CN102634230A - Red 1:2 chromium-complexed acidic dye composition, and synthesis and dyeing application thereof - Google Patents
Red 1:2 chromium-complexed acidic dye composition, and synthesis and dyeing application thereof Download PDFInfo
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- CN102634230A CN102634230A CN2012100809322A CN201210080932A CN102634230A CN 102634230 A CN102634230 A CN 102634230A CN 2012100809322 A CN2012100809322 A CN 2012100809322A CN 201210080932 A CN201210080932 A CN 201210080932A CN 102634230 A CN102634230 A CN 102634230A
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- SLQLABLFVOWTGA-ZCXUNETKSA-N Cc(c(/N=N\c1cc(S(O)(=O)=O)cc([N+]([O-])=O)c1O)c1O)n[n]1-c1ccccc1 Chemical compound Cc(c(/N=N\c1cc(S(O)(=O)=O)cc([N+]([O-])=O)c1O)c1O)n[n]1-c1ccccc1 SLQLABLFVOWTGA-ZCXUNETKSA-N 0.000 description 1
- UBHXEBULYUUOHN-SEYXRHQNSA-N Cc1n[nH]c(O)c1/N=N\c(ccc([N+]([O-])=O)c1)c1O Chemical compound Cc1n[nH]c(O)c1/N=N\c(ccc([N+]([O-])=O)c1)c1O UBHXEBULYUUOHN-SEYXRHQNSA-N 0.000 description 1
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Abstract
The invention relates to a red chromium-complexed acidic dye composition, which is composed of dyestuff in a certain proportion according to general formulas (1, 2, 3 and 4). Components of the acidic dye composition are 1:2 chromium-complexed acidic dye, and the acidic dye composition is prepared by synthetizing. The red chromium-complexed acidic dye composition is bright in color light and has excellent chromaticity and various color fastness properties, excellent migrating property and permeability are worthy of commending. Besides, the red chromium-complexed acidic dye composition has excellent compatibility and can be used as red components in three-primary colors of the acidic dye. The general formulas (1, 2, 3 and 4) are shown.
Description
Technical field
The present invention relates to a kind of metallized dye compsn, particularly, the present invention relates to a kind of red 1:2 chromium complexed acidic dye composite and synthetic and tint applications.
Background technology
The 1:2 metallized dye is to be developed by exploitation on the basis of acid mordant dye and 1:1 metallized dye.This type dyestuff can dye in neutrality is bathed, and neutral dye therefore is otherwise known as.This type dyestuff is compared with above-mentioned two types of dyestuffs and general matching stain, has fabric, good hand touch, the excellent characteristics of fastness do not damaged.Its dyeing is simpler and easy than acid mordant dye, does not have metallic dyeing waste-water.Therefore the 1:2 metallized dye has developed into the dye class of a type of important wool, silk and tynex and BLENDED FABRIC thereof.
The present invention is intended to develop a kind of red 1:2 chromium complexed acidic dye composite that is used for wool, silk and tynex and BLENDED FABRIC thereof.
The variety development of red 1:2 chromium complexed acidic dyestuff is just implemented as far back as the 70-80 age in last century.Wherein representative patent has:
DE?2501039(1975)(Ciba-Geigy)
GB?1450669(1976)(Bayer)
GB?1492683(1977)(Ciba-Geigy)
US?4083839(1978)(Ciba-Geigy)
GB?2027734(1979)(Bayer)
DE?2835493(1980)(Bayer)
DE?3326954(1984)(Sandoz)
EP?0260562(1987)(Bayer)
DE?3631751(1988)(Bayer)
US?4077764(1978)(Hoechst)
The coloured light of above-mentioned matching stain kind, dyeing behavior and dyefastness respectively have quality.Use separately, be difficult to satisfy and adapt to normal dyeing requirement.
As the dyestuff of other classification, adopt the 1:2 metallized acid dye of 2 kinds or multiple different structure to piece together selectively and mix, can effectively improve its dyeing color and luster, tint applications performance and each item dyefastness.
The inventor notices the patent CN 101128545 (2008) that Dystar company delivers.This patent discloses the metal complex dye mixtures of various color and lusters, and obtains certain tint applications effect.
