CN1223282A - Dye mixtures and the use thereof - Google Patents
Dye mixtures and the use thereof Download PDFInfo
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- CN1223282A CN1223282A CN 98127161 CN98127161A CN1223282A CN 1223282 A CN1223282 A CN 1223282A CN 98127161 CN98127161 CN 98127161 CN 98127161 A CN98127161 A CN 98127161A CN 1223282 A CN1223282 A CN 1223282A
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Abstract
The invention relates to dye mixtures comprising at least one dye of formula (1), together with at least one dye of formula (2). The dye mixtures are suitable for dyeing or printing natural or synthetic polyamide fibre materials, especially in combination with other dyes and especially from short liquors. The dye mixture is distinguished by generally good properties, especially good uptake and good solubility. Wherein R1, R2, R3, R4 and R5 are defined in the specification.
Description
The present invention relates to the mixture of blue anthraquinone dyes, described dye mixture is suitable for by water-bath natural tynex or synthesizing polyamides textile fiber material being dyeed, has extraordinary colour fastness performance, especially light fastness, and will demonstrate good dye uptake when especially combining, especially when short liquor ratio with other dyestuff.
The invention still further relates to: utilize the blue anthraquinone dyes mixture, natural tynex or synthetic polyamide fiber are carried out three primary color dyeing or method for printing.Particularly, painted being characterised in that in different concentration that obtains all can produce uniform color and constant tone.
Therefore, the present invention relates to dye mixture, described mixture comprises: the dyestuff of at least a structural formula (1),
R in the formula
1Be hydrogen, C
1-C
4Alkyl or C
1-C
4Alkoxyl group, R
2Be hydrogen, C
1-C
4Alkyl; And the dyestuff of at least a structural formula (2),
R in the formula
3Be hydrogen, C
1-C
4Alkyl or C
1-C
4Alkoxyl group, R
4Be hydrogen, C
1-C
4Alkyl, R
5Be the C that is cut off or do not cut off by oxygen by oxygen
2-C
6Alkyl, precondition are to work as R
2, R
3And R
4Be hydrogen and R
5During for ethyl, R
1It is not methyl.
Be used for R
1, R
2, R
3And R
4C
1-C
4Alkyl example be selected from respectively: methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl and isobutyl-, especially methyl and ethyl, preferably methyl.
Be used for R
1And R
3C
1-C
4The example of alkoxyl group is selected from respectively: methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy and isobutoxy, especially methoxyl group and oxyethyl group, preferably methoxyl group.
Be used for R
5C
2-C
6The example of alkyl is an ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, isobutyl-, amyl group and hexyl.Described alkyl group can be by oxygen at interval.As being had: methoxymethyl, ethoxyl methyl and 2-methoxy ethyl, especially methoxymethyl group by the example of oxygen alkyl group at interval.
Preferred R
1Be hydrogen, methyl or methoxy, especially hydrogen.
Preferred R
2Be hydrogen, methyl or ethyl, especially hydrogen.
Preferred R
3Be hydrogen, methyl or methoxy, especially hydrogen.
Preferred R
4Be hydrogen, methyl or ethyl, especially hydrogen.
Preferred R
5Be C
2-C
4Alkyl, especially propyl group or ethyl are more preferably ethyl.
Preferably, in the dye mixture, R
4And R
3Be selected from respectively: hydrogen, methyl or methoxy, R
2And R
4Be hydrogen, R
5Be C
2-C
4Alkyl.
Particularly preferably be, in the dye mixture, R
1, R
2, R
3And R
4Be hydrogen, R
5Be ethyl.
Dye mixture according to the present invention preferably comprises: in the total amount of structural formula (1) and (2) dyestuff, from 5-95 weight %, especially from 20-80 weight %, more preferably from the dyestuff of the structural formula (1) of 40-60 weight %.
The anthraquinone dye of structural formula (1) and (2) is known, maybe can be similar to known dyestuff and be prepared.For example, make the dyestuff of structural formula (1) and (2) by the compound reaction that makes 1-amino-4-bromo anthraquinone-2-sulfonic acid and structural formula (11) or (12)
R in the formula
1, R
2, R
3, R
4And R
5As above definition.Preferably, at alkali sodium bicarbonate for example, and catalyzer at for example 50-100 ℃, especially under 65-85 ℃ temperature, reacts in the aqueous solution for example under the existence of copper and cupric chloride mixture.
For example can prepare according to dye mixture of the present invention by each dyestuff is mixed.This mixing process is for example at suitable grinding machine, for example in ball mill or the nail formula pulverizer, or carries out in kneader or mixing machine.
For example also can prepare dye mixture by the moisture dye mixture of spraying drying.
In addition, also can prepare dye mixture of the present invention by being total to the synthetic method, described synthesis example altogether is as being: make the compound reaction of the compound and the structural formula (12) of 1-amino-4-bromo anthraquinone-2-sulfonic acid and aforesaid structural formula (11) simultaneously.
In addition, the invention still further relates to and utilize dye mixture of the present invention to natural tynex or synthetic polyamide fiber material dyes or method for printing, described dye mixture comprises the dyestuff of at least a structural formula (1) and the dyestuff of at least a structural formula (2).Suitable synthetic polyamide fiber material is for example polyamide 6 .6 or daiamid-6 fiber material, and suitable natural polyamide fiber material for example is a wool.Conventional dyeing or printing method all are applicable to dyeing of the present invention and printing method.
