CN1056636C - Dye composition and dyeing method using same - Google Patents

Dye composition and dyeing method using same Download PDF

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Publication number
CN1056636C
CN1056636C CN94117236A CN94117236A CN1056636C CN 1056636 C CN1056636 C CN 1056636C CN 94117236 A CN94117236 A CN 94117236A CN 94117236 A CN94117236 A CN 94117236A CN 1056636 C CN1056636 C CN 1056636C
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dyestuff
yellow
dyeing
general formula
dyes
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CN1103877A (en
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桧原利夫
关冈辽一
高桥阳介
中村升
清水完二
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Dystar Japan Ltd
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Dystar Japan Ltd
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Priority claimed from JP6054444A external-priority patent/JPH07238232A/en
Priority claimed from JP07971194A external-priority patent/JP3226707B2/en
Priority claimed from JP14382994A external-priority patent/JP3161906B2/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046Mixtures of two or more azo dyes
    • C09B67/0051Mixtures of two or more azo dyes mixture of two or more monoazo dyes

Abstract

To obtain a solid polyelectrolyte having a satisfactory film strength,a high ionic conductivity, and an excellent processability by using a composite comprising an electrolyte and a (co)polymer obtained from at least one specific compound. The electrolyte is made of a composite comprising a (co)polymer (a) and at least one electrolyte selected preferably from among alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts (e.g. LiCF3), the (co)polymer (a) being a polymer of at least one compound (b) selected from among 2-(meth)acryloyloxyethyl carbamates represented by the formula, CH2=C(R<1>)COO(CH2)2NHCOOR<2> (wherein R<1> us H or CH3 and R<2> is a linear, branched, or cyclic organic group which has one or more alkylene groups and may contain one or more elements other than C, H, and O) and/or a copolymer of the compound (b) with other monomer(s).

Description

Dye component and use the staining of this dye component
The present invention relates to reactive dye composition yellow chemically-reactive dye combinations and use the staining of this dye component.The orange series reaction dyestuff composition that the present invention also relates to the green reaction dye component that formed by the allotment of yellow reaction dyestuff and blue chemically-reactive dyes further, formed by yellow reaction dyestuff and red reactive dyes allotment and in this orange series dye component, add blue chemically-reactive dyes again after the brown serial reaction dyeing constituent that forms of modulation.The invention still further relates to yellow, redness and blue each composition the dyeing kinetics unanimity reaction dyestuff composition and use the staining of this dye component.
Chemically-reactive dyes is because it is bright and lustrous, tone abundant, and every fastness is good, and is used widely.But chemically-reactive dyes is owing to the difference of its reactive group kind, and dyeing kinetics there are differences.And the difference of structure also can produce the difference of dyeing kinetics.For example, the general formula of free acid shape (R-1)
Figure C9411723600041
(in the formula, R 0, R 1And R 2Expression hydrogen atom or C 1~C 3Alkyl, R 3Expression hydrogen atom, halogen atom or C 1~C 3Alkyl, X are represented-CH=CH 2,-C 2H 4OSO 3H or-C 2H 4The Cl yl)
The Vinyl-Sulfone Type red reactive dyes of expression is in the exhaustion dyeing method, and is little to the interdependence of inorganic salt, and photostabilization, fastness to chlorine are good.In addition, the general formula of free acid shape (R-2).
(in the formula, R 1, R 2And same meaning shown in X and the above-mentioned general formula (R-1), Y represents hydroxyl or X, W represent hydrogen atom, carboxyl, sulfonic group or-SO 2X base, m represent 0 or 1) the Vinyl-Sulfone Type red reactive dyes of expression is similarly in exhaustion dyeing, and little to the interdependence of inorganic salt, fastness to chlorine, enhancing (pile-on properties) are good.Therefore, make full use of these good characteristics, using primary red in the dyeing of form and aspect broadness has just become numerous users' requirement.
But the dyeing kinetics of this dyestuff is fast, for example, uses this orchil, for obtaining orange form and aspect, when the fusion yellow dyes dyes, though such as general formula (Y-1)
Figure C9411723600052
(in the formula, same meaning shown in X and the general formula (R-1))
Shown yellow reaction dyestuff is little to the interdependence of inorganic salt, photostabilization, and fastness to chlorine is good, but because dyeing kinetics is slower than orchil shown in above-mentioned general formula (R-1) and (R-2), carries out with tinctorial, and stained cloth is yellow from being changed to band redly.This is very disadvantageous to obtaining dyeing reproducibility.
Therefore, need the consistent with it yellow reaction dyestuff of exploitation dyeing kinetics, this is not limited in orange dyeing, in green dyeing and brown colouring, to the blue chemically-reactive dyes that uses with the yellow reaction dyestuff, also require the corresponding to dyestuff of selective staining speed or develop.
The present inventor has carried out various discussions for satisfying above-mentioned requirements, has finished the present invention.
