Background technology
The present invention relates to a kind of navy blue reactive dye composition, by compound synergic, thereby significantly improve its tint applications performance and dyefastness.
One of component of the navy blue reactive dye composition the present invention relates to is a kind of copper-containing metal Jia Za class (Formazan) dyestuff.
Hoechst company in 1986 delivers patent US4607098 and discloses following structure Jia Za type reactive dyestuffs and synthetic method thereof.
This dye structure is different from Hoechst company and delivers the structure of the disclosed Jia Za of patent US4336190 type reactive dyestuffs in nineteen eighty-two.
The structure difference of dyestuff m and dyestuff n is the difference that it becomes number of rings.The former is the dicyclo type, and latter is tricyclic.This patent points out, dicyclo Xing Jia Za type reactive dyestuffs have good tint applications performance.Commendable, the synthetic cost of dyestuff m is far below dyestuff n.
Since tricyclic Jia Za type reactive dyestuffs self-discovery, be subject to the attention of dyestuff circle always.Numerous research shows , Jia Za type reactive dyestuffs, beautiful in colour, is far superior to conventional azo reactive dye.Compare , Jia Za type reactive dyestuffs with anthraquinone type with triphendioxazine type reactive dyestuffs and there is the better and same consistency of dying of other color and luster dyestuffs.
The further development research of dicyclo Xing Jia Za type reactive dyestuffs, be not subject to due attention.
Last century end, Korea S Kyung-In Synthetic Corporation delivered the new structure that patent US5858026 discloses dicyclo Xing Jia Za type reactive dyestuffs in 1999.Its general formula is:
Korean Patent KR20030094982 and KR20040031792 disclose dicyclo Xing Jia Za type reactive dye compositions.This binomial patent report, dicyclo Xing Jia Za type reactive dyestuffs and tricyclic Jia Za type reactive dyestuffs blending, or the inner diverse structure blending of dicyclo Xing Jia Za type reactive dyestuffs, can further improve application performance and some dyefastness of dyestuff.
Up to now, the further further investigation to dicyclo type first Za type reactive dyestuffs, not yet be seen in patent report.
The inventor thinks after having verified by lot of experiments the related content that Korean Patent KR 20030094982 and KR 20040031792 announce, the inner isomery blending of dicyclo Xing Jia Za type reactive dyestuffs and dicyclo Xing Jia Za type reactive dyestuffs and tricyclic Jia Za type reactive dyestuffs carry out blending, really can improve in varying degrees certain tint applications performance.
But practice shows, the reactive dye compositions that Korean Patent KR20030094982 and KR20040031792 provide or miscellany, as the commercial dye kind, the real difficulty of its overall application performance meets the requirement of current printing and dyeing industry.
The inventor is by research trial in earnest, find pleasantly surprisedly, in the miscellany formed at general formula (1) dyestuff and general formula (2-A) dyestuff and/or general formula (2-B) dyestuff, add a kind of disazo dyes kind of copper metal complex of the same type and carry out blending as the 3rd component, can obtain unexpected pleasurable effect.
The structure of the disazo dyes kind of the copper-containing metal that the inventor adopts is as shown in general formula (3).It is blue to grey black that the color and luster of this class dyestuff is.
The time that this class dyestuff is disclosed in patent early.At first the patent of delivering is:
GB?1162144(1969)(Hoechst)、DE?1544538(1970)(Hoechst)。Dyestuff is good at the light fastness excellence.Hewlett-Packard Commpany delivers the at first dye component using this class application as ink for ink-jet print of patent GB 2318798 (1997).Other patent is also announced this reactive dyestuffs kind can make ink for ink-jet print with matching stain, substantive dyestuff blending.
, though dyestuff has excellent dyefastness, there is defect in general formula (3) in dyeing keratin-fiber, and for example level-dyeing property and enhancing rate are to be improved.Bright and lustrous degree has much room for improvement.
The inventor's test practice shows, of the present invention by the dye composition navy blue reactive dye composition that blending forms by a certain percentage shown in dye composition shown in dye composition shown in one or more general formulas (1), one or more general formulas (2-A) or general formula (2-B) and one or more general formulas (3), take in the length of its component dyestuff concurrently, its application performance significantly increases and improves.
Navy blue reactive dye composition of the present invention is with low cost, have excellent dyefastness, adjustable coloured light and good enhancing rate, degree of fixation and other color and luster reactive dyestuffs are with the consistency of dying, therefore, there is wide development space as commercial dye.
The blending data of the copper-containing metal bi-azo active dye shown in general formula (3), can consult following patent:
EP?0668328(1995)(Hoechst)
CN?1444635(2003)(Dystar)
CN?1626582(2005)(Dystar)
CN 101374913 (2009) (Everlight USA, Inc.)
The data of relevant prompting ternary mixture provided by the present invention or composition, be not seen in the patent report.
