Background technology
The present invention relates to red reactive dye composition and application thereof that a kind of reactive dyestuffs that contain cyanogen ammonia triazinyl participate in composition.
As far back as 1973, Ciba-Geigy company delivered United States Patent (USP) (US 3758470), disclosed the structure and the application characteristic thereof of the reactive dyestuffs that adopt cyanogen ammonia triazinyl.
At the beginning of the nineties in last century, Hoechst company is to structure, the synthetic method of all kinds of reactive dyestuffs that contain cyanogen ammonia triazinyl and should be used as the deep research of system.The patent that Hoechst company delivers continuously has:
US?5015731(1991)(Hoechst)
US?5200512(1993)(Hoechst)
US?5225544(1993)(Hoechst)
US?5290922(1994)(Hoechst)
US?5290923(1994)(Hoechst)
US?5349057(1994)(Hoechst)
WO?90/13603(1990)(Hoechst)
WO?90/13604(1990)(Hoechst)
Above-mentioned patent relates to each class formation that contains cyanogen ammonia triazinyl, the reactive dyestuffs of various color and lusters.Patent shows that all kinds of reactive dyestuffs that contain cyanogen ammonia triazinyl have good enhancing rate and degree of fixation.What be worth proposition is that these class reactive dyestuffs have very excellent every dyefastness, for example light fastness, sweat proof light fastness, fastness to chlorinated water, fastness to chlorine-bleaching, resisting hydrogen peroxide fastness and fastness to hot pressing etc.These class reactive dyestuffs are easy to discharge, have the good antiacid performance of fading.
Hoechst company in US 5225544 (1993) (Hoechst), discloses the red reactive dyes of time array structure in the above-mentioned exploitation that contains cyanogen ammonia triazinyl reactive dyestuffs.
Said structure is the representative structure of the dyestuff of general formula (2) expression.
The another kind of red reactive dyes that the present invention relates to is the dyestuff of general formula (1) expression, and its representative structure is the C.I. REACTIVE Red 195.The structure of this kind at first is published in the patent US 4341699 (1982) that SUMITOMO CHEMICAL company applies for.It is red that this kind coloured light is blue light, has certain dyefastness, and with low cost, thereby the concern on the boundary that extremely prints and dyes.
But secular application practice shows, the defective that this kind dyeing kinetics is slow, reactivity is poor, enhancing rate is low etc., the industrial widespread use that has a strong impact on and incur loss through delay this kind.
In the research that improves the C.I. REACTIVE Red 195, the inventor is by a large amount of tint applications experimental studies, find dyestuff by general formula (1) expression pleasantly surprisedly, red reactive dye composition with the dyestuff of general formula (2) expression is formed with certain proportion has very excellent dyefastness and application performance.
The inventor finds pleasantly surprisedly, the every dyefastness and the application performance of red reactive dye composition of the present invention, not only significantly be better than it and form dyestuff---the dyestuff of general formula (1) expression, and obviously be better than the reactive dye compositions that US 6165231 (2000) (Dystar) is provided.
The inventor confirms, the application performance of red reactive dye composition of the present invention can adapt to harsh day by day printing and dyeing demand effectively, thereby have wide industrial practice prospect.
Summary of the invention
The inventor is by experimental study, and the orchil composition that is surprised to find the red reactive dyes compound of the red reactive dyes compound that contains one or more general formulas (1) expression and one or more general formulas (2) expression has very excellent dyeing behavior and every fastness.
Application data shows that the dyeing behavior of red reactive dye composition of the present invention is compared with its component dyestuff, and tangible lifting and improvement are all arranged.
It should be noted that the dyeing behavior of red reactive dye composition of the present invention, compare, also improve to some extent and improve with the reactive dye compositions that US 6165231 (2000) (Dystar) is provided.
Red reactive dye composition provided by the invention is the dyestuff of general formula (2) expression shown in below the dyestuff of general formula (1) expression shown in below one or more are selected from by combination or blended by a certain percentage and one or more are selected from.