The present invention is made of following content, that is, free acid shape by general formula (Y-1)
Figure C9411723600061
(in the formula, X represents-CH=CH 2,-C 2H 4OSO 3H or-C 2H 4Cl) Biao Shi yellow reaction dyestuff and free acid shape by general formula (Y-2)
Figure C9411723600062
(in the formula, X and above-mentioned shown in same meaning) expression the yellow reaction dyestuff or free acid shape by general formula (Y-3)
(in the formula, T represents amino or methyl, X and above-mentioned shown in same meaning) expression the yellow reaction dyestuff be major ingredient reactive dye composition yellow chemically-reactive dye combinations and by yellow reaction dyestuff shown in yellow reaction dyestuff shown in yellow reaction dyestuff shown in the above-mentioned general formula (Y-1) and the above-mentioned general formula (Y-2) or the above-mentioned general formula (Y-3) and free acid shape by following general formula (Y-4)
Figure C9411723600071
(in the formula, X and above-mentioned shown in same meaning) the yellow reaction constituent formed of the yellow reaction dyestuff of expression and the staining of using these reactive dye composition yellow chemically-reactive dye combinations.The present invention also is included in the general formula (B-1) of fusion free acid shape in the above-mentioned yellow reaction dye component
The general formula (B-2) of (in the formula, the same meaning shown in X and above-mentioned (Y-1)) and free acid shape
(in the formula, A represents phenylene, C 2~C 3Alkylidene group or C 2~C 3Alkylidene group oxygen base C 2~C 3Alkylidene group, R are represented hydrogen atom, C 1~C 3Alkyl, phenyl or A-SO 2X, X and above-mentioned shown in same meaning, Z represents chlorine atom, fluorine atom, hydroxyl, cyanogen amino, sulfo group ethylamino or sulfo group phenylamino) the green reaction dye component that forms of at least a kind of blue chemically-reactive dyes among the blue chemically-reactive dyes group of expression and the staining of using these reaction dyestuff compositions.
In addition, the present invention also is included in red reactive dyes shown in the general formula (R-1) of fusion free acid shape in the above-mentioned reactive dye composition yellow chemically-reactive dye combinations (in the formula, R 0, R 1And R 2Expression hydrogen atom or C 1~C 3Alkyl, R 3Expression hydrogen atom, halogen atom or C 1~C 3Alkyl, X are represented-CH=CH 2,-C 2H 4OSO 3H or-C 2H 4Cl) and/or red reactive dyes shown in the general formula (R-2)
(in the formula, R 1, R 2And the same meaning shown in X and the above-mentioned general formula (R-1), Y represents hydroxyl or X, W represent hydrogen atom, carboxyl, sulfonic group or-SO 2X, m represent 0 or 1)
Orange reaction dyestuff composition that forms and the staining of using these reaction dyestuff compositions.
The present invention also is included in brown reactive dye component that at least a kind of blue chemically-reactive dyes that fusion in the above-mentioned orange reaction dyestuff composition selects forms and the staining of using these reaction dyestuff compositions further from the group who is made of the blue chemically-reactive dyes shown in above-mentioned general formula (B-1) and (B-2).
Below, describe the present invention in detail.
In the above-mentioned general formula (B-2), the C that represents with R 1~C 3Alkyl has, for example methyl, ethyl, n-propyl, sec.-propyl.The C that represents with A 2~C 3Alkylidene group or C 2~C 3Alkylidene group oxygen base C 2~C 3Alkylidene group has, for example the inferior heptyl of ethylidene, propylidene, 3-oxa-pentylidene and 4-oxa-.
-A-SO 2The object lesson of X has β-(β-chloroethyl alkylsulfonyl) ethyl, γ-(β-chloroethyl alkylsulfonyl) propyl group, γ-(β-sulfuric acid ethylsulfonyl) propyl group, β-(vinylsulfonyl) ethyl, β-(β-(β-chloroethyl alkylsulfonyl) oxyethyl group) ethyl, γ-(γ-(β-sulfuric acid ethylsulfonyl) propoxy-) propyl group, β-(β-(vinylsulfonyl) oxyethyl group) ethyl etc.Wherein, be good with sulfuric acid second sulphonyl ethyl, sulfuric acid second sulphonyl propyl group and sulfuric acid second sulphonyl ethoxyethyl etc. especially.
In addition, when Z is fluorine, be phenylene as A, then dyeing kinetics is too fast, and is inadvisable.
In addition, among general formula (R-1) and (R-2), R 0, R 1, R 2And R 3The C of expression 1~C 3The example of alkyl has methyl, ethyl, n-propyl, sec.-propyl.R 3The halogen atom of expression has bromine atoms and chlorine atom.
A and-A-SO 2X can exemplify the group that exemplifies in above-mentioned (B-2), and preferred group similarly is subjected in (R-1) and (R-2) preferably in (B-2).
Dyestuff shown in general formula (Y-1)~(Y-4), (B-1), (B-2), (R-1) and (R-2) is all known, can be synthetic by known synthetic method.
Each chemically-reactive dyes that constitutes dye component of the present invention all exists with the form of free acid or its salt, but usually, and is as its salt, preferable with an alkali metal salt such as lithium salts, sodium salt, sylvite and calcium salt or alkaline earth salt.
