Navy blue reactive dye composition and the tint applications on fiber thereof
Technical field
The present invention relates to a kind of reactive dye compositions and the tint applications on filamentary material thereof.Particularly, the present invention relates to navy blue reactive dye composition and the tint applications on filamentary material thereof.
Background technology
Triphendioxazine type reactive dyestuffs are continue the new color system of Application and Development after prevailing anthraquinone type reactive dyestuffs in blue active dye for many years.
The coloring intensity of triphendioxazine type reactive dyestuffs, higher than anthraquinone type and azo reactive dye, is 4-6 times of anthraquinone type, and coloured light vividness and anthraquinone type approach, and fiber is had to very high substantivity.
The triphendioxazine precursor structure, for plane, linear ring more than five yuan, be orange.Introduce amino or substituent amino to precursor structure, be blue.As introduce hydroxyl or alkoxyl group, take on a red color.These groups of introducing generally double as the abutment of active group simultaneously.
The triphendioxazine blue active dye is dye wherein with fastest developing speed.External each major company, as the companies such as Bayer, Hoechst, Sumitomo, vapour bar, De Sida are all competitively delivering numerous patents aspect the new variety of this class blue active dye of exploitation.
The characteristics of triphendioxazine type blue active dye are bright-coloured, the excellent every fastness of coloured light and good dyeability.The development research of current these class blue active dye new variety mainly concentrates on and improves degree of fixation, adapts to low salt dyeing, improves level-dyeing property and consistency and improve fastness to chlorine-bleaching and light fastness.It should be noted that the chemosynthesis complexity of triphendioxazine type blue active dye.Wherein the oxidation ring-closure reaction is essential step.Reaction not only relates to the purity of product but also affects the vividness of dyestuff.The spent acid that reaction produces has a strong impact on environmental protection.This is also the focus of each major company's research and development.
Another approach that improves the defect of triphendioxazine type blue active dye be adopt with the same color and luster of other type or heterochromatic damp reactive dyestuffs carry out composite, to learning from other's strong points to offset one's weaknesses, reduce the cost, the broadened application scope, give full play to its characteristics.
The patent that external each major company delivers aspect composite has:
US 4705524(1987)(Hoechst)
US 4834769(1989)(Sandoz)
JP 1043567 (1989) (Sumitomo)
US 5085668(1992)(Hoechst)
US 5207801(1993)(Ciba-Geigy)
US 0603823 (1993) (Sumitomo)
JP 5032912 (1993) (Sumitomo)
US 5352246(1994)(Hoechst)
US 5346510(1994)(BASF)
JP 6192589 (1994) (Sumitomo)
US 5484459(1996)(Hoechst Celanese)
US 5456726 (1996) (Sumitomo)
DE 19505742(1996)(Bayer)
JP 11071534 (1999) (Sumitomo)
JP 11172133 (1999) (Sumitomo)
JP 11199792 (1999) (Sumitomo)
JP 2001098183 (2001) (Sumitomo)
US 6358287(2002)(Dystar)
US 6800099(2004)(Dystar)
The composite composition dyestuff that these patents adopt is, azo-type, anthraquinone type, first
type and phthalocyanine type reactive dyestuffs, and the triphendioxazine reactive dyestuffs of diverse structure.
The triphendioxazine type blue active dye the present invention relates to, be the kind of early development, and part commercialization puts goods on the market.Its structural formula is shown in general formula (1).Disclose this dye structure and preparation method and be stated from following patent:
US 4705524(1987)(Hoechst)
US 4782150(1988)(Hoechst)
US 4774333(1988)(Hoechst)
US 4785098(1988)(Hechst)
US 4845213(1989)(Bayer)
US 4885385(1989)(Hoechst)
The triphendioxazine type blue active dye kind that the inventor shows topic carries out finding after lot of experiments, and the triphendioxazine type blue active dye kind coloured light that topic is shown is gorgeous, have excellent dyefastness and good enhancing rate.
But regrettably, topic show the level-dyeing property of dyestuff poor, due to the coloured light reason, be difficult to and other color and luster forms three primary colors, affect its range of application, and the part fastness, for example fastness to chlorine remains further to be improved.It should be noted that topic shows the preparation of dyestuff difficulty, cost is higher, and the production serious three wastes remains synthesis technique further to be improved.