General formula (1)
In the formula:
Z
1For-CH
2CH
2OSO
3M or-CH=CH
2
R
1And R
2Be H, C independently respectively
1-C
4Alkyl, C
1-C
4Alkoxyl group or-SO
3M;
R
3Be H or C
1-C
4Alkyl;
R
4Be H or C
1-C
4Alkyl;
X is Cl, F or NHCN;
M is H or alkali metal cation;
P is 0 or 1;
General formula (2)
In the formula:
Z
2For-CH
2CH
2OSO
3M or-CH=CH
2
R
5And R
6Be H, C independently respectively
1-C
4Alkyl, C
1-C
4Alkoxyl group or sulfonic group;
R
7Be H or C
1-C
4Alkyl;
R
8And R
9Be H, C independently respectively
1-C
4Alkyl, C
1-C
4Alkoxyl group or sulfonic group;
M is H or alkali metal cation.
The present invention also provides the application of above-mentioned red reactive dye composition at the dyeing aspect of hydroxyl and/or formamido-material, particularly filamentary material.
Specific implementation method
In a preferred implementation, form by the dye composition of one or more general formulas (1) expression and the dye composition of one or more general formulas (2) expression in the red reactive dye composition of the present invention.
In reactive dye compositions of the present invention, the dye composition of general formula (1) expression: the weight ratio of the dye composition of general formula (2) expression is 90~10: 10~90, is preferably 70~30: 30~70, be preferably 60~40: 40~60.
One preferred embodiment in, in the general formula (1)-SO
2Z
1Group is positioned on the benzene nucleus
The contraposition of group or a position; R in the general formula (1)
1And R
2Group is separately located on the benzene nucleus respectively
The ortho position of group, contraposition or a position.
Another preferred embodiment in, what link to each other with diazo left side in the general formula (1) is benzene nucleus or naphthalene nuclear derivatives.
One preferred embodiment in, link to each other with diazo left side in the general formula (1) be benzene nucleus the time, p equals 0, R
4Group is positioned on the benzene nucleus-contraposition or a position of N=N-group.
Another preferred embodiment in, link to each other with diazo left side in the general formula (1) examine for naphthalene the time, under the situation of p=1, sulfonic acid group is positioned at 5 that naphthalene is examined; Under the situation of p=0, R
4Group is positioned at 4,5,6 or 7 on the naphthalene nuclear.
One preferred embodiment in, general formula (2) right side-SO
3The M group is positioned on the benzene nucleus
The contraposition of group, a position or ortho position; The R on right side in the general formula (2)
8And R
9Group is separately located on the benzene nucleus respectively
The contraposition of group, a position or ortho position.
Another preferred embodiment in, general formula (2) left side-SO
2Z
2Group is positioned on the benzene nucleus-ortho position, a position or the contraposition of N=N-group; The R in left side in the general formula (2)
5And R
6Group 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 example:
Dyestuff 1-1
Dyestuff 1-2
Dyestuff 1-3
Dyestuff I-4
Dyestuff I-5
Dyestuff I-6
Dyestuff I-7 or
Dyestuff I-8.
The dye composition of general formula (2) expression for example comprises following example:
Dyestuff 2-1
Dyestuff 2-2
Dyestuff 2-3
Dyestuff 2-4
Dyestuff 2-5
Dyestuff 2-6
Dyestuff 2-7 or
Dyestuff 2-8.
The reactive dye compound of general formula (1) and general formula (2) expression is known dye.
Following patent has been announced the structure and the synthetic method thereof of the dyestuff of general formula (1) expression, and they are:
US 4341699 (1982) (Sumitomo)
US 5131917 (1992) (Sumitomo)
JP 5117538 (1993) (Sumitomo)
US 5324329 (1994) (Sumitomo)
US 5359040 (1994) (Sumitomo)
The structure and the synthetic method thereof of the dyestuff of general formula (2) expression can be consulted US 5225544 (1993) (Hoechst)
The full content of above-mentioned document is referred among the present invention.