Blending ratio and these dyestuffs of fusion of yellow in the dye component of the present invention, redness and blue each dyestuff, the blending ratio of each dyestuff is as follows when obtaining green colouring material constituent, orange dye constituent and brown based dye constituent.(reactive dye composition yellow chemically-reactive dye combinations)
When constituting reactive dye composition yellow chemically-reactive dye combinations by yellow reaction dyestuff shown in general formula (Y-1) and (Y-2), dyestuff accounts for 80~50% (weight) shown in the general formula (Y-1), dyestuff accounts for 20~50% (weight) shown in the general formula (Y-2), accounts for dyestuff shown in 80-60% (weight), the general formula (Y-2) with dyestuff shown in the general formula (Y-1) and accounts for 20~40% (weight) for good.
When constituting reactive dye composition yellow chemically-reactive dye combinations by dyestuff shown in general formula (Y-1), (Y-2) and (Y-4), in the 100 weight part mixtures that dyestuff shown in the general formula (Y-2) of dyestuff and 20~60% (weight) shown in the general formula (Y-1) of 80~40% (weight) is formed, dyestuff 5~30 weight parts shown in the fusion general formula (Y-4).Especially account for 50~60 weight parts with dyestuff shown in the general formula (Y-1), it is good that dyestuff shown in the general formula (Y-2) accounts for the blending ratio scope that dyestuff shown in 20~30 weight parts and the general formula (Y-4) accounts for 10~20 weight parts.
The mix proportions of yellow reaction dyestuff shown in general formula (Y-1) and (Y-3) accounts for dyestuff shown in 60~40% (weight) and the general formula (Y-3) with dyestuff shown in the general formula (Y-1), and to account for 40~60% (weight) scope be good.
By dye set yellowly reactive dye constituent shown in general formula (Y-1), (Y-3) and (Y-4) time, in per 100 weight part mixtures of forming by dyestuff shown in the general formula (Y-3) of dyestuff and 40~60% (weight) shown in the general formula (Y-1) of 60~40% (weight), the dyestuff shown in fusion 5~30 weight part general formulas (Y-4).More excellent three's blending ratio is, the yellow reaction dyestuff accounts for 45~55 weight parts shown in the general formula (Y-1), the yellow reaction dyestuff accounts for 25~35 weight parts shown in the general formula (Y-3), and the yellow reaction dyestuff accounts for 10~20 weight parts shown in the general formula (Y-4).(blue reaction dyestuff composition)
In reactive dye composition yellow chemically-reactive dye combinations, carry out fusion, during modulation green reaction dye component, use at least a kind of blue chemically-reactive dyes among the blue chemically-reactive dyes group shown in the general formula (B-1) and (B-2), preferred blue composition is the mixture of being made up of the blue chemically-reactive dyes shown in the general formula (B-2) of blue chemically-reactive dyes and 65~35% (weight) shown in the general formula (B-1) of 35~65% (weight).
In addition, blue chemically-reactive dyes shown in the general formula (B-1) is following general formula (B-1-1) and general formula (B-1-2)
Figure C9411723600111
Figure C9411723600121
(in the formula, X and above-mentioned shown in same meaning) shown in the mixture of blue chemically-reactive dyes, mixture by dyestuff shown in the general formula (B-1-2) of dyestuff and 40~5% (weight) shown in the general formula (B-1-1) of 60~95% (weight) is formed can produce extremely good effect in solvability with aspect the level-dyeing property of fiber.(green reaction dye component)
The ratio of the blue reactive dye of fusion is in the yellow reaction dyestuff, and with respect to yellow reaction dyestuff 100 weight parts, blue chemically-reactive dyes is 5~5000 weight parts, is good with 10~1000 weight parts.(orange reaction dyestuff composition)
The ratio of the yellow reaction dyestuff of fusion in red reactive dyes is, red reactive dyes with respect to 100 weight parts, binary and ternary reactive dye composition yellow chemically-reactive dye combinations all are 5~5000 weight parts, are good with 10~1000 weight parts especially wherein.(brown is reaction dyestuff composition)
With respect to 100 weight part red reactive dyes, the blended amount of binary and ternary reactive dye composition yellow chemically-reactive dye combinations all is 5~5000 weight parts, serve as preferred wherein with 10~1000 weight parts, and, the fusion total amount of blue chemically-reactive dyes is 5~5000 weight parts, serves as preferred with 10~1000 weight parts wherein.
In dye component of the present invention,, during other the reactive dye of red colour system, yellow system or blue system of fusion, in the scope of 10% (weight),, can freely select again the almost not influence of its characteristic as blended amount for the needs of matching colors.
Filamentary material as the object of staining of the present invention, at first can enumerate cellulosic fibre, particularly, can enumerate cotton, viscose rayon, copper rayon, fiber crops etc., these fibers and trevira, triacetate fiber, diacetate fiber, polyacrylonitrile fibre, tynex, so also applicable with the blending product of fibers such as wool, silk.
When using reaction dyestuff composition of the present invention that cellulosic fibre is carried out exhaustion dyeing, in the presence of alkali such as sodium bicarbonate, yellow soda ash, Quilonum Retard, sodium hydroxide, triethylamine and inorganic salt such as saltcake, salt, dye.At this moment the consumption of alkali be generally per 1 liter of dye bath with 10~30 the gram.The usage quantity of inorganic salt is advisable about restraining with per 1 liter of dye bath 30~50.
In addition, dyeing temperature is 40~80 ℃, is excellent with 50~60 ℃.After the dyeing, product dyed thereby soaped and wash processing, dry then.