The inventor is surprised to find that and adopts that 2 monoazo-dyes are disposable to carry out complex reaction on the basis of a large amount of experimental studies, makes the mixture of general formula (2) dyestuff, general formula (3) dyestuff and general formula (4) dyestuff that contain different ratios.This mixture mixes with general formula (1) dyestuff more by a certain percentage, makes the red chromium complexed acidic of 1:2 of the present invention dye composite.
Therefore, the red chromium complexed acidic of 1:2 of the present invention dye composite is made up of 4 components.
Pleasurable is that the dyeing color and luster of dye composite of the present invention can be adjusted arbitrarily; Its dyeing migration property and perviousness all are superior to the reference dyestuff of CN 101128545 (2008).The present invention adopts disposable chromium complex reaction, not only can reduce the dyestuff cost of manufacture, and can reduce the consumption of the expensive general formula of valency (1) dyestuff.
The inventor confirms that the present invention has broad application prospects.
Summary of the invention
The inventor is on the basis of a large amount of research trials; Find pleasantly surprisedly; The red 1:2 chromium of the present invention complexed acidic dye composite can contain the dye composition that general formula (1), general formula (2), general formula (3) and general formula (4) are represented separately; The dye composition of preferably being represented separately by general formula (1), general formula (2), general formula (3) and general formula (4) is formed, and has gorgeous, the excellent dyeing behavior of coloured light and good each item dyefastness.
The red 1:2 chromium of the present invention complexed acidic dye composite, the dyeing color and luster can be adjusted arbitrarily, and its dyeing migration property and perviousness all are superior to CN 101128545 (2008) reference dyestuff (Dystar), have better level-dyeing property.
The present invention adopts disposable chromium complex reaction, not only can reduce the dyestuff cost of manufacture, and can reduce the consumption of the dyestuff of the expensive general formula of valency (1) expression.
The present invention should have broad application prospects.
The dye composition of the general formula among the present invention (1) expression is:
General formula (1)
In the formula:
R
1And R
2Be H, CH independently respectively
3, C
2H
5, or phenyl;
R
3For H or
R wherein
5Be H, CH
3, SO
2NH
2, Cl or CONH
2
R
4Be H or NO
2
n
1Be 1 or 3;
M is an alkali metal cation;
The dye composition of the general formula among the present invention (2) expression is:
General formula (2)
In the formula:
R
6And R
7Be H, SO independently respectively
3H, NO
2Or Cl group;
R
8For H or
R wherein
11Be H, CH
3, SO
2NH
2, Cl or CONH
2
R
9Be H, NO
2Or Cl group;
R
10For H or
R wherein
12Be H, CH
3, SO
2NH
2, Cl or CONH
2
n
2Be 2;
M is an alkali metal cation;
The dye composition of the general formula among the present invention (3) expression is:
General formula (3)
In the formula:
R
6And R
7Be H, SO independently respectively
3H, NO
2Or Cl group;
R
8For H or
R wherein
11Be H, CH
3, SO
2NH
2, Cl or CONH
2
n
3Be 3;
M is an alkali metal cation;
The dye composition of the general formula among the present invention (4) expression is:
General formula (4)
In the formula:
R
9Be H, NO
2Or Cl group;
R
10For H or
R wherein
12Be H, CH
3, SO
2NH
2, Cl, CONH
2
n
4Be 1 or 3;
M is an alkali metal cation.
The present invention also provides the preparation method of above-mentioned red 1:2 chromium complexed acidic dye composite, and it comprises the steps:
1) press 0.8-1.2: 0.8-1.2: 0.9-1.3 is preferably 1: 1: the mol ratio of 1.0-1.1 makes general formula (5) and (6) carry out the chromium complex reaction with aqueous solution complex salt, obtains the mixture of the dye composition of general formula (2), general formula (3) and general formula (4) expression; With
General formula (5)
General formula (6)
2) by 95-80: the weight ratio of 5-20 is mixed the dye composition of above-mentioned mixture with general formula (1) expression.
The present invention also provides the application of above-mentioned red chromium complexed acidic dye composite aspect the dyeing of protein fibre and tynex and BLENDED FABRIC thereof.