Wait to dye or the textile materials of stamp can be multiple finished form fiber for example, yarn, the form of fabric or knitted fabrics, especially carpet.
In addition, dye mixture of the present invention also is applicable to the dyeing according to short liquor ratio, for example is used for the successive staining or is used for intermittence or successive foam dyeing method.
Usually, dye mixture according to the present invention is characterised in that: have good performance, for example good solubility in cold soln, stability, with good retention,, and be attached to good homogeneous dye uptake on the multiple filamentary material especially with other dyestuff good mixing.
Utilize dye mixture of the present invention, dyeing or stamp that the method according to this invention is carried out is characterized in that: have good comprehensive performances, especially good wear resistance, moisture-proof lubricant nature, wet abrasive resistance and photostabilization, especially good ozone resistance.
In dye mixture of the present invention, the dyestuff of structural formula (1) and (2) can exist with the form of its free sulfonic, and perhaps preferred form with its salt exists, for example with an alkali metal salt, the form of alkaline earth salt or ammonium salt, perhaps the form with organic amine salt exists.Concrete example comprises: sodium salt, lithium salts and ammonium salt, and the salt of trolamine.
Dye mixture of the present invention also comprises other additive, for example sodium-chlor, dispersion agent or dextrin usually.
In addition, dye liquor or seal slurry also can comprise other additive, wetting agent for example, defoamer, levelling agent or influence the reagent of textile materials performance, for example softening agent, be used for fire-retardant finish or anti-soil, anti-water and oil-resisting additive, and water-based softening agent and natural or synthetic thickening agent, for example alginate and ether of cellulose.
Dye mixture according to the present invention is particularly suitable for dyeing and the stamp, especially dyeing and the stamp that carries out according to the three primary colors principle that combine and carry out with other dyestuff.Three primary colors mechanism is interpreted as: obtaining the required amount of desired tone, and yellow or orange to suitable selection, red and blue dyes carries out other color matching.
In addition, the invention still further relates to and utilize dye mixture of the present invention that natural tynex or synthetic polyamide fiber material are carried out three primary color dyeing or method for printing, dye mixture of the present invention comprises: the dyestuff of the dyestuff of at least a structural formula (1) and at least a structural formula (2), with at least a orchil and at least a yellow or orange dye, mixture of the present invention comprises the dyestuff of at least a structural formula (1) and the dyestuff of at least a structural formula (2) is arranged by above-mentioned advantage especially.
When in three primary color dyeing or printing method, being used as orchil, preferably have the dyestuff of a kind of structural formula (3) at least according to dyestuff of the present invention:
R in the formula
6Be hydrogen; Halogen; Replace or the last C that replaces
1-C
8Alkyl, on phenyl ring by C
1-C
4Alkyl replaces or unsubstituted benzenesulfonyl or methylsulfonyl phenoxy base, cyclohexyl oxygen carbonyl amino; C
2-C
4Alkanoyl amido; Unsubstituted benzamido or halogenated benzamido on phenyl ring; Or
, R in the formula
9Be C
1-C
8Alkyl or by C
1-C
4Alkyl replaces or unsubstituted phenyl or cyclohexyl, R
10Be hydrogen or C
1-C
8Alkyl, perhaps radicals R
9And R
10Connected nitrogen-atoms forms azepines ring, R together
7Be hydrogen, halogen, C
1-C
8Alkyl, or C
2-C
4Alkanoyl amido, R
8Be hydrogen, halogen or the phenoxy group that does not replace or replace.
R
6, R
7And R
8Be respectively for example fluorine as halogen, chlorine or bromine, preferably chlorine or bromine.
Be used for R
6, R
7, R
9And R
10C
1-C
8The example of alkyl is respectively methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl and octyl group.As C
1-C
8The R of alkyl
6Can replace, for example by halogen, for example chlorine or fluorine, especially fluorine replace.Wherein the example that can mention is a trifluoromethyl group.
Be used for R
6And R
7C
2-C
4The example of alkanoyl amido is respectively kharophen, propionamido and butyrylamino.
Radicals R
8As phenoxy group is unsubstituted, is perhaps for example replaced by following groups on phenyl ring, and described group is: C
1-C
4Alkyl, for example methyl or ethyl, C
1-C
4Alkoxyl group, for example methoxy or ethoxy; C
2-C
4Alkanoyl amido, for example kharophen or propionamido; Hydroxyl; Sulfo group or halogen be fluorine for example, chlorine or bromine.
When being used as orchil in three primary color dyeing or printing method, particularly, dyestuff according to the present invention has the dyestuff of a kind of structural formula (3) at least, R in the formula
6Be halogen; The C unsubstituted or halogen replaces
1-C
4Alkyl is preferably trifluoromethyl, or
, R in the formula
9Be C
1-C
4Alkyl, phenyl or cyclohexyl, preferred cyclohexyl, R
10Be hydrogen or C
1-C
4Alkyl is preferably methyl or ethyl, especially methyl, perhaps radicals R
9And R
10Connected nitrogen-atoms forms azepines ring, R together
7Be hydrogen, halogen, C
2-C
4Alkanoyl amido is preferably hydrogen or halogen, R
8Be hydrogen, on halogen or the phenyl ring by halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group or by C
2-C
4The phenoxy group that alkanoyl amido does not replace or replaces is preferably hydrogen or phenyl ring and is replaced or unsubstituted phenoxy by halogen.