And reaction dyestuff composition of the present invention is not only in exhaustion dyeing, and be applied to continuous dyeing, when rolling the volume cold-stacking dyeing, its dyeing kinetics unanimity, the scope of application is quite wide.
Below, in conjunction with the embodiments and comparative example, the present invention is specified.Only otherwise exceed its context, the present invention is not limited by these embodiment.Embodiment 1
Will be by following structural (Y-1-a)
Figure C9411723600131
Shown in reactive dye 0.03 gram and following structural (Y-3-a)
Figure C9411723600141
Shown in the dye component formed of reactive dye 0.01 gram be dissolved among 30 ℃ the water 170ml, add saltcake 10 grams, be modulated into dye bath.Cotton 10 grams are immersed wherein, after 25 minutes, add the aqueous sodium carbonate 30ml of 100 grams per liters, after 5 minutes,, be warming up to 60 ℃ with 1 ℃/minute speed heating 30 minutes in vibration under the same temperature with the vibration of oscillatory type dyeing machine.After 60 minutes, take out stained cloth, washing in this temperature dyeing, after the aqueous acetic acid neutralization of 2 grams per liters, washing, hot wash, in the Hostapal of 2 grams per liters CT-40 (registered trademark, HOECHST JAPAN company produces) soap is bathed, in 100 ℃, soaped 10 minutes, then washing, drying.Its result obtains the good yellow product dyed thereby of level-dyeing property.Embodiment 2-1~2-5
With dye well following structural (Y-4-a) shown in structural formula (Y-1-a) and (Y-3-a) among the embodiment 1 And following structural (Y-3-b) Shown in dyestuff by the amount of Table 1 fusion, use the method dyeing identical with embodiment 1, obtain the good yellow product dyed thereby of level-dyeing property.
Table 1
Embodiment No Dyestuff is formed (g)
〔Y-1-a〕 〔Y-3-a〕 〔Y-4-a〕 〔Y-3-b〕
2-1 2-2 2-3 2-4 2-5 0.4 0.06 0.1 0.08 0.23 0.2 0.03 0.06 - - - 0.01 0.03 - 0.09 - - - 0.05 0.16
Embodiment 3
Remove and change dyestuff shown in the structural formula (Y-1-a) among the embodiment 2-2 into following structural (Y-1-b)
Figure C9411723600152
Shown in outside the chemically-reactive dyes, press the dyeing of method shown in the embodiment 2-2.Its result obtains the good yellow product dyed thereby of level-dyeing property.Embodiment 4
Chemically-reactive dyes used among the embodiment 2-2 (Y-1-a), (Y-3-a) and (Y-4-a) are become its lithium salts separately, weigh 50 grams, 30 grams and 20 grams respectively, be dissolved in the 1000ml hot water, be cooled to 25 ℃, do not have dyestuff to separate out, keep the aqueous solution state of homogeneous.
This shows that this dye component has fabulous solubleness, and this characteristic shows that it is suitable for making the aqueous constituent of high density, and meaning can be by continuous dyeing, roll volume cold-stacking dyeing legal system gets dark yellow product dyed thereby.Embodiment 5
Divided by following structural formula (Y-2-a) Shown in dyestuff 0.01 gram replace shown in the structural formula (Y-3-a) among the embodiment 1 outside the dyestuff, by the method dyeing identical with embodiment 1, its result obtains the good yellow product dyed thereby of level-dyeing property.Embodiment 6
Except that the dyeing temperature among the embodiment 5 is changed into 50 ℃, by the method dyeing identical with embodiment 5.
Its result, it is good to obtain level-dyeing property, the xanchromatic product dyed thereby that the degree of depth is substantially the same manner as Example 5.
This means at 50 ℃ with 60 ℃ of dyeing, can both obtain the product dyed thereby of same depth.Embodiment 7-1~7-4
In the dyestuff shown in structural formula in embodiment 5 (Y-1-a), (Y-2-a), add yellow reaction dyestuff shown in the aforementioned structural formula (Y-4-a), its mix proportions is as shown in table 2.All the other are all identical with embodiment 5.Its result obtains the good yellow product dyed thereby of level-dyeing property.
Table 2
Embodiment No Dyestuff is formed (g)
〔Y-1-a〕 〔Y-2-a〕 〔Y-4-a〕
2-1 2-2 2-3 2-4 0.055 0.02 0.13 0.27 0.025 0.03 0.04 0.07 0.02 0.02 0.02 -
Embodiment 8
Replace dyestuff shown in the structural formula (Y-1-a) among the embodiment 7-1 with chemically-reactive dyes shown in the aforementioned structural formula (Y-1-b), all the other are identical with embodiment 7-1.Its result obtains the good yellow product dyed thereby of level-dyeing property.Embodiment 9
(Y-1-a) used among the embodiment 7-1, (Y-2-a) and (Y-4-a) are become its lithium salts separately, weigh 50 grams, 30 grams and 20 grams respectively, be dissolved in the 1000ml hot water, be cooled to 25 ℃, do not have dyestuff to separate out, keep the aqueous solution state of homogeneous.