For this reason, the present invention successfully adopts the approach of composite dye composite, and the improvement topic is shown the above-mentioned defect of dyestuff, and the maintenance topic is shown the original characteristics of dyestuff, reduces costs the broadened application scope.
The inventor is by a large amount of experiments, find pleasantly surprisedly, the dyestuff meaned by the dyestuff by general formula (2) expression and general formula (1) carries out the approach of composite dye composite, the improvement topic is shown the defect of dyestuff effectively, the maintenance topic is shown the original characteristics of dyestuff, reduce costs the broadened application scope.
The dyestuff that adopts general formula (2) to mean carries out composite, is not seen in patent and document record.
The series dye that general formula (2) means, be known dye, is stated from following patent:
US 5849887(1998)(Ciba Speciality Chemicals Corp.)
US 6537332(2003)(Ciba Speciality Chemicals Corp.)
CN 101215427 (2008) (Tianjin De Kai company)
CN 10148133 (2009) (Tianjin De Kai company)
CN 101481530 (2009) (Tianjin De Kai company)
Summary of the invention
The inventor by a large amount of research trials after, find the dye composite that one or more dark blue reactive dye compounds of general formula (1) expression and one or more dark blue reactive dye compounds that general formula (2) means form pleasantly surprisedly, there is very excellent dyeing behavior and every dyefastness.
What be worth proposition is, this navy blue reactive dye composition is compared with its composition dyestuff, not only keep the original excellent dyefastness of dye composition shown in general formula (1), and significantly improve its level dyeing performance and consistency, thereby effectively expand its Application Areas.
Be, navy blue reactive dye composition of the present invention can be adjusted coloured light effectively particularly pleasantly surprisedly, and can form three primary colors with yellow, the red reactive dyes kind of each routine.
Navy blue reactive dye composition provided by the invention comprise that certain proportion mixes one or more be selected from below shown in the dye composition that means of general formula (1) and one or more be selected from below shown in the dye composition that means of general formula (2).
general formula (1)
In formula:
R
1and R
2be H or Cl independently respectively, be preferably Cl;
Z
1and Z
2be independently-CH respectively
2cH
2oSO
3m or-CH=CH
2;
X is-OSO
3m,
or-NHCO-V-COOM;
Y is-(CH
2)
n-group;
V is-(CH
2)
m-group;
N and m are respectively an integer in 1~4 independently, are preferably 2 or 3;
M is H or alkali metal cation, is preferably H, potassium or sodium ion, more preferably sodium ion.
General formula (2)
In formula:
T is-NHCOQ or-SO
2z
3;
Q is-CHWCH
2w or-CW=CH
2;
W is Cl or Br, is preferably Br;
Z
3for-CH
2cH
2oSO
3m ,-CH=CH
2,-CH
2cH
2oH or-CH
2cH
2cl, be preferably-CH
2cH
2oSO
3m or-CH=CH
2;
R
3and R
4be H, halogen, C independently respectively
1-C
4alkyl, C
1-C
4alkoxyl group, sulfonic group, be preferably H, C
1-C
2alkoxyl group or sulfonic group;
R
5for sulfonic group;
P is 0,1 or 2, is preferably 1.
M is H or alkali metal cation.
The present invention also provides the application of above-mentioned navy blue reactive dye composition aspect cellulose base fiber fabric dyeing.
Navy blue reactive dye composition provided by the invention has excellent dyeing behavior and every dyefastness, and commonly used red with other, the consistency of the excellence that Yellow active dye dyes altogether.
Embodiment
Dye composite of the present invention comprises the dye composition of one or more general formulas (1) expression and the dye composition that one or more general formulas (2) mean.
In dye composite of the present invention, the dye composition that general formula (1) means (being called for short the dyestuff I) is 90-10: 10-90, preferably 70-30: 30-70 with the weight ratio of the dye composition (being called for short the dyestuff II) that general formula (2) means.