The practical implementation method
The red chromium complexed acidic of the present invention dye composite preferably is made up of the dye composition of general formula (1), general formula (2), general formula (3) and general formula (4) expression in certain proportion.
One preferred embodiment in, said general formula (1), general formula (3) and the represented dye composition of general formula (4) are symmetric form 1:2 chromium complexed acidic dyestuff, the dyestuff of said general formula (2) expression is asymmetric 1:2 chromium complexed acidic dyestuff.
One preferred embodiment in, said general formula (1) dye composition: general formula (2) dye composition: general formula (3) dye composition: weight ratio=5～25% of general formula (4) dye composition: 40～80%: 5～15%: 5～35%; Be preferably 5～20%: 45～75%: 5～15%: 10～30%.
One preferred embodiment in, in the general formula (1)
Group is positioned on the benzene nucleus-contraposition or a position of N=N-group; R in the general formula (2)
9Group is positioned on the benzene nucleus-contraposition or a position of N=N-group; R in general formula (1) and the general formula (2)
5, R
11And R
12Group is separately located in respectively on the benzene nucleus-ortho position, a position or the contraposition of N-N-group.
Another preferred embodiment in, the R in the general formula (4)
9Group is positioned on the benzene nucleus-contraposition or a position of N=N-group; R in general formula (3) and the general formula (4)
11And R
12Group is separately located in respectively on the benzene nucleus-ortho position, a position or the contraposition of N-N-group.
The dye composition of general formula (1) expression for example comprises following instance:
Dyestuff 1-1
Dyestuff 1-2
Dyestuff 1-3
Dyestuff I-4
Dyestuff I-5
Dyestuff I-6 or
Dyestuff I-7.
The dye composition of general formula (2) expression is for example to comprise following instance:
Dyestuff 2-1
Dyestuff 2-2
Dyestuff 2-3
Dyestuff 2-4
Dyestuff 2-5 or
Dyestuff 2-6.
The dye composition of general formula (3) expression is for example to comprise following instance:
Dyestuff 3-1
Dyestuff 3-2
Dyestuff 3-3
Dyestuff 3-4
Dyestuff 3-5 or
Dyestuff 3-6.
The dye composition of general formula (4) expression is for example to comprise following instance:
Dyestuff 4-1
Dyestuff 4-2
Dyestuff 4-3
Dyestuff 4-4
Dyestuff 4-5 or
Dyestuff 4-6.
The dyestuff of general formula (1), general formula (2), general formula (3) and general formula (4) expression is the known dye compound.
The dyestuff of general formula (1) expression, its series of products structure and compound method thereof are seen following patent:
EP?0241414(1987)(Ciba-Geigy)
DE?3631751(1988)(Bayer)
US?4077764(1978)(Hoechst)
GB?1112032(1968)(Bayer)
The dyestuff of general formula (2) expression, the structure of its series of products and compound method thereof are seen following patent:
DE?2835493(1980)(Bayer)
The dyestuff of general formula (3) expression, the structure of its series of products and compound method thereof are seen following patent:
DE?3631751(1988)(Bayer)
The dyestuff of general formula (4) expression, the structure of its series of products and compound method thereof are seen following patent:
GB?792206(1958)(ICI)
GB?925997(1960)(Ciba)
GB?1493474(1977)(Ciba-Geigy)
The mixture of the dye composition that general formula (2), general formula (3), general formula (4) represent is separately produced in the reaction of the disposable chromium network of the present invention, sees following examples.
Red 1:2 chromium complexed acidic dye composite of the present invention also can contain the dye additive of various conventional uses in dyeing and dye formulations, and its consumption can be selected by actual needs, does not have special qualification, generally is no more than 20 weight %.Inorganic salts for example is like NaCl, NaSO
4, content 0-10 weight %, dispersant 0-10 weight %, the pH regulator agent, like SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate, dibasic, content 0-5 weight %, dust-proofing agent 0-10 weight %, solubility promoter 1-15 weight %.The present composition also can be made up of general formula (1) dyestuff and general formula (2) dyestuff of above-mentioned weight ratio basically.