This shows that this dye component has fabulous solubleness, and this characteristic shows that it is suitable for the aqueous constituent of compounding high concentration, and meaning can be by continuous dyeing, roll volume cold-stacking dyeing method obtains dark yellow product dyed thereby.Embodiment 10+1~10-7
Will be as dyestuff shown in the embodiment 2-2 formula of (Y-1-a) of yellow composition, (Y-3-a) and (Y-4-a), general formula (B-1-1-a), (B-1-2-a) and (B-2-a) as blue composition Shown in chemically-reactive dyes be dissolved in 30 ℃ of water of 170ml by usage quantity shown in the table 3 respectively, add 10 gram saltcake, make dyeing pot, insert cotton 10 grams, after 25 minutes, add the aqueous sodium carbonate 30ml of 100 grams per liters with the vibration of oscillatory type dyeing machine, vibration is after 5 minutes under uniform temp, with 1 ℃/minute speed heating 30 minutes, rise to 60 ℃.
Make 6 of above-mentioned dyeing pots respectively, when dyeing temperature, time reach 1. 35 ℃, 2. 40 ℃, 3. 50 ℃, 4. 60 ℃, 5. 60 ℃ * 10 minutes, 6. 60 ℃ * 60 minutes, take out cotton from each dyeing pot, washing, aqueous acetic acid neutralization with 2 grams per liters, washing is then in 80 ℃ of hot washes 10 minutes, then, in the Hostapal of 2 grams per liters CT-40 soap is bathed, in 100 ℃ soaped 10 minutes after, the washing, drying.From 1. being the green of certain form and aspect to stained cloth 6., deepen gradually, illustrate that the dyeing kinetics of yellow dyes and blue dyes is very consistent.
Table 3
Embodiment No Dyestuff is formed (g)
〔Y-1-a〕 〔Y-3-a〕 〔Y-4-a〕 〔B-1-1-a〕 〔B-1-2-a〕 〔B-2-a〕
10-1 10-2 10-3 10-4 10-5 10-6 10-7 0.06 0.06 0.06 0.05 0.06 0.08 0.05 0.04 0.04 0.04 0.03 0.025 0.03 0.03 - - - 0.015 0.01 0.02 0.02 0.05 - 0.04 0.05 - 0.03 0.025 - - 0.01 - - - 0.005 - 0.05 0.05 - 0.05 0.03 0.03
* level-dyeing property is good especially, dyeing kinetics is consistent.Embodiment 11-1~11-10
Blue dyes 0.03 restrained shown in the structural formula (B-2-a) in using the 0.03 gram replacement embodiment 10-7 of blue dyes shown in the table 4, all the other were identical with embodiment 10-7.The green of the same form and aspect of gained stained cloth is along with the variation of dyeing time deepens gradually.Show yellow very consistent with blue dyeing kinetics.Table 4
Figure C9411723600201
Table 4 (continuing)
Figure C9411723600211
Embodiment 12
Remove and use following structural (Y-1-b) and (Y-3-c) respectively
Figure C9411723600221
Shown in the yellow reaction dyestuff replace among the embodiment 10-7 shown in the structural formula (Y-1-a) and (Y-3-a) outside the yellow dyes, all the other are identical with embodiment 10-7.
Its result, stained cloth is certain green, deepens gradually with tinctorial, and this shows yellow very consistent with blue dyeing kinetics.Embodiment 13-1~13-7
Will as dyestuff shown in the embodiment 7-1 formula of (Y-1-a) of yellow composition, (Y-2-a) and (Y-4-a), as dyestuff shown in the said structure formula (B-1-1-a) of blue composition, (B-1-2-a) and (B-2-a) respectively by the amount of Table 5 fusion, with the method dyeing identical with embodiment 10-1~10-7, its result, the dyeing kinetics of yellow dyes and blue dyes is very consistent.
Table 5
Embodiment No Dyestuff is formed (g)
〔Y-1-a〕 〔Y-2-a〕 〔Y-4-a〕 〔B-1-1-a〕 〔B-1-2-a〕 〔B-2-a〕
13-1 0.06 0.04 - 0.05 - -
13-2 0.06 0.04 - - - 0.05
13-3 0.06 0.04 - 0.04 0.01 0.05
13-4 0.05 0.03 0.015 0.05 - -
13-5 0.08 0.025 0.01 - - 0.05
13-6 0.02 0.03 0.01 0.03 - 0.03
13-7 0.05 0.03 0.02 0.025 0.005 0.03
* level-dyeing property is good especially, the dyeing kinetics unanimity.Embodiment 14-1~14-10
Blue reactive dye 0.03 restrained shown in the structural formula (B-2-a) in blue chemically-reactive dyes 0.03 gram replacement embodiment 13-7 shown in the usefulness table 6, all the other were identical with embodiment 13-7.The green of the same form and aspect of gained stained cloth deepens gradually with tinctorial.This shows yellow very consistent with blue dyeing kinetics.Table 6
Figure C9411723600241
Table 6 (continuing) Embodiment 15 removes with following structural (Y-1-b) and (Y-2-b) Shown in the yellow reaction dyestuff replace among the embodiment 13-7 shown in the structural formula (Y-1-a) and (Y-2-a) outside the yellow reaction dyestuff, all the other are identical with embodiment 13-7.