When especially being used as the orchil of structural formula (3) in three primary color dyeing or printing method, dyestuff of the present invention has the dyestuff of structural formula (4):
R in the formula
7Be hydrogen or halogen.
When being used as yellow or orange dye in three primary color dyeing or printing method, dyestuff of the present invention preferably has the dyestuff of at least a structural formula (5) or (6):
R in the formula
11Be hydrogen, C
1-C
4Alkyl or the phenyl that does not replace or replace, R
12For moieties is substituted or unsubstituted C
1-C
4Alkoxyl group, or 4, the dibasic N-of 6-(1,3,5-triazines-2-yl) amino, or N-C
1-C
4Alkyl-N-(1,3,5-triazines-2-yl) amino group, R
13, R
14And R
15Be respectively hydrogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
2-C
4Alkanoyl amido, halogen or sulfo group, R
16Be hydrogen, C
1-C
4Alkyl, or in phenyl ring, be substituted or unsubstituted benzenesulfonyl.
As phenyl groups R
11Be for example to be replaced by following groups or unsubstituted, described group is C
1-C
4Alkyl, for example methyl or ethyl; C
1-C
4Alkoxyl group, for example methoxy or ethoxy; C
2-C
4Alkanoyl amido, for example kharophen or propionamido, hydroxyl, sulfo group, or halogen, for example fluorine, chlorine or bromine.
As being used for R
12N-(1,3,5-triazines-2-yl) amino, or N-C
1-C
4Alkyl-N-(1,3,5-triazines-2-yl) amino group is selected from the group that is replaced in the 4-and the 6-position of triazine ring by following group respectively, and described substituted radical is: halogen is fluorine or chlorine for example, hydroxyl; C
1-C
4Alkoxyl group, for example methoxy or ethoxy; C
1-C
4Alkylthio, for example thiomethyl or sulphur ethyl, amino; At moieties by hydroxyl, sulfo group, sulfato, carboxyl, C
2-C
4Alkanoyl amido is perhaps by C
1-C
4Alkoxyl group, methylamino-for example, ethylamino, the 2-hydroxyethylamino, 2-methoxyethyl amino, N-methyl-N-(2-sulfoethyl) amino, dimethylamino or diethylin replace or the single or N of unsubstituted N-, N-two-C
1-C
4Alkylamino, cycloalkyl ring is by C
1-C
4Alkyl replaces or unsubstituted C
5-C
7Naphthene amino, for example hexamethylene amino; Phenylamino or phenyl ring are by C
1-C
4Alkyl, C
1-C
4Alkoxyl group, carboxyl, C
2-C
4Alkanoyl amido, sulfo group or replaced or unsubstituted N-C by halogen
1-C
4Alkyl-N-phenylamino; Morpholino or piperidines-1-base.
Be used for R
11, R
13, R
14, R
15And R
16C
1-C
4The example of alkyl is respectively methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl.
Be used for R
12, R
13, R
14And R
15C
1-C
4The example of alkoxyl group is respectively methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert.-butoxy.As C
1-C
4The R of alkoxyl group
12Can be the group that moieties is for example replaced by following group, described group comprises: halogen is fluorine for example, chlorine or bromine; Hydroxyl; C
1-C
4Alkoxyl group is methoxy or ethoxy for example; Amino; N-list-C
1-C
4Alkylamino is methylamino-or ethylamino for example; N, N-two-C
1-C
4Alkylamino is dimethylamino or diethylin for example; C
2-C
4Alkanoyl amido is kharophen or propionamido for example; Carboxyl; Sulfo group or sulfato.For as C
1-C
4The R of alkoxyl group
12Group, the preferably group that replaced by sulfato of moieties substituted group, especially moieties.
Be used for R
13, R
14And R
15C
2-C
4The example of alkanoyl amido is respectively kharophen, propionamido and butyrylamino.
Radicals R as benzenesulfonyl
16For unsubstituted, the perhaps group that replaced by following group of phenyl ring for example, described substituting group comprises: C
1-C
4Alkyl, for example methyl or ethyl, C
1-C
4Alkoxyl group, for example methoxy or ethoxy; C
2-C
4Alkanoyl amido, for example kharophen or propionamido; Hydroxyl; Sulfo group or halogen, fluorine for example, chlorine or bromine.
When being used as yellow or orange dye in three primary color dyeing or printing method, dyestuff of the present invention preferably has the dyestuff of at least a structural formula (5) or (6): R wherein
11Be hydrogen, C
1-C
4Alkyl or by C
1-C
4Alkyl, C
1-C
4Alkoxyl group or replaced or unsubstituted phenyl by halogen; R
12For moieties replaces or unsubstituted C by hydroxyl or by sulfato
1-C
4Alkoxyl group, or the group of following structural formula
R in the formula
17And R
18Be respectively hydrogen or C
1-C
4Alkyl, R
19Be C
1-C
4Alkoxyl group, hydroxyl, halogen, the single or N of amino or N-, N-two-C
1-C
4Alkylamino; R
20For by hydroxyl, C
1-C
4Alkoxyl group, C
2-C
4Alkanoyl amido, carboxyl or replaced or unsubstituted C by sulfo group
1-C
4Alkyl, or by halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
2-C
4Alkanoyl amido or replaced by sulfo group or phenyl that the end replaces;
R
13And R
14Be respectively hydrogen or sulfo group, R
15Be hydrogen, C
1-C
4Alkyl, or C
1-C
4Alkoxyl group, R
16Be hydrogen or C
1-C
4Alkyl.