Summary of the invention
The inventor, by experimental study, is surprised to find the blue active dye compound of the blue active dye compound, one or more general formulas (2-A) or general formula (2-B) expression that contain one or more general formulas (1) and mean and the dark blue dye composition of the black-and-blue reactive dye compound that one or more general formulas (3) mean and has very excellent dyeing behavior and every fastness.
What be worth proposition is, the tint applications performance of navy blue reactive dye composition of the present invention and every dyefastness, take in the length that it forms the characteristic of dyestuff concurrently, make up some defect that it forms dyestuff, navy blue reactive dye composition of the present invention, not only keep its good dyefastness that forms dyestuff, and obvious improvement all occurs in its level-dyeing property, enhancing rate, consistency.Navy blue reactive dye composition of the present invention, cost of manufacture is cheap, can form three primary colors with conventional red, yellow dye and use.Can predict, navy blue reactive dye composition of the present invention has wide prospects for commercial application.
Navy blue reactive dye composition provided by the invention comprises the dye composition that dye composition, one or more general formulas (2-A) or the general formula (2-B) of one or more general formulas (1) expression that certain proportion mixes mean, and the dye composition of one or more general formulas (3) expression:
In formula:
M is H, alkali metal cation or ammonium ion;
Y
1for CH
2cH
2oSO
3m or-CH=CH
2;
X is Cl or F;
P
1, q
1, r
1be respectively 0 or 1 independently;
R
1for H or C
1-C
4alkyl;
R
11and R
12be H, C independently respectively
1-C
4alkyl, C
1-C
4alkoxyl group, Cl or-SO
3m;
In formula:
M is H, alkali metal cation or ammonium ion;
Y
2for-CH
2cH
2oSO
3m or-CH=CH
2;
X is Cl or F;
P
2, q
2and r
2be respectively 0 or 1 independently;
R
2for H or C
1-C
4alkyl;
R
4for H, C
1-C
4alkyl, C
1-C
4alkoxyl group, halogen or hydroxyl;
R
13and R
14be H, C independently respectively
1-C
4alkyl, C
1-C
4alkoxyl group, sulfonic group or Cl.
In formula:
M is H, alkali metal cation or ammonium ion;
Y
3for-CH
2cH
2oSO
3m or-CH=CH
2;
X is Cl or F;
P
3and q
3be respectively 0 or 1 independently;
R
3for H or C
1-C
4alkyl;
R
5for H, C
1-C
4alkyl, C
1-C
4alkoxyl group, halogen or hydroxyl;
R
15and R
16be H, C independently respectively
1-C
4alkyl, C
1-C
4alkoxyl group, sulfonic group or Cl.
In formula:
M is H, alkali metal cation or ammonium ion;
Y
4for-CH
2cH
2oSO
3m or-CH=CH
2;
R
6for H, C
1-C
4alkyl, C
1-C
4alkoxyl group, sulfonic group or Cl;
R
7for H, C
1-C
4alkyl or carboxyl;
R
8for H, sulfonic group or-SO
2y
4group;
R
9and R
10be H, C independently respectively
1-C
4alkyl, C
1-C
4alkoxyl group, sulfonic group or Cl.
The present invention also provides the application of above-mentioned navy blue reactive dye composition at the dyeing aspect of hydroxyl and/or formamido-material, particularly filamentary material.
The dyeing behavior of navy blue reactive dye composition of the present invention all has clear improvement and improves.Dye composite is synthetic with low cost.Dye composite is taken in the length of its component concurrently, and not only enhancing rate and consistency have clear improvement, and can also guard excellent fastness ability.
Specific implementation method
Dye composite of the present invention comprises the dye composition of dye composition, one or more general formulas (2-A) or general formula (2-B) expression that one or more general formulas (1) mean, and the dye composition of one or more general formulas (3) expression.
In dye composite of the present invention, the weight ratio of the dye composition (being called for short dyestuff 2-B) that the dye composition (being called for short dyestuff 2-A) that the dye composition that one or more general formulas (1) mean (being called for short dyestuff 1) and one or more general formulas (2-A) mean or general formula (2-B) mean and the dye composition (being called for short dyestuff 3) of one or more general formulas (3) expression is 5~30: 20~50: 30~70, be preferably 10~30: 20~40: 40~60, more preferably 10~25: 25~40: 45~55.
One preferred embodiment in, general formula (1), general formula (2-A) and general formula (2-B) left side-SO
3the M group, work as p
1, p
2, p
3equal at 1 o'clock, be positioned on benzene nucleus
position or contraposition between group.General formula (1), general formula (2-A) and general formula (2-B) middle part-SO
3the M group, work as r
1, r
2equal at 1 o'clock, position or contraposition between be positioned on benzene nucleus-N=N-group.
Another preferred embodiment in, general formula (1), general formula (2-A) and general formula (2-B) downside-SO
3the M group, work as q
1, q
2, q
3equal at 1 o'clock, be positioned on benzene nucleus
the contraposition of group, a position or ortho position; The R of general formula (2-A) and general formula (2-B) downside
4and R
5, be separately located on benzene nucleus respectively
the contraposition of group, a position or ortho position.