Its result, stained cloth is certain green, deepens gradually with tinctorial, and this shows yellow very consistent with blue dyeing kinetics.
In following each embodiment, each dyestuff so that free acid form is represented all uses its sodium salt.Embodiment 16
Will be by following structural (R-1-a) as orchil Shown in dyestuff 0.05 gram, as the following structural (Y-1-a ') of yellow dyes
Figure C9411723600272
Shown in dyestuff 0.025 gram, following structural (Y-3-a ')
Figure C9411723600273
Shown in dyestuff 0.015 gram and following structural (Y-4-a ')
Figure C9411723600281
Shown in the dye component formed of dyestuff 0.01 gram be dissolved in 30 ℃ of water of 170ml, add saltcake 10 grams, make dyeing pot, insert cotton 10 grams, after 25 minutes, add the aqueous sodium carbonate 30ml of 100 grams per liters with the vibration of oscillatory type dyeing machine, after vibrating 5 minutes under the same temperature, with 1 ℃/minute speed heating 30 minutes, rise to 60 ℃.
Make 6 jars of same dye baths, reach at dyeing temperature 1. following~during 6. temperature, from each dyeing pot, take out cotton, washing, after the aqueous acetic acid neutralization of 2 grams per liters, washing, hot wash, in the HostapalCT-40 of 2 grams per liters soap is bathed, in 100 ℃ soaped 10 minutes after, washing, drying.
①…35℃,②…40℃,③…50℃,④…60℃
5. ... 60 ℃ * 10 minutes, 6. ... 60 ℃ * 60 minutes
1. be certain orange to 6. stained cloth, deepen gradually, the dyeing kinetics of orchil and yellow dyes is very consistent.Comparative example 1
Use yellow dyes 0.05 gram shown in 0.05 gram of orchil shown in the said structure formula (R-1-a) and the said structure formula (Y-1-a '), by operating with embodiment 16 same procedure, 6. with 60 ℃ of dyeing temperatures, 60 minutes painted dying cloth of dyeing time is benchmark, dying cloth and form and aspect respectively more 1.~5., found that from 5. to 1., redness deepens, and form and aspect change.This is because the dyeing kinetics of orchil and the dyeing kinetics of yellow dyes there are differences.Embodiment 17-1~17-5
Except that with the mix proportions of dyestuff is by changing shown in the table 7 shown in structural formula (R-1-a), (Y-1-a '), (Y-3-a ') and (Y-4-a ') among the embodiment 16, all the other are identical with embodiment 16.
Dyeing kinetics of all orchils and yellow dyes is all very consistent as a result for it.Comparative example 2
The composition of dyestuff shown in structural formula (R-1-a), (Y-1-a '), (Y-3-a ') and (Y-4-a ') among the embodiment 16 by changing shown in the table 7, is used the method dyeing identical with embodiment 16.Its result, because dyeing kinetics is inconsistent, along with the variation of dyeing time, form and aspect also change.
Table 7
Dyestuff is formed (g) The tone of product dyed thereby Appendix
〔R-1-a〕 〔Y-1-a′〕 〔Y-3-a′〕 〔Y-4-a′〕
17-1 17-2 17-3 17-4 17-5 comparative example 2 0.05 0.15 0.2 0.05 0.2 0.05 0.03 0.01 0.02 0.1 0.18 0.01 0.015 0.015 0.01 0.06 0.07 0.035 0.005 0.002 - 0.03 0.05 0.005 Orange orange big reddish orange is orange Along with the variation of dyeing time, form and aspect slightly change dyeing initial stage yellow by force
Embodiment 18-1~18-22
The dyestuff shown in the structural formula, all the other are identical with embodiment 16 in dyestuff shown in the structural formula (R-1-a) among the embodiment 16 being changed into table 8-A and table 8-B.
Its result, it is certain orange that stained cloth is, and deepen gradually, shows that the dyestuff speed of red reactive dye and yellow reaction dyestuff is very consistent.Table 8A Table 8B Embodiment 19
Except that replacing with dyestuff shown in following structural (Y-1-b) among the embodiment 16 shown in the structural formula (Y-1-a ') the yellow dyes, all the other are identical with embodiment 16.
Its result, it is certain orange that stained cloth is, and deepen gradually, shows that the dyeing kinetics of orchil and yellow dyes is very consistent.
Figure C9411723600321
Embodiment 20-1~20-3
Blue dyes shown in chemically-reactive dyes shown in said structure formula (R-1-a), (Y-1-a '), (Y-3-a ') and (Y-4-a ') and following structural (B-1-1-a '), (B-2-a ') is pressed fusion shown in the table 9, use the method dyeing identical with embodiment 16.
It is certain brown that stained cloth is, and deepen along with the variation of dyeing time.This shows that redness, yellow are very consistent with blue dyeing kinetics.
Figure C9411723600322
Figure C9411723600331
Table 9
Embodiment No Dyestuff is formed (g)
〔R-1-a〕 〔Y-1-a′〕 〔Y-3-a′〕 〔Y-4-a′〕〕 〔B-1-1-a′〕 〔B-2-a′〕
20-1 20-2 20-3 0.05 0.05 0.05 0.03 0.03 0.03 0.02 0.02 0.02 0.01 0.01 - 0.05 0.03 - - 0.03 0.05
Embodiment 21
Except that replacing with yellow reaction dyestuff shown in following structural (Y-3-d) among the embodiment 16 shown in the structural formula (Y-3-a ') the yellow reaction dyestuff, all the other are identical with embodiment 16.