Be used for R
1, R
18And R
20C
1-C
4The example of alkyl is respectively: methyl, and ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the sec-butyl and the tertiary butyl are preferably methyl and ethyl.As C
1-C
4The R of alkyl
17And R
18Methyl more preferably.As C
1-C
4The R of alkyl
20Can be replaced by following group, described substituting group comprises: hydroxyl; C
1-C
4Alkoxyl group, for example methoxy or ethoxy; C
2-C
4Alkanoyl amido, for example ethanoyl or propionamido; Carboxyl; Sulfo group or sulfato.For being used as C
1-C
4The R of alkyl
20, the group that the preferred group that replaces, especially sulfo group replace.
Be used for R
19C
1-C
4The example of alkoxyl group is methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert.-butoxy, preferred methoxyl group and oxyethyl group.
Be used for R
19N-single-or N, N-two-C
1-C
4The example of alkylamino is methylamino-, ethylamino, dimethylamino and diethylin.
As phenyl groups R
20For unsubstituted, or replaced by following group, described substituting group for example comprises: halogen is fluorine for example, chlorine or bromine; C
1-C
4Alkyl, for example methyl or ethyl; C
1-C
4Alkoxyl group, for example methoxy or ethoxy; C
2-C
4Alkanoyl amido, for example kharophen or propionamido; Or sulfo group.For R as phenyl
20, preferred group, especially the sulfo group phenyl group that replaces.
In three primary color dyeing of the present invention or printing method particularly preferred embodiment, be used as the dyestuff that has a kind of structural formula (5) at least of yellow or orange dye: R in the formula
11Be hydrogen, C
1-C
4Alkyl or phenyl, especially methyl or phenyl, R
12The C that is replaced by sulfato for moieties
1-C
4Alkoxyl group, the group of especially 2-sulfato oxyethyl group, or following structural formula
R in the formula
18Be C
1-C
4Alkyl, especially methyl, R
19Be C
1-C
4Alkoxyl group, especially methoxyl group, R
20C for the sulfo group replacement
1-C
4Alkyl, especially 2-sulfo group ethyl.
In three primary color dyeing of the present invention or printing method particularly preferred embodiment,, have the dyestuff of a kind of structural formula (7) and (8) at least as the yellow or the orange dye of structural formula (6):
R in the formula
15Be C
1-C
4Alkyl, especially methyl, preferably, dyestuff, especially dye mixture that dye mixture comprises at least a structural formula (7) and structural formula (8) comprise wherein R
15Be bonded on the azo group in the ortho position and be the dyestuff of the structural formula (7) of methyl, and the dyestuff of structural formula (8).
The preferred embodiment of three primary color dyeing of the present invention or printing method comprises uses following dyestuff: as the dyestuff of at least a structural formula of orchil (3), R in the formula
6Be halogen, trifluoromethyl or
R in the formula
9Be cyclohexyl, R
10Be methyl, R
7Be hydrogen or halogen, R
8Be hydrogen or halogenated phenoxy;
As the dyestuff of yellow or at least a structural formula of orange dye (5), R in the formula
11Be hydrogen, C
1-C
4Alkyl or phenyl, especially methyl or phenyl; R
12Be moieties by sulfato, the C that the group of especially 2-sulfato oxyethyl group, or following structural formula replaces
1-C
4Alkoxyl group,
R in the formula
18Be C
1-C
4Alkyl, especially methyl, R
19Be C
1-C
4Alkoxyl group, especially methoxyl group, R
20C for the sulfo group replacement
1-C
4Alkyl, especially 2-sulfo group ethyl, the dyestuff of perhaps at least a structural formula (7) and (8), wherein, R
15Be C
1-C
4Alkyl, especially methyl; And the dye mixture that comprises the dyestuff of the dyestuff of structural formula (1) and structural formula (2), wherein R
1, R
2, R
3And R
4Be hydrogen, and R
5Be C
2-C
4Alkyl, especially ethyl.
The especially preferred embodiment of three primary color dyeing of the present invention or printing method comprises uses following dyestuff: as the dyestuff of at least a structural formula (4) of orchil, R in the formula
7For hydrogen or halogen with as the wherein R that comprises of yellow or orange dye
15Be bonded on the azo group in the ortho position and be the dyestuff of the structural formula (7) of methyl, and the dye mixture of the dyestuff of structural formula (8); And the dye mixture that comprises the dyestuff of the dyestuff of structural formula (1) and structural formula (2), wherein R
1, R
2, R
3And R
4Be hydrogen, and R
5Be ethyl.
Be used for the dyestuff of three primary color dyeing of the present invention or printing method or be the form of its free sulfonic, perhaps preferably exist with the form of its salt.