The preparation method of red 1:2 chromium complexed acidic dye composite of the present invention comprises that the dye composition with the expression of above-mentioned general formula (1) to general formula (4) mixes by the weight ratio of regulation.Mix available various ordinary method, like the mechanically mixing method.During mixing, the dye composition of general formula (1), general formula (2), general formula (3) and general formula (4) expression can powder type, or with particle form, or exists with aqueous solution form.For example, mixing step can carry out in suitable shredder such as ball mill or needle mill and in kneader or mixing machine.Yet, one preferred embodiment in, earlier the dye composition mixture of preparation general formula (2), (3) and (4) expression mixes with the dye composition that general formula (1) is represented then by a certain percentage.
Temperature in the network complex reaction is 85-100 ℃, is preferably 90-100 ℃, and the reaction times is preferably 4-8 hour, is preferably 5-6 hour, and reaction preferably in aqueous solvent, is particularly carried out in water.Used water-soluble complex salt for example is chromium sulphate, chromium chloride, chromium nitrate, Plessy's green or their mixture in the reaction.Be adjusted to 8-12 to the pH value of reaction mixture with alkali metal hydroxide (like sodium hydroxide) in the reaction process, particularly 9-11.
Red 1:2 chromium complexed acidic dye composite of the present invention is suitable for dyeing and various widely material, the particularly application aspect the dyeing of protein fibre, tynex and BLENDED FABRIC thereof etc.
Red 1:2 chromium complexed acidic dye composite of the present invention can be applied to filamentary material and is fixed on the fiber with several different methods as known in the art, for example can dye with dip-dye method or pad dyeing method.
Embodiment
One, synthetic embodiment
Synthetic embodiment 1
The red 1:2 chromium of the present invention complexed acidic dye composite that the present embodiment preparation preferably is made up of dyestuff 1-1, dyestuff 2-5, dyestuff 3-1 and dyestuff 4-2.
Synthetic operation:
Dyestuff 1-1 is a known dye, its compound method can consult DE 3631751 (1988) (Bayer) with US 4077764 (1978) (Hoechst) or commercially available.
Monoazo-dyes A and each 0.14mol of monoazo-dyes B are placed the water of 3000ml.
The structural formula of monoazo-dyes A is:
The structural formula of monoazo-dyes B is:
Above-mentioned solution is under condition of stirring, and adding 20%NaOH adjusting PH is 10, and reaction solution is warming up to reflux temperature.In 30 minutes, dripping the chromium sulphate aqueous solution (the 0.16mol chromium sulphate is dissolved in 200ml water) under this temperature, and constantly to add 20%NaOH solution be 10 with the PH that keeps reaction solution.
This chromium complex reaction temperature maintenance is at 98-100 ℃, and the chromium complex reaction needs 5-6 hour approximately, carries out situation with the thin plate detection reaction, and disappearing with monoazo-dyes B is reaction end.
After the chromium complex reaction, reaction solution is lowered the temperature, is saltoutd, filters and be dry, makes the mixture filter cake of dyestuff 2-5, dyestuff 3-1 and dyestuff 4-1.
Through liquid-phase chromatographic analysis (SHIMADZU LC-20AT SPD high performance liquid chromatograph system, chromatographic column model: Inertsil ODS-SP, 5um 4.6x250mm; Moving phase: 37% water (4g/L tetrabutyl phosphonium bromide aqueous ammonium): 63% organic phase (methyl alcohol (chromatographically pure); Flow velocity: 1.0mL/min; Column temperature: 40 ℃ of wavelength: 254nm), this dye mixture contains following dye component:
Dyestuff 2-5 60.1%
Dyestuff 3-1 9.8%
Dyestuff 4-2 30.1%
Above-mentioned dye composition mixture and dye composition 1-1 (available from Bayer company) are pressed 95:5 respectively; 90:10; 80:20 pieces together mixed, makes red 1:2 chromium complexdyes compsn of the present invention, and confirms its content through high-efficient liquid phase analysis, makes dyestuff and sees table 1:
Table 1
" % " in the table 1 all representes weight %, is benchmark with the gross weight of dye composite.