It is certain orange that stained cloth is, and along with the variation of dyeing time deepens gradually, show red consistent with the dyeing kinetics of xanchromatic dyestuff. Embodiment 22
Remove with following structural (B-1-1-a ') and (B-1-2-a ') Shown in 4: 1 mixtures of blue reactive dye replace among the embodiment 20-2 shown in the structural formula (B-1-1-a ') outside the blue dyes, all the other are identical with embodiment 20-2.
It is certain brown that stained cloth is, and deepen along with the variation of dyeing time, and this shows that redness, yellow are very consistent with blue dyeing kinetics.Embodiment 23-1~23-17
Except that replacing with blue dyes shown in the table 10 among the embodiment shown in the structural formula (B-2-a ') the blue dye, all the other are identical with embodiment 20-2.It is certain brown that stained cloth is, and deepen along with the variation of dyeing time, and this shows that redness, yellow are very consistent with blue dyeing kinetics.Table 10 Table 10 (continuing) Embodiment 24-1~24-3
With redness is dyed shown in the structural formula (R-1-a) among the orchil replacement embodiment 20-2 of embodiment 17-15,17-17 among the table 8-B and 17-20, all the other are identical with embodiment 20-2 except that respectively.
It is certain brown that stained cloth is, and deepen gradually along with the variation of dyeing time, and this dyeing kinetics that shows redness, yellow, blue each dyestuff is very consistent.Embodiment 25
With dyestuff shown in structural formula (R-1-a), (Y-1-a '), (Y-3-a '), (Y-4-a '), (B-1-1-a ') and (B-2-a '), press and form the modulation padding liquor shown in the table 11, in order to padding cloth, to be rolled to the liquid rate 70% of taking, in 100 ℃ of dryings 3 minutes.
Then, this cotton is padded with the chemical liquids of forming shown in the table 12, be rolled to the liquid rate 80% of taking, in 102 ℃ of steam sets 30 seconds, 60 seconds and 120 seconds, after the washing, aqueous acetic acid neutralization with 2 grams per liters, washing, hot wash again in Hostapal CT-40 soap is bathed, soaped 10 minutes in 100 ℃ then, washing, drying.Its result, it is certain brown that stained cloth is, and deepen gradually, illustrates that the dyeing kinetics of orchil, yellow dyes and blue dyes is very consistent.
Table 11 padding liquor is formed
Component content (g/l)
〔R-1-a〕 2.0
〔Y-1-a′〕 2.5
〔Y-3-a′〕 1.5
〔Y-4-a′〕 1.0
〔B-1-1-a′〕 2.5
〔B-2-a′〕 2.5
Sodium alginate (medium viscosity product) 2.0
Between-nitrobenzene sodium sulfonate 10.0
Sodium hexametaphosphate 99 2.0 interfacial agents (Leonil SR-J, 2ml/lHOECHST JAPAN company produces)
Table 12 chemical liquids is formed
Component content (g/l)
Saltcake 200
Yellow soda ash 40
Figure C9411723600391
Aqueous sodium hydroxide solution embodiment 26
Except that replacing with 0.015 gram of dyestuff shown in following structural (Y-2-a ') among the embodiment 16 shown in 0.03 gram of yellow dyes shown in the structural formula (Y-1-a ') and structural formula (Y-3-a ') the yellow dyes, all the other are identical with embodiment 16.The result shows that the dyeing kinetics of orchil and yellow dyes is very consistent.
Figure C9411723600392
Embodiment 27-1~27-5
Except that replace among embodiment 17-1~17-5 the blending ratio of dyestuff, each dyestuff shown in the structural formula (Y-3-d ') press shown in the table 13 variation with dyestuff shown in the above-mentioned structural formula (Y-2-a '), all the other are identical with embodiment 17-1~17-5.The result shows that the dyeing kinetics of orchil and yellow dyes is very consistent.Comparative example 3
Except that replacing with dyestuff shown in above-mentioned (Y-2-d ') in the comparative example 2 shown in the structural formula (Y-3-a ') the yellow dyes, all the other are identical with comparative example 2.Because dyeing kinetics is inconsistent, along with the variation of time, form and aspect also change.