Suitable salt for example is an alkali metal salt, alkaline earth salt or ammonium salt, or organic amine salt.The example that can mention has sodium salt, lithium salts, and sylvite and ammonium salt, or one-, two-or the salt of three-thanomin.
Be used for dyestuff of the present invention and can also comprise other additive, for example sodium-chlor or dextrin.
Three primary color dyeing of the present invention or printing method can be used for conventional dyeing or printing method.Dewater and dyestuff beyond, dye liquor or seal slurry also can comprise other additive, wetting agent for example, defoamer, levelling agent, or influence the reagent of textile materials performance, for example softening agent is used for fire-retardant finish or anti-soil, anti-water and oil-resisting additive, and water-based softening agent and natural or synthetic thickening agent, for example alginate and ether of cellulose.
In addition, three primary color dyeing of the present invention or printing method also are applicable to the dyeing according to short liquor ratio, for example are used for the successive staining or are used for intermittence or successive foam dyeing method.
The consumption that is used for the various dyestuffs of dye bath or seal slurry can change in big scope by desirable depth of shade according to the present invention; Usually, in dyestuff or seal slurry, proved the advantageously consumption of 0.01-15% already.
Dyeing preferably under the pH of 3-7, is especially carried out under the pH of 4-7.Liquor ratio can be selected in very wide scope, for example from 1: 5 to 1: 50, preferably from 1: 5 to 1: 30.Dyeing is especially carried out under 80-105 ℃ temperature preferably at 70 to 110 ℃.
In three primary color dyeing or printing method, the dyestuff that is used for the inventive method is characterised in that, even the uniform color that is produced under different concentration, good retention, the good color tone unchangeability, good fastness and solvability, especially well bonding properties.
Be applicable to for example wool of natural polyamide material according to three primary color dyeing of the present invention or printing method, be particularly useful for synthesizing polyamides the material for example dyeing or the stamp of polyamide 6 or polyamide 66, and be applicable to the dyeing or the stamp of wool and synthesizing polyamides mixed goods or yarn.
Described textile materials can be multiple finished form, fiber for example, and yarn, fabric or knitted fabrics especially are the form of carpet.
The present invention has obtained having the level dyeing of comprehensive fastness performance, especially good wear resistance, wet fastness, wet abrasive resistance and photostabilization.
In addition, the invention still further relates to spissated aqueous dye solutions, described solution comprises: in the gross weight of dye liquor from 5-50 weight %, especially from 10-50 weight %, preferably from the dye mixture of 20-50 weight %, described dye mixture comprises: the dyestuff of the dyestuff of at least a structural formula (1) and at least a structural formula (2), preferred R
1, R
2, R
3, R
4And R
5Definition as mentioned above.
In addition, concentrated aqueous dye solutions according to the present invention also comprises following additive, for example urea, N-Methyl pyrrolidone, hexanolactam or polyoxyethylene glycol.In addition, the material that also comprises mould fungus inhibition and/or bacterial growth according to concentrated aqueous solution of the present invention.
Dye liquor of the present invention demonstrates good preservation stability, and is suitable for for example-5 storing the several months to+40 ℃ temperature.
In addition, dye liquor of the present invention also demonstrates good stability in hard water, and can dilute with any desirable ratio water, for example is used to prepare dye liquor, and the precipitation of dissolving dye can not occur.
In the following example, all umbers are weight part.Temperature is degree centigrade.Relation between relation between weight part and the parts by volume and gram and the cubic centimetre is identical.
Embodiment 1 is the preparation dye mixture, and this dye mixture comprises: be equivalent to structural formula (101) and (102) compound, be the free acid attitude one of them dyestuff and be equivalent to structural formula (103) compound, be the dyestuff of free acid attitude; A), obtain being referred to as below 100 parts the mixture of dye mixture A with 50 parts of the dyestuffs of structural formula (101) and 50 parts of uniform mixing in mixing machine of dyestuff of structural formula (103);
B), obtain being referred to as below 100 parts the mixture of dye mixture B with 50 parts of the dyestuffs of structural formula (102) and 50 parts of uniform mixing in mixing machine of dyestuff of structural formula (103);
Embodiment 2
1 part of level dyeing auxiliary agent (based on the condenses of high fatty amine and oxyethane) is added in 2000 parts of softening waters in room temperature.With 4 parts of SODIUM PHOSPHATE, MONOBASIC and 0.6 part of Sodium phosphate dibasic the pH value of water-bath is adjusted to 6 then.Then, the mixture with four kinds of dyestuffs as described below is added into wherein; Described dye mixture is: 0.11 part is equivalent to dyestuff structural formula (104), that be the free acid attitude, 0.11 part is equivalent to dyestuff structural formula (105), that be the free acid attitude, 0.1 part is equivalent to dyestuff structural formula (106), that be the free acid attitude and 0.11 part of dye mixture A.Then, 100 parts of polyamide 6 .6 filamentary materials (helanca tricot) are placed resulting dye liquor, and dye bath is heated to about 96 ℃ through 45 minutes.Insulation is 45-60 minute under this temperature, cools the temperature to 70 ℃ then, and takes out painted material, and water washs and carries out drying then.The result obtains the printed fabrics of hunchbacked brown accent.