One preferred embodiment in, general formula (1) is selected from as X
during group ,-SO
3be positioned on benzene nucleus-(CH of M group
2)
nthe ortho position of-group, a position or contraposition; In general formula (1), X is selected from
during group ,-SO
3be positioned on benzene nucleus-(CH of M group
2)
nthe ortho position of NHCO-group, a position or contraposition.
Another preferred embodiment in, in general formula (2), R
3group and R
4ortho position, a position or the contraposition of be separately located in respectively on benzene nucleus-N=N-group of group.
One preferred embodiment in, in general formula (2), R
5ortho position, a position or the contraposition of be positioned on benzene nucleus-N=N-group of group.
Another preferred embodiment in, in general formula (2), ortho position, a position or the contraposition of be positioned on benzene nucleus-N=N-group of-NHCOQ group.
In the present invention, the dye composition that general formula (1) means for example comprises following example:
In the present invention, the dyestuff that general formula (2) means for example comprises following example:
The reactive dyestuffs that general formula (1) and general formula (2) mean are known dye.
Structure and the synthetic method of the reactive dyestuffs that general formula (1) means, see following patent:
US 4705524(1987)(Hoechst)
US 4782150(1988)(Hoechst)
US 4774333(1988)(Hoechst)
US 4785098(1988)(Hoechst)
US 4845213(1989)(Bayer)
US 4885385(1989)(Hoechst)
Structure and the synthetic method of the reactive dyestuffs that general formula (2) means, see following patent:
US 5849887(1998)(Ciba Speciality Chemicals Corp.)
US US 6537332(2003)(Ciba Speciality Chemicals Corp.)
CN 101215427 (2008) (Tianjin De Kai company)
CN 10148133 (2009) (Tianjin De Kai company)
CN 101481530 (2009) (Tianjin De Kai company)
The full content of above-mentioned document is referred in the present invention.
Navy blue reactive dye composition 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 according to actual needs, and there is no particular limitation, generally is no more than 20 % by weight.For example, electrolyte salt, as sodium sulfate or Repone K, content 0~10 % by weight, preferably 2~6 % by weight; PH adjusting agent, as SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic, content 0~5 % by weight, preferred 0.5~2.5 % by weight, dust-proofing agent 0~10 % by weight, preferred 0.1~2 % by weight; Solubility promoter 1~15 % by weight, preferred 0.1~3 % by weight.The present composition also can be basically by general formula (1) dyestuff of above-mentioned weight ratio with general formula (2) dyestuff forms or be comprised of general formula (1) dyestuff and general formula (2) dyestuff of above-mentioned weight ratio.
The preparation method of navy blue reactive dye composition of the present invention comprises above-mentioned general formula (1) dyestuff and general formula (2) dyestuff weight ratio is in accordance with regulations mixed.Mix available various ordinary method, as the mechanically mixing method.During mixing, general formula (1) dyestuff and general formula (2) dyestuff can powder types, or with particle form, or exist with aqueous solution form.For example, mixing step can suitable shredder as ball mill or needle mill in and in kneader or mixing machine, carry out.
Navy blue reactive dye composition of the present invention is suitable for dyeing and various materials widely thereof, particularly contain the material of carboxylic acid and/or formamido-, filamentary material more especially, for example cotton, flax and hemp fibre, and Mierocrystalline cellulose and regenerated cellulose, polyester or polyamide fiber material etc.
Navy blue reactive dye composition of the present invention can be applied to filamentary material and be fixed on fiber by several different methods as known in the art, for example can be dyeed by dip-dye method or pad dyeing method.
Embodiment
Every testing method of embodiment
The properties of the present embodiment is tested by following every testing method
1, Salt And Alkali Tolerance solubleness: take a certain amount of dyestuff, add distilled water 65mL to be configured to dye liquor in the 250mL Erlenmeyer flask.Erlenmeyer flask is put in the vibration dyeing machinery, after 60 ℃ of insulation 5min, adds 200g/L Na
2sO
425mL, continue to add 200g/LNa after insulation 5min
2cO
310mL, then carry out suction filtration (during suction filtration, pressure 0.075Mpa, 5A qualitative filter paper) after being incubated 30min, observe the filter paper residual condition.Reduce dye strength (G/L), until residual without dyestuff on filter paper, the Salt And Alkali Tolerance that dye strength now (G/L) is dyestuff dissolves.