The structural formula of the component of the red chromium complexed acidic of the 1:2 of this synthetic operation dye composite is:
Dyestuff 1-1
Dyestuff 2-5
Dyestuff 3-1
Dyestuff 4-2
Synthetic embodiment 2
The red 1:2 chromium of the present invention complexed acidic dye composite that the present embodiment preparation is made up of dyestuff 1-2, dyestuff 2-2, dyestuff 3-2 and dyestuff 4-1.
Synthetic operation:
Dyestuff 1-2 is a known dye, its compound method press DE 3631751 (1988) (Bayer) with US 4077764 (1978) (Hoechst) or commercially available.
Monoazo-dyes C and each 0.14mol of monoazo-dyes D are placed the water of 1500ml respectively.
The structural formula of monoazo-dyes C is:
The structural formula of monoazo-dyes D is:
Above-mentioned two kinds of solution are under condition of stirring; Adding 20%NaOH adjusting PH is 10, and the dye solution that the dye solution that is dissolved with monoazo-dyes C and 1/4 is dissolved with monoazo-dyes D mixes, and is warming up to reflux temperature; In 30 minutes, dripping the chromium sulphate aqueous solution (the 0.16mol chromium sulphate is dissolved in 200ml water) under this temperature; And constantly drip remaining 3/4 be dissolved with monoazo-dyes D dye solution, meanwhile, continuing to add 20%NaOH solution is 10 with the PH that keeps reaction solution.
This chromium complex reaction temperature maintenance is at 98-100 ℃, and the chromium complex reaction needs 5-6 hour approximately, carries out situation with the thin plate detection reaction, and disappearing with monoazo-dyes D is reaction end.
After the chromium complex reaction, reaction solution is lowered the temperature, is saltoutd, filters and be dry, makes the mixture filter cake of dyestuff 2-2, dyestuff 3-2 and dyestuff 4-2.
Through liquid-phase chromatographic analysis (SHIMADZU LC-20AT SPD high performance liquid chromatograph system, chromatographic column model: Inertsil ODS-SP, 5um 4.6x 250mm; Moving phase: 37% water (4g/L tetrabutyl phosphonium bromide aqueous ammonium): 63% organic phase (methyl alcohol (chromatographically pure); Flow velocity: 1.0mL/min; Column temperature: 40 ℃ of wavelength: 254nm), this dye mixture contains following dye component:
Dyestuff 2-5 79.5 weight %
Dyestuff 3-1 7.0 weight %
Dyestuff 4-2 13.5 weight %
Above-mentioned dye mixture and dyestuff 1-2 are pressed 95:5 respectively; 90:10; 80:20 pieces together mixed, makes red 1:2 chromium complexdyes compsn of the present invention, and confirms its content through high-efficient liquid phase analysis, makes dyestuff and sees table 2:
Table 2
" % " in the table 2 all representes weight %, is benchmark with the gross weight of dye composite.
The structural formula of the component of the red chromium complexed acidic of the 1:2 of this synthetic operation dye composite is:
Dyestuff 1-2
Dyestuff 2-2
Dyestuff 3-2
Dyestuff 4-2
Two, application performance embodiment
Each item testing method of embodiment
Each item performance of present embodiment is tested by following each item testing method
1, solubleness: take by weighing a certain amount of dyestuff in the beaker of 250ml, add the hot water of 80 ℃ of 100ml, carry out suction filtration (during suction filtration, pressure 0.075Mpa, 5A qualitative filter paper) after 5 minutes, observe the filter paper residual condition with the mechanical stirrer stirring.Reduce dye strength (G/L), no dyestuff is residual on filter paper, and the dye strength (G/L) of this moment is the solubleness of dyestuff.
2, dyeing nylon exhaustion rate test: the dye liquor preparation, press the acid dyeing dyeing of nylon.After dyeing finishes, test the absorbancy of dyeing residual liquid and the absorbance of the preceding dye liquor of dyeing respectively.
Exhaustion rate=(absorbance of dye liquor before the absorbance/dyeing of 1-dyeing back dye liquor) * 100%
3, migration property test: will dye cloth specimen and equal size, the cloth specimen stitching all around of being unstained that shape is consistent, put into the blank solution that is added with auxiliary agent, buffered soln but does not have dyestuff, dye according to common process.Test moves dyes power part that back calico Dry Sack accounts for former stained cloth, and it is outstanding more than 60% that migration property reaches, not poor less than 30%.