Embodiment 3: according to embodiment 2 described processing, different is to replace 0.11 part of dye mixture A with 0.11 part of dye mixture B, and the result has obtained the polyamide fabric that same quilt is dyed hunchbacked brown accent.
Embodiment 4 and 5: according to embodiment 2 described processing, different is replaces the orchil of 0.1 part of structural formula (106) with 0.1 part of following dye mixture, and described dye mixture comprises: 20 parts are equivalent to structural formula (107), are the compound that the dyestuff of free acid attitude and 80 parts are equivalent to one of the structural formula as providing in the following table 1, the dyestuff that is the free acid attitude; The result has obtained the polyamide fabric that same quilt is dyed hunchbacked brown accent.
Table 1 embodiment dyestuff
Embodiment 6-9: according to embodiment 2 described processing, different is replaces the orchil of 0.1 part of structural formula (106) with 0.1 part of following dye mixture, and described dye mixture comprises: 80 parts are equivalent to structural formula (108), are the compound that the dyestuff of free acid attitude and 20 parts are equivalent to one of the structural formula as providing in the following table 2, the dyestuff that is the free acid attitude; The result has obtained the polyamide fabric that same quilt is dyed hunchbacked brown accent.Table 2 embodiment dyestuff
Embodiment 10 and 11: according to embodiment 2 described processing, different is compound, the dyestuff substitute structure formula (104) that is the free acid attitude and the yellow dyes of (105) that usefulness is equivalent to one of structural formula as providing in the following table 3, and the result has obtained the polyamide fabric that same quilt is dyed hunchbacked brown accent.The various dyestuffs that provide in following table 3, to be dyed filamentary material, its consumption is 0.22 part.
Table 3:
The embodiment dyestuff
Preparation example: 880 parts of water are placed the sulfonation flask, and add 382 parts of 1-amino-4-bromo-anthraquinone-2-sulfonic acid, 82 parts of 3-propionamido--aniline and 75 parts of 3-acetylaminohydroxyphenylarsonic acid aniline.After adding 201 parts of sodium bicarbonates, with this mixture heating up to 75 ℃.Under constant agitation, add 1 part of copper and 1 part of cupric chloride then.After 6 hours, reaction is finished.Add the hydrochloric acid of 2180 parts of water and 345 part 32%.Stirred 30 minutes at 80 ℃, and products therefrom is carried out suction strainer through suction filter, 25 parts of hydrochloric acid warm water solution that are used in 800 parts of water are washed.The result obtains being still 780 parts of moistening products, and this product comprises the dyestuff of structural formula (101) and (103), and its weight ratio is 50: 50.
Embodiment 12: the concentrated aqueous solutions for preparation structural formula (101) and (103) dyestuff is suspended in the wet product that obtains in 28.5 parts of preparation examples in 31.1 parts of softening waters.Then, under the 7-7.2pH value, with 10.1 parts of trolamines this dye paste that neutralizes.Then, add 30.0 parts of ε-Ji Neixianan and 0.3 portion of commercially available biocides, and make the dye liquor clarification by filtration.This formula for dye liquor composed as follows:
34.8 the dye mixture of weight % structural formula (101) and (103) is the form of the salt of trolamine, wherein the weight ratio of dyestuff as mentioned above,
30.0 weight % ε-Ji Neixianan,
0.3 the biocides that weight % is commercially available and
34.9 weight % water.
Resulting prescription can be-5 to+40 ℃ of stably stored, and polyamide fabric is dyed blue cast.
Embodiment 13: 1 part of level dyeing auxiliary agent (based on the condenses of high fatty amine and oxyethane) is added in 2000 parts of softening waters in room temperature.With 4 parts of SODIUM PHOSPHATE, MONOBASIC and 0.6 part of Sodium phosphate dibasic the pH value of water-bath is adjusted to 6 then.Then, the mixture with four kinds of dyestuffs as described below is added into wherein; Described dye mixture comprises: 0.11 part is equivalent to dyestuff structural formula (104), that be the free acid attitude, 0.11 part is equivalent to dyestuff structural formula (105), that be the free acid attitude, 0.1 part is equivalent to the dye mixture A of dyestuff structural formula (108), that be the free acid attitude and 0.11 part of embodiment 1.Then, 100 parts of polyamide 6 .6 filamentary materials (helanca tricot) are placed resulting dye liquor, and dye bath is heated to about 96 ℃ through 45 minutes.Insulation is 45-60 minute under this temperature, cools the temperature to 70 ℃ then, and takes out painted material, and water washs and carries out drying then.The result obtains the printed fabrics of hunchbacked brown accent.
Embodiment 14: according to embodiment 13 described processing, different is to obtain the dye mixture A that dye mixture B replaces 0.11 part of embodiment 1 with 0.11 part of embodiment 1, and the result has obtained the polyamide fabric that same quilt is dyed hunchbacked brown accent.
The staining procedure I
With 10 parts of polyamide 6 .6 fabrics comprise 2 grams per liter ammonium acetates and with the water dye liquor (500 part) of acetate with pH regulator to 5 in dye.According to the ratio of the liquid formulations of embodiment 12, count 2% with fibre weight.At 98 ℃ dyeing times from 30-90 minute.Take out painted polyamide 6 .6 then, and wash and drying with conventional method.