Red 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 by actual needs, and there is no particular limitation, generally is no more than 20 weight %.For example, electrolyte salt, as sodium sulfate or Repone K, content 0~10 weight %, preferred 2~6 weight %; The pH regulator agent, as SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic, content 0~5 weight %, preferred 0.5~2.5 weight %, dust-proofing agent 0~10 weight %, preferred 0.1~2 weight %; Solubility promoter 1~15 weight %, preferred 0.1~3 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 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 carry out in suitable shredder such as ball mill or needle mill and in kneader or mixing machine.
Red reactive dye composition of the present invention is suitable for dyeing and various widely material thereof, the material that particularly contains 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.
Red reactive dye composition of the present invention can be applied to filamentary material and is affixed 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
Every testing method of embodiment
Every performance of present embodiment is tested by following every testing method
1, woolen dyed enhancing rate test:
Wool yarn is pressed 98 ℃ of heating process dyeing of matching stain, 0.5%, 1%, 2%, 4%o.w.f (dyestuff is heavy to fabric).Dyeing back fabric is tested its Apparent Depth K/S value and record with the Datacolor color measurement instrument after fixed temperature and humidity is handled.
2, colour fastness to perspiration test: measure by international standard ISO 105-E04.
3, fastness to soaping test: measure by international standard ISO 105-C10.
4, color fastness to water test: measure by international standard ISO 105-E01.
5, colour fasteness to sunlight test: measure by international standard ISO 105-B02.
Dye type shown in the according to the form below 1 and consumption thereof by ordinary method uniform mixing in this area, are prepared the various red reactive dye compositions of the embodiment of the invention with various dye components.
" % " in the table 1 all represents weight %, is benchmark with the gross weight of dye composite.
Table 1
Numbering |
The reactive dyestuffs title |
Form |
1 |
A |
70% dyestuff 1-1+30% dyestuff 2-1 |
2 |
B |
50% dyestuff 1-1+50% dyestuff 2-1 |
3 |
C |
30% dyestuff 1-1+70% dyestuff 2-1 |
4 |
D |
70% dyestuff 1-4+30% dyestuff 2-4 |
5 |
E |
50% dyestuff 1-4+50% dyestuff 2-4 |
6 |
F |
30% dyestuff 1-4+70% dyestuff 2-4 |
7 |
Reference X |
100% dyestuff 1-1 |
8 |
Reference Y |
100% dyestuff 2-1 |
9 |
Reference Z |
50% reactive red C.I.195+50% reactive red C.I.198 |
* reference Z is (Dystar) cited embodiment of US 6165231 (2000).
Embodiment 1
Woolen dyed enhancing rate test (the K/S value at absorbing wavelength 520nm place)
Measure the enhancing rate of following dyestuff as stated above, test result is recorded in the table 2
Table 2
By table 2 as seen:
1) red reactive dye composition of the present invention is used for woolen dyed going up and shows its excellent application performance.
2) red reactive dye composition of the present invention all apparently higher than its weighted mean of forming dyestuff, embodies the effect of compound synergic at woolen dyed enhancing rate measured value.
3) red reactive dye composition of the present invention, its enhancing rate on wool is apparently higher than (Dystar) conventional dye combinations of US 6165231 (2000).Consult the dyeing enhancing rate data of dye composite B and dye composite reference Z in the table 2.
Embodiment 2
Colour fastness to perspiration
Measure the colour fastness to perspiration of following dyestuff as stated above, test result is recorded in the table 3
Table 3
By table 3 as seen:
Red reactive dye composition of the present invention has good fastness to perspiration.
Embodiment 3
Fastness to soaping and color fastness to water
Measure fastness to soaping, color fastness to water and the color fastness to sea water of following dyestuff as stated above, test result is recorded in the table 4
Table 4
By table 4 as seen:
Red reactive dye composition of the present invention has good fastness to soaping and color fastness to water, is better than the corresponding fastness of dye composite reference Z.
Embodiment 4
Sun-resistant fastness
Measure the sun-resistant fastness of following dyestuff as stated above, test result is recorded in the table 5
Table 5
By table 5 as seen:
Red reactive dye composition of the present invention has good sun-resistant fastness.