium salt of general formula (3) expression,
(in the formula (3), Z
1, Z
2, Z
3, Z
4Represent hydrogen atom, alkyl, hydroxyalkyl or hydroxy alkoxy alkyl respectively independently).
9. an ink composite is characterized in that containing at least a any described tris-azo compound or its salt as claim 1～8.
10. an ink-jet printer loads the container that contains the described ink composite of claim 9.
11. the described ink composite of claim 9 is used in a spray ink Printing recording method.
12. a spray ink Printing recording method, the material that is recorded in the inkjet printing methods as claimed in claim 11 is an information transmission sheet.
13. spray ink Printing recording method as claimed in claim 12 is characterized in that the information transmission contains porousness white inorganics with sheet.
14. a colouring agent is painted by any described tris-azo compound or its salt of claim 1～8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP403311/2003 | 2003-12-02 | ||
| JP2003403311 | 2003-12-02 | ||
| JP292599/2004 | 2004-10-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1886467A true CN1886467A (en) | 2006-12-27 |
Family
ID=37584040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480035579 Pending CN1886467A (en) | 2003-12-02 | 2004-11-26 | Trisazo compound, ink composition, and colored object |
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| Country | Link |
|---|---|
| CN (1) | CN1886467A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911510A (en) * | 2012-10-25 | 2013-02-06 | 上海贝通色彩科技有限公司 | Ink-jet dye compound and preparation method thereof |
| CN107087414A (en) * | 2014-11-17 | 2017-08-22 | Dfi化学有限公司 | Black trisazo dyes and preparation method and application |
-
2004
- 2004-11-26 CN CN 200480035579 patent/CN1886467A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911510A (en) * | 2012-10-25 | 2013-02-06 | 上海贝通色彩科技有限公司 | Ink-jet dye compound and preparation method thereof |
| CN102911510B (en) * | 2012-10-25 | 2014-05-28 | 上海贝通色彩科技有限公司 | Ink-jet dye compound and preparation method thereof |
| CN107087414A (en) * | 2014-11-17 | 2017-08-22 | Dfi化学有限公司 | Black trisazo dyes and preparation method and application |
| CN114656799A (en) * | 2014-11-17 | 2022-06-24 | 朗盛德国有限责任公司 | Black trisazo dye and preparation method and application thereof |
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Open date: 20061227 |