The staining procedure II
With 10 parts of polyamide 6 .6 fabrics comprise 1 grams per liter monosodium phosphate and with the water dye liquor (500 part) of Di-Sodium Phosphate with pH regulator to 6 in dye.According to the ratio of the liquid formulations of embodiment 12, count 2% with fibre weight.At 98 ℃ dyeing times from 30-90 minute.Take out painted polyamide 6 .6 then, and wash and drying with conventional method.
Dyeing step mule III
10 parts of wools are dyeed in 500 parts of water dye liquors.In the weight of fiber, this solution comprises 2% liquid formulations according to embodiment 12, and 5% calcines the acetate (80%) of saltcake and 2%.At 98 ℃ dyeing times from 30-60 minute.
Claims (19)
1. dye mixture comprises: the dyestuff of at least a structural formula (1),
R in the formula
1Be hydrogen, C
1-C
4Alkyl or C
1-C
4Alkoxyl group, R
2Be hydrogen, C
1-C
4Alkyl; And the dyestuff of at least a structural formula (2),
R in the formula
3Be hydrogen, C
1-C
4Alkyl or C
1-C
4Alkoxyl group, R
4Be hydrogen, C
1-C
4Alkyl, R
5Be the C that is cut off or do not cut off by oxygen by oxygen
2-C
6Alkyl, precondition are to work as R
2, R
3And R
4Be hydrogen and R
5During for ethyl, R
1It is not methyl.
2. according to the dye mixture of claim 1, R wherein
1And R
3Be selected from respectively: hydrogen, methyl or methoxy, R
2And R
4Be hydrogen, R
5Be C
2-C
4Alkyl.
3. according to the dye mixture of claim 1 or 2, R wherein
1, R
2, R
3And R
4Be hydrogen, R
5Be ethyl.
4. according to each dye mixture of claim 1-3,, comprise, especially from the dyestuff of the structural formula (1) of 20-80 weight % from 5-95 weight % in the dyestuff total amount of structural formula (1) and (2).
5. one kind is dyeed or method for printing to natural or synthetic polyamide fiber material, and this method comprises that use is according to each dye mixture of claim 1-4.
6. according to the method for claim 5, this method comprise use according to claim 1-4 each dye mixture and other dyestuff.
7. be used for three primary color dyeing or method for printing according to claim 6, this method comprises use according to each dye mixture of claim 1-4, and at least a orchil and at least a yellow or orange dye.
8. according to the method for claim 7, this method comprises the dyestuff that uses at least a structural formula (3):
R in the formula
6Be hydrogen; Halogen; Replace or unsubstituted C
1-C
8Alkyl; On phenyl ring respectively by C
1-C
4Alkyl replaces or unsubstituted benzenesulfonyl or methylsulfonyl phenoxy base; Cyclohexyl oxygen carbonyl amino; C
2-C
4Alkanoyl amido; Unsubstituted benzamido or halogenated benzamido on phenyl ring; Or
, R in the formula
9Be C
1-C
8Alkyl or respectively by C
1-C
4Alkyl replaces or unsubstituted phenyl or cyclohexyl, R
10Be hydrogen or C
1-C
8Alkyl, perhaps radicals R
9And R
10Connected nitrogen-atoms forms azepines ring, R together
7Be hydrogen, halogen, C
1-C
8Alkyl, or C
2-C
4Alkanoyl amido, R
8Be hydrogen, halogen or the phenoxy group that does not replace or replace.
9. method according to Claim 8, wherein R
6Be halogen; The C unsubstituted or halogen replaces
1-C
4Alkyl, or
, R in the formula
9Be C
1-C
4Alkyl, phenyl or cyclohexyl, R
10Be hydrogen or C
1-C
4Alkyl, perhaps radicals R
9And R
10Connected nitrogen-atoms forms azepines ring, R together
7Be hydrogen, halogen, C
2-C
4Alkanoyl amido, R
8Be hydrogen, on halogen or the phenyl ring by halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group or by C
2-C
4The phenoxy group that alkanoyl amido does not replace or replaces.
10. according to Claim 8 or 9 method, wherein R
6Be halogen, trifluoromethyl, or
, R in the formula Chinese style
9Be cyclohexyl, R
10Be methyl or ethyl, perhaps radicals R
9And R
10Connected nitrogen-atoms forms azepines ring, R together
7Be hydrogen or halogen, R
8For hydrogen or phenyl ring are replaced or unsubstituted phenoxy by halogen.
11. each method according to Claim 8-10, this method look are drawn together the orchil of the dyestuff of utilization structure formula (4) as structural formula (3):
R in the formula
7Be hydrogen and halogen.
12., comprise that at least a dyestuff with structural formula (5) or (6) is used as yellow or orange dye according to the method for claim 7:
R in the formula
11Be hydrogen, C
1-C
4Alkyl or the phenyl that does not replace or replace, R
12For moieties is substituted or unsubstituted C
1-C
4Alkoxyl group, or 4, the dibasic N-of 6-(1,3,5-triazines-2-yl) amino, or N-C
1-C
4Alkyl-N-(1,3,5-triazines-2-yl) amino group, R
13, R
14And R
15Be respectively hydrogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
2-C
4Alkanoyl amido, halogen or sulfo group, R
16Be hydrogen, C
1-C
4Alkyl, or in phenyl ring, be substituted or unsubstituted benzenesulfonyl.