4, the water colour of anti-chlorination fastness test:, measure by international standard ISO 105E03 with the dyeing nylon fabric.
5, colour fastness to perspiration test:, measure by international standard ISO 105-E04 with the dyeing nylon fabric.
6, fastness to soaping test:, measure by international standard ISO 105-C10 with the dyeing nylon fabric.
Dye type shown in the according to the form below 3 and consumption thereof by ordinary method uniform mixing in this area, are prepared the various red 1:2 chromium complexed acidic dye composite of the embodiment of the invention with various dye components.
" % " in the table 3 all representes weight %, is benchmark with the gross weight of dye composite.
Table 3
* reference dyestuff X is one of compsn that relates among the patent CN 101128545 (2008).
Embodiment 1
The red 1:2 chromium of the present invention complexed acidic dye composite coloured light
In the red 1:2 chromium of the present invention complexed acidic dye composite; The dye composition of general formula (1) expression is the orchil of inclined to one side gold-tinted; The dye composition of general formula (2) expression is the orchil of inclined to one side blue light, and through once synthetic general formula (2) dyestuff that makes, general formula (3) dyestuff and the dye composite of general formula (4) dyestuff composition are the orchils that has a little blue light.
The coloured light of carmoisine compsn of the present invention is comparatively pure; And adopt the dye composite of general formula (1) dyestuff, general formula (2) dyestuff, general formula (3) dyestuff and general formula (4) dyestuff composition to compare with the dye composite that only adopts general formula (1) dyestuff and general formula (2) dyestuff to form, reach identical coloured light and can use the ratio that reduces general formula (1) dyestuff.Because general formula (1) cost of dye is higher, thereby reduced the cost of dyestuff.
Embodiment 2
The solubleness test
Measure the solubleness of following dyestuff as stated above, test result is recorded in the table 4
Table 4
Visible by table 4:
The red 1:2 chromium of the present invention complexed acidic dye composite has solubleness preferably, and level-dyeing property is better.
Embodiment 3
Dyeing nylon exhaustion rate is measured
Measure the exhaustion rate of following dyestuff as stated above, test result is recorded in the table 5
Table 5
Visible by table 5:
The red 1:2 chromium of the present invention complexed acidic dye composite have a splendid dyeing exhaustion rate.
Embodiment 4
Migration property can be measured
Measure following dye movement metachromia as stated above, test result is recorded in the table 6
Table 6
Visible by table 6:
The red 1:2 chromium of the present invention complexed acidic dye composite migration property is superior to the reference dyestuff greatly, has excellent more level dyeing performance.
Embodiment 4
The water dungeon of anti-chlorination degree
Measure the water colour of anti-chlorination fastness of following dyestuff as stated above, test result is recorded in the table 7
Table 7
Visible by table 7:
The red 1:2 chromium of the present invention complexed acidic dye composite has the excellent water dungeon of anti-chlorination degree.
Embodiment 5
Colour fastness to perspiration
Measure the colour fastness to perspiration of following dyestuff as stated above, test result is recorded in the table 8
Table 8
Visible by table 8:
The red 1:2 chromium of the present invention complexed acidic dye composite has good fastness to perspiration.
Embodiment 6
Fastness to soaping
Measure the fastness to soaping of following dyestuff as stated above, test result is recorded in the table 9
Table 9
Visible by table 9:
The red 1:2 chromium of the present invention complexed acidic dye composite has good fastness to soaping.