2, enhancing rate test: pure cotton fabric is pressed to 60 ℃ of constant temperature dyeings of reactive dyestuffs, and dyeing concentration is 0.5%, 1%, 2%, 4%, 6%o.w.f (dyestuff is to the fabric weight).After dyeing, fabric, after fixed temperature and humidity is processed, is tested its Apparent Depth K/S value record with the Datacolor color measurement instrument.
3, degree of fixation test: the dye liquor preparation, press 60 ℃ of constant temperature dyeings of reactive dyestuffs.After dyeing finishes, the cloth specimen in the B dye bath is carried out to washing according to the following steps, and by dyeing residual liquid, the washing raffinate of each step concentrates on constant volume in the volumetric flask of a 500mL.When B dye bath cloth specimen carries out soap boiling, in the A dye bath, also add the detergent of same amount to carry out soap boiling.The A dye bath is cooled to room temperature after soaping and finishing, and constant volume is 500mL.A after constant volume, B dyeing residual liquid are diluted to certain multiple MA, MB, test absorptance values XA, the XB of its diluent when maximum absorption wavelength (XA, XB should between 0.2~0.7).
The * 100% of degree of fixation=(1-XBMB/XAMA)
4, just dye rate and degree of exhaustion test: the dye liquor preparation, press 60 ℃ of constant temperature dyeings of reactive dyestuffs.Respectively before adding alkali and on dye and finish to sample before soap boiling, measure the absorbance of dyeing residual liquid, with dye liquor absorbance before dyeing relatively.
Just dye rate=(1-adds the absorbance of the absorbance of dye liquor before alkali/front dye liquor of dyeing) * 100%
Degree of exhaustion=the absorbance of dye liquor before the absorbance of front dye liquor/dyeing (1-soap) * 100%
5, move the test of staining index MI value: two onesize A, B cloth specimen are dropped into and be added with in the dye bath of dyestuff, sodium sulfate, after 60 ℃ of dyeing 30min, take out the B cloth specimen, the B cloth specimen is put in the blank dye bath that only contains sodium sulfate, put into onesize calico C simultaneously, continue to add sodium carbonate fixation 60min after dyeing (move and dye) 20min.The color strength (K/S) that compares B cloth specimen and C cloth specimen.
Move color strength (K/S) * 100% of the color strength (K/S) of staining index MI=C cloth specimen/B cloth specimen
6, colour fastness to chlorinated water test: measure by international standard ISO 105 E03.
7, colour fastness to perspiration test: measure by international standard ISO 105-E04.
8, fastness to soaping test: measure by international standard ISO 105-C10.
9, color fastness to water test: measure by international standard ISO 105-E01.
10, color fastness to sea water test: measure by international standard ISO 105-E02.
11, colour fasteness to sunlight test: measure by international standard ISO 105-B02.
12, the photochromic fastness test of sweat proof: measure by Japanese standard JIS L0888.
Dye type shown according to the form below 1 and consumption thereof evenly mix various dye components by ordinary method in this area, the various navy blue reactive dye compositions of the preparation embodiment of the present invention.
" % " in table 1 all means % by weight, and the gross weight of dye composite of take is benchmark.
Table 1
Numbering |
The reactive dyestuffs title |
Form |
1 |
A |
70% dyestuff I-2+30% dyestuff II-1 |
2 |
B |
50% dyestuff I-2+50% dyestuff II-1 |
3 |
C |
30% dyestuff I-2+70% dyestuff II-1 |
4 |
D |
70% dyestuff I-1+30% dyestuff II-3 |
5 |
E |
50% dyestuff I-1+50% dyestuff II-3 |
6 |
F |
30% dyestuff I-1+70% dyestuff II-3 |
7 |
Reference W |
100% dyestuff I-2 |
8 |
Reference X |
100% dyestuff I-1 |
9 |
Reference Y |
100% dyestuff II-1 |
10 |
Reference Z |
100% dyestuff II-3 |
Embodiment 1
The coloured light of navy blue reactive dye composition of the present invention
The dyestuff color and luster that logical formula I means is bright-coloured blueness, because coloured light is very gorgeous, is not suitable for use in three primary colors, and range of application is less, and the dyestuff color and luster that logical formula II means is dark navy.