13. according to the method for claim 12, wherein R
11Be hydrogen, C
1-C
4Alkyl, or replaced or unsubstituted phenyl by following groups, described group is C
1-C
4Alkyl, C
1-C
4Alkoxyl group, or halogen, R
12For moieties by hydroxyl or sulfato replace or the end replaces C
1-C
4Alkoxyl group, or the group of following structural formula
R in the formula
17And R
18Be respectively hydrogen or C
1-C
4Alkyl, R
19Be C
1-C
4Alkoxyl group, hydroxyl, halogen, the single or N of amino or N-, N-two-C
1-C
4Alkylamino, R
20For by hydroxyl, C
1-C
4Alkoxyl group, C
2-C
4Alkanoyl amido, carboxyl or replaced or unsubstituted C by sulfo group
1-C
4Alkyl, or by halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
2-C
4Alkanoyl amido or replaced or unsubstituted phenyl by sulfo group; R
13And R
14Be respectively hydrogen or sulfo group, R
15Be hydrogen, C
1-C
4Alkyl or C
1-C
4Alkoxyl group, R
16Be hydrogen or C
1-C
4Alkyl.
14. the method according to claim 12 or 13 comprises: the dyestuff of at least a structural formula (5) is used as yellow or orange dye, in the formula, R
11Be hydrogen, C
1-C
4Alkyl or phenyl, R
12For moieties by sulfato especially 2-sulfato oxyethyl group, or the C that replaces of the group of following structural formula
1-C
4Alkoxyl group,
R in the formula
18Be C
1-C
4Alkyl, especially methyl, R
19Be C
1-C
4Alkoxyl group, especially methoxyl group, R
20C for the sulfo group replacement
1-C
4Alkyl, especially 2-sulfo group ethyl.
15., comprise the yellow or the orange dye that the dyestuff of at least a structural formula (7) and (8) are used as structural formula (6) according to the method for claim 12 or 13:
R in the formula
15Be C
1-C
4Alkyl.
16., comprise wool or synthetic polyamide fiber material dyes or stamp according to each method of claim 5-15.
17., comprise synthetic polyamide fiber material dyeed or stamp according to the method for claim 16.
18. be used for wool or synthetic polyamide fiber material dyes or the purposes of stamp according to the dye mixture of claim 1.
19. a spissated aqueous dye solutions comprises: in the dye liquor gross weight from 5-50 weight %, according to each dye mixture of claim 1-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98127161 CN1223282A (en) | 1997-12-10 | 1998-12-09 | Dye mixtures and the use thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97810963.5 | 1997-12-10 | ||
| CN 98127161 CN1223282A (en) | 1997-12-10 | 1998-12-09 | Dye mixtures and the use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1223282A true CN1223282A (en) | 1999-07-21 |
Family
ID=5229854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98127161 Pending CN1223282A (en) | 1997-12-10 | 1998-12-09 | Dye mixtures and the use thereof |
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| Country | Link |
|---|---|
| CN (1) | CN1223282A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088078C (en) * | 2000-01-03 | 2002-07-24 | 海门市江滨化工二厂 | Improved process for preparing anthraquinone oxadiazole type reduced red |
| CN102604411A (en) * | 2012-01-19 | 2012-07-25 | 上海雅运纺织化工股份有限公司 | Synthesis and dyeing application of anthraquinone type blue acid dye compound |
| CN102604427A (en) * | 2012-01-19 | 2012-07-25 | 上海雅运纺织化工股份有限公司 | Anthraquinone blue acidic dye composition and dyeing application of composition on fiber |
| CN102604428A (en) * | 2012-01-19 | 2012-07-25 | 上海雅运纺织化工股份有限公司 | Anthraquinone type blue acidic dye composition and its application in fibers |
| CN104447431A (en) * | 2014-12-19 | 2015-03-25 | 江苏华尔化工有限公司 | Method of preparing 1,4-diaminoanthraquinone-2-sulfonic acid |
-
1998
- 1998-12-09 CN CN 98127161 patent/CN1223282A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088078C (en) * | 2000-01-03 | 2002-07-24 | 海门市江滨化工二厂 | Improved process for preparing anthraquinone oxadiazole type reduced red |
| CN102604411A (en) * | 2012-01-19 | 2012-07-25 | 上海雅运纺织化工股份有限公司 | Synthesis and dyeing application of anthraquinone type blue acid dye compound |
| CN102604427A (en) * | 2012-01-19 | 2012-07-25 | 上海雅运纺织化工股份有限公司 | Anthraquinone blue acidic dye composition and dyeing application of composition on fiber |
| CN102604428A (en) * | 2012-01-19 | 2012-07-25 | 上海雅运纺织化工股份有限公司 | Anthraquinone type blue acidic dye composition and its application in fibers |
| CN102604411B (en) * | 2012-01-19 | 2014-06-11 | 上海雅运纺织化工股份有限公司 | Synthesis and dyeing application of anthraquinone type blue acid dye compound |
| CN104447431A (en) * | 2014-12-19 | 2015-03-25 | 江苏华尔化工有限公司 | Method of preparing 1,4-diaminoanthraquinone-2-sulfonic acid |
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