One preferred embodiment in, general formula (1), general formula (2-A), general formula (2-B) right side-SO
2y
1group ,-SO
2y
2group and-SO
2y
3group is separately located on benzene nucleus respectively
group or
group or
the contraposition of group, a position or ortho position.The R on general formula (1), general formula (2-A), general formula (2-B) right side
11, R
12, R
13, R
14, R
15and R
16group is separately located on benzene nucleus respectively
group or
group or
the contraposition of group, a position or ortho position.
Another preferred embodiment in, general formula (3) left side-SO
2y
4position or contraposition between be positioned on benzene nucleus-N=N-group of group; The R in general formula (3) left side
6group, the ortho position of position or be positioned on benzene nucleus-O-group between be positioned on benzene nucleus-N=N-group.
In the present invention, the dye composition that general formula (1) means for example comprises following example:
In the present invention, the dye composition that general formula (2-A) means for example comprises following example:
In the present invention, the dye composition that general formula (2-B) means for example comprises following example:
In the present invention, the dye composition that general formula (3) means for example comprises following example:
General formula (1), general formula (2-A) and the reactive dye compound (2-B) meaned are known dye.
Structure and the synthetic method of the reactive dye compound that general formula (1) means, see following patent:
US?4607098(1986)(Hoechst)
US?5858026(1999)(Kyung-In?Synthetic?Corp)
KR?20030094982
KR20040031792
Structure and the synthetic method of general formula (2-A) and the reactive dye compound that (2-B) means, see following patent:
CN?1422907(2003)(Dystar)
CN?1247707(2006)(Dysrtar)
The full content of above-mentioned document is referred in the present invention.
Structure and the synthetic method of the reactive dye compound that general formula (3) means, see following patent:
GB?1162144(1969)(Hoechst)
DE?1544538(1970)(Hoechst)
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 be comprised of general formula (1) dyestuff of above-mentioned weight ratio and general formula (2) dyestuff and general formula (3) dyestuff.
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 and general formula (3) 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 and general formula (3) 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 affixed 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, 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.
2, 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%
3, 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
4, colour fastness to perspiration test: measure by international standard ISO 105-E04.
5, fastness to soaping test: measure by international standard ISO 105-C10.
6, color fastness to water test: measure by international standard ISO 105-E01.
7, colour fasteness to sunlight test: measure by international standard ISO 105-B02.
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
* reference X is Korean Patent KR20030094982 and the cited embodiment of KR20040031792
* reference Y is (Dystar) cited embodiment of CN 1444635 (2003)
Embodiment 1
The coloured light of navy blue reactive dye composition of the present invention
The dyestuff color and luster that general formula (1) and general formula (2-A) or general formula (2-B) mean is sky blue and color and luster is more shallow, can not be used as the three primary colors blue color component, and the dyestuff color and luster that general formula (3) means is black-and-blue.
The coloured light of reactive dye compositions of the present invention can be adjusted the ratio of general formula (1) dyestuff and general formula (2-A) dyestuff and/or general formula (2-B) dyestuff and general formula (3) dyestuff as required, thereby make mixture effectively with other redness, yellow dyes, form the three primary colors combination, improve its actual application value.
Embodiment 2
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 2
Table 2
From table 2:
Navy blue reactive dye composition of the present invention, compare with the reference dyestuff, and its enhancing rate increases significantly.
Embodiment 3
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 3
Table 3
From table 3:
1) the first rate of dying of navy blue reactive dye composition of the present invention is compared with the reference dyestuff, all make moderate progress, reduced the first rate of dying of reference dyestuff, avoided dying on the dyestuff the too fast look flower phenomenon caused, improve level-dyeing property, shown, red yellow with conventional three primary colors good consistency when dying;
2) navy blue reactive dye composition of the present invention has still kept higher degree of exhaustion.
Embodiment 4
Moving staining index measures
Be determined as follows as stated above the staining index that moves of dyestuff, test result is recorded in table 4
Table 4
From table 4:
Navy blue reactive dye composition of the present invention has good moving and dyes and the level dyeing performance.
Embodiment 5
Colour fastness to perspiration
Be determined as follows as stated above the colour fastness to perspiration of dyestuff, test result is recorded in table 5
Table 5
From table 5:
Navy blue reactive dye composition of the present invention has excellent fastness to perspiration.
Embodiment 6
Fastness to soaping and color fastness to 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 6
Table 6
From table 6:
Navy blue reactive dye composition of the present invention has excellent fastness to soaping and color fastness to water.
Embodiment 7
Sunlight fastness
Be determined as follows as stated above the sunlight fastness of dyestuff, test result is recorded in table 7
Table 7
From table 7:
Navy blue reactive dye composition of the present invention still has good sunlight fastness.