Table 13
Dyestuff is formed (g) The tone of product dyed thereby Appendix
〔R-1-a〕 〔Y-1-a′〕 〔Y-2-a′〕 〔Y-4-a′〕
27-1 27-2 27-3 27-4 27-5 comparative example 3 0.03 0.15 0.2 0.05 0.2 0.05 0.03 0.015 0.02 0.1 0.18 0.01 0.015 0.01 0.01 0.06 0.07 0.035 0.005 0.002 - 0.03 0.05 0.005 Orange orange big reddish orange is orange The very consistent dyeing initial stage of dyeing kinetics is yellow strong
Embodiment 28-1~28-22
Except that replacing with 0.015 gram of dyestuff shown in structural formula (Y-2-a ') among embodiment 18-1~18-22 shown in 0.03 gram of yellow dyes shown in the structural formula (Y-1-a ') and structural formula (Y-3-a ') the yellow dyes, all the other are identical with embodiment 18-1~18-22.The result shows that the dyeing speed of orchil and yellow dyes is very consistent.Embodiment 29
Except that replacing with dyestuff shown in structural formula (Y-1-b) among the embodiment 26 shown in the structural formula (Y-1-a ') the dyestuff, all the other are identical with embodiment 26.The result shows that the dyeing kinetics of orchil and yellow dyes is very consistent.Embodiment 30-1~30-3
Except that dyestuff 0.02 gram shown in 0.035 gram of dyestuff shown in the yellow dyes utilization structure formula (Y-1-a ') and the structural formula (Y-2-a '), all the other are identical with embodiment 20-1~20-3.The result shows that the dyeing kinetics of orchil and yellow dyes is very consistent.Embodiment 31
Except that replacing with yellow reaction dyestuff shown in following structural (Y-2-c) among the embodiment 26 shown in the structural formula (Y-2-d) the yellow reaction dyestuff, all the other are identical with embodiment 26.
It is certain orange that stained cloth is, and along with the variation of dyeing time deepens gradually, show red consistent with the dyeing kinetics of xanchromatic dyestuff. Embodiment 32
Except that with among 4: 1 mixtures replacement embodiment 30-2 of dyestuff shown in structural formula (B-1-1-a ') and (B-1-2-a ') shown in the structural formula (B-1-1-a ') the blue dyes, all the other are identical with embodiment 30-2.It is certain brown that stained cloth is, and along with the variation of dyeing time deepens gradually.This dyeing kinetics that shows redness, yellow and blue dyes is very consistent.Embodiment 33-1~33-17 and 34-1~3
Except that dyestuff 0.02 gram shown in 0.035 gram of dyestuff shown in the yellow dyes utilization structure formula (Y-1-a ') and the structural formula (Y-2-a '), all the other are identical with 24-1~3 with embodiment 23-1~23-17.The result shows that the dyeing kinetics of orchil, yellow dyes and blue dyes is very consistent.Embodiment 35
Except that replacing with dyestuff shown in structural formula (Y-2-a ') among the embodiment 25 shown in the structural formula (Y-3-a ') the dyestuff, all the other are identical with embodiment 25.The result shows that the dyeing kinetics of orchil, yellow dyes and blue dyes is very consistent.Embodiment 36
Use each 0.05 gram of yellow dyes shown in 0.15 gram of orchil shown in the following structural (R-2-a '), structural formula (Y-1-a ') and (Y-2-a '), use the method identical to dye, obtain orange product dyed thereby with embodiment 16.The dyeing kinetics of orchil and yellow dyes is very consistent.
Figure C9411723600421
Because the dyeing kinetics of the red series dyes composition of dye component of the present invention and Yellow series dyestuff composition and blue series dyes composition is consistent, its form and aspect can not change owing to the length of dyeing time.
Use this dye component, can carry out from orange to the brown good dyeing of form and aspect circulation ratio.And constituent of the present invention is little to the interdependence of inorganic salt, photostabilization, fastness to chlorine excellence.

Claims (3)

1. Yellow active dye composition is characterized in that: by the general formula (Y-1) of the free acid shape of 80-50% (weight)
Figure C9411723600021
In the formula, X represents-CH=CH 2,-C 2H 4OSO 3H or-C 2H 4The general formula (Y-2) of the free acid shape of Yellow active dye that Cl represents and 20-50% (weight)
Figure C9411723600022
In the formula, the Yellow active dye of the same expression of definition of X is formed;
Or by the general formula (Y-3) of the free acid shape of the Yellow active dye of the general formula (Y-1) of 60-40% (weight) expression and 40-60% (weight)
Figure C9411723600023
In the formula, T represents amino or methyl, and the Yellow active dye of the same expression of definition of X is formed.
2. Yellow active dye composition as claimed in claim 1, it is characterized in that this Yellow active dye composition is made up of the Yellow active dye of general formula (Y-2) expression of the Yellow active dye of the general formula (Y-1) of 80-60% (weight) expression and 20-40% (weight).
3. the staining of cellulose fibre product is characterized in that, uses claim 1 or 2 described reactive dye compositionss.
CN94117236A 1993-10-15 1994-10-14 Dye composition and dyeing method using same Expired - Fee Related CN1056636C (en)

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JP6054444A JPH07238232A (en) 1994-02-28 1994-02-28 Reactive dye composition
JP54444/1994 1994-02-28
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JP07971194A JP3226707B2 (en) 1994-03-25 1994-03-25 Reactive dye composition
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CN101880473B (en) * 2010-06-29 2013-05-08 浙江科永化工有限公司 Active orange dye composition
CN102311667B (en) * 2010-07-08 2013-12-04 上海雅运纺织化工股份有限公司 Navy reactive dye composition and dying application thereof on fiber
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CN105440736A (en) * 2015-12-22 2016-03-30 浙江亿得化工有限公司 Composite yellow reactive dye for wool and preparation method thereof
CN106833017B (en) * 2016-11-28 2018-09-11 浙江瑞华化工有限公司 A kind of blue active dye composition and its preparation method and application

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