Claims (9)
1. red chromium complexed acidic dye composite, this dye composite contain the dye composition of general formula (1), general formula (2), general formula (3) and general formula (4) expression:
General formula (1)
In the formula:
R
1And R
2Be H, CH independently respectively
3, C
2H
5, or phenyl;
R
3For H or
R wherein
5Be H, CH
3, SO
2NH
2, Cl or CONH
2
R
4Be H or NO
2
n
1Be 1 or 3;
M is an alkali metal cation;
General formula (2)
In the formula:
R
6And R
7Be H, SO independently respectively
3H, NO
2Or Cl group;
R
8For H or
R wherein
11Be H, CH
3, SO
2NH
2, Cl or CONH
2
R
9Be H, NO
2Or Cl group;
R
10For H or
R wherein
12Be H, CH
3, SO
2NH
2, Cl or CONH
2
n
2Be 2;
M is an alkali metal cation;
General formula (3)
In the formula:
R
6And R
7Be H, SO independently respectively
3H, NO
2Or Cl group;
R
8For H or
R wherein
11Be H, CH
3, SO
2NH
2, Cl or CONH
2
n
3Be 3;
M is an alkali metal cation;
General formula (4)
In the formula:
R
9Be H, NO
2Or Cl group;
R
10For H or
R wherein
12Be H, CH
3, SO
2NH
2, Cl, CONH
2
n
4Be 1 or 3;
M is an alkali metal cation.
2. the described red chromium complexed acidic dye composite of claim 1; It is characterized in that; Said general formula (1), general formula (3) and the represented dye composition of general formula (4) are symmetric form 1:2 chromium complexed acidic dyestuff, and the dyestuff of said general formula (2) expression is asymmetric 1:2 chromium complexed acidic dyestuff.
3. the described red chromium complexed acidic dye composite of claim 1; It is characterized in that said general formula (1) dye composition: general formula (2) dye composition: general formula (3) dye composition: weight ratio=5～25% of general formula (4) dye composition: 40～80%: 5～15%: 5～35%; Be preferably 5～20%: 45～75%: 5～15%: 10～30%.
4. the described red chromium complexed acidic dye composite of claim 1 is characterized in that,
R in the general formula (2)
9Group is positioned on the benzene nucleus-contraposition or a position of N=N-group;
R in general formula (1) and the general formula (2)
5, R
11And R
12Group is separately located in respectively on the benzene nucleus-ortho position, a position or the contraposition of N-N-group.
5. the described red chromium complexed acidic dye composite of claim 1 is characterized in that,
R in the general formula (4)
9Group is positioned on the benzene nucleus-contraposition or a position of N=N-group;
R in general formula (3) and the general formula (4)
11And R
12Group is separately located in respectively on the benzene nucleus-ortho position, a position or the contraposition of N-N-group.
6. the red chromium complexed acidic dye composite described in each among the claim 1-4 is characterized in that, the dye composition of general formula (1) expression is:
Dyestuff 1-1
Dyestuff 1-2
Dyestuff 1-3
Dyestuff I-4
Dyestuff I-5
Dyestuff I-6 or
Dyestuff I-7;
The dye composition of general formula (2) expression is:
Dyestuff 2-1
Dyestuff 2-2
Dyestuff 2-3
Dyestuff 2-4
Dyestuff 2-5 or
Dyestuff 2-6.
7. the red chromium complexed acidic dye composite described in each among the claim 1-3 and 5, the dye composition of general formula (3) expression is:
Dyestuff 3-1
Dyestuff 3-2
Dyestuff 3-3
Dyestuff 3-4
Dyestuff 3-5 or
Dyestuff 3-6;
The dye composition of general formula (4) expression is:
Dyestuff 4-1
Dyestuff 4-2
Dyestuff 4-3
Dyestuff 4-4
Dyestuff 4-5 or
Dyestuff 4-6.
8. the preparation method of the described red chromium complexed acidic dye composite of claim 1 is characterized in that it comprises the steps:
1) by 0.8-1.2: the mol ratio of 0.8-1.2: 0.9-1.3 makes general formula (5) and (6) carry out the chromium complex reaction with aqueous solution complex salt, obtains the mixture of the dye composition of general formula (2), general formula (3) and general formula (4) expression; With
General formula (5)
General formula (6)
2) by 95-80: the weight ratio of 5-20 is mixed the dye composition of described mixture with general formula (1) expression.
9. each described red 1:2 chromium complexed acidic dye composite application aspect the dyeing of protein fibre and tynex and BLENDED FABRIC thereof in the claim 1～8.
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| CN111500117A (en) * | 2019-01-31 | 2020-08-07 | 精工爱普生株式会社 | Ink composition for ink jet printing and recording method |
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| CN111057397B (en) * | 2019-12-31 | 2021-08-24 | 浙江科永化工有限公司 | Reactive red dye composition, dye product and application thereof |
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