The coloured light of reactive dye compositions of the present invention can be adjusted the ratio of logical formula I dyestuff and logical formula II dyestuff as required, thereby makes mixture effectively with other redness, yellow dyes, form the three primary colors combination, improves its actual application value.
Embodiment 2
The test of Salt And Alkali Tolerance solubleness
Be determined as follows as stated above the Salt And Alkali Tolerance solubleness of dyestuff, test result is recorded in table 2.
Table 2
From table 2:
Navy blue reactive dye composition of the present invention, have Salt And Alkali Tolerance solubleness preferably, and level-dyeing property is better.
Embodiment 3
Enhancing rate test (the K/S value at absorbing wavelength 620nm place)
Be determined as follows as stated above the enhancing rate of dyestuff, test result is recorded in table 3.
Table 3
From table 3:
1) navy blue reactive dye composition of the present invention, compare with the dyestuff that logical formula I means, its enhancing rate significantly improves;
2) the enhancing rate measured value of navy blue reactive dye composition of the present invention, be much higher than the weighted mean that it forms dyestuff, embodied the effect of compound synergic.
Embodiment 4
Degree of fixation is measured
Be determined as follows as stated above the degree of fixation of dyestuff, test result is recorded in table 4.
Table 4
From table 4:
Navy blue reactive dye composition of the present invention, still can keep higher degree of fixation.
Embodiment 5
Just dying rate and degree of exhaustion measures
Be determined as follows as stated above first rate and the degree of exhaustion of dying of dyestuff, test result is recorded in table 5.
Table 5
From table 5:
1) the navy blue reactive dye composition of the present invention first rate of dying is compared with the dyestuff that general formula (1) means with degree of exhaustion, all increases and improves, and shows, red yellow with conventional three primary colors good consistency when dying;
2) first rate and the degree of exhaustion measured value of dying of navy blue reactive dye composition of the present invention, the weighted mean that all higher than it, forms dyestuff, illustrate that dye composite has better dyeing capacity, is conducive to the set of dyestuff.
Embodiment 6
Moving staining index measures
Be determined as follows as stated above the staining index that moves of dyestuff, test result is recorded in table 6.
Table 6
From table 6:
Navy blue reactive dye composition of the present invention has improved the poor problem of reactive dyestuffs migration property that logical formula I means, has good level-dyeing property.
Embodiment 7
The chlorinated water resist fastness
Be determined as follows as stated above the colour fastness to chlorinated water of dyestuff, test result is recorded in table 7.
Table 7
From table 7:
Navy blue reactive dye composition of the present invention has good chlorinated water resist fastness, can effectively improve the poor problem of dyestuff chlorinated water resist fastness that logical formula I means.
Embodiment 8
Colour fastness to perspiration
Be determined as follows as stated above the colour fastness to perspiration of dyestuff, test result is recorded in table 8.
Table 8
From table 8:
Navy blue reactive dye composition of the present invention has excellent fastness to perspiration.
Embodiment 9
Fastness to soaping, color fastness to water and color fastness to sea water
Be determined as follows as stated above fastness to soaping, color fastness to water and the color fastness to sea water of dyestuff, test result is recorded in table 9.
Table 9
From table 9:
Navy blue reactive dye composition of the present invention has excellent fastness to soaping, color fastness to water and color fastness to sea water.
Embodiment 10
Sunlight fastness
Be determined as follows as stated above the sunlight fastness of dyestuff, test result is recorded in table 10.
Table 10
From table 10:
The characteristics of the dyestuff that navy blue reactive dye composition of the present invention still keeps logical formula I to mean, have good sunlight fastness.
Embodiment 11
The photochromic fastness of sweat proof
Be determined as follows as stated above the photochromic fastness of sweat proof of dyestuff, test result is recorded in table 11.
Table 11
From table 11:
The characteristics of the dyestuff that navy blue reactive dye composition of the present invention still keeps logical formula I to mean, have good sweat proof light fastness.