CN104194385A - Azo 1:2 metal complex dye composition and application thereof in dyeing - Google Patents
Azo 1:2 metal complex dye composition and application thereof in dyeing Download PDFInfo
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- CN104194385A CN104194385A CN201410409169.2A CN201410409169A CN104194385A CN 104194385 A CN104194385 A CN 104194385A CN 201410409169 A CN201410409169 A CN 201410409169A CN 104194385 A CN104194385 A CN 104194385A
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Abstract
The invention provides an azo 1:2 metal complex dye composition and application thereof in dyeing. The dye composition comprises one or more dye compounds disclosed as general formula (1) and one or more dye compounds disclosed as general formula (2). Compared with the dyes disclosed as general formula (I), the homochromatism of the nylon/wool blend fabric initial bath dyeing of the azo 1:2 metal complex dye composition is obviously enhanced and improved, and the compatibility is obviously improved. The azo 1:2 metal complex dye composition is especially suitable for dyeing of sensitive color systems, thereby greatly widening the dyeing application range of the dye composition.
Description
Technical field
The present invention relates to a kind of azo-group 1:2 metallized dye composition and tint applications thereof.Particularly, the present invention relates to a kind of azo-group 1:2 chromium complex dyestuff composition and tint applications thereof.
Background technology
The present invention relates to a kind of single sulfonic acid type 1:2 metallized dye composition and tint applications thereof.
By China's classification, 1:2 metallized dye can be divided into K type (without sulfonic group), S type (single sulfonic group) and M type (disulfonic acid base) 1:2 metallized dye.S type (single sulfonic group) 1:2 metallized dye is compared with another 2 class dyestuffs, has good overall quality index, such as level-dyeing property, water-soluble, wet colour fastness etc.This class dyestuff is with low cost owing to synthesizing, dyeing is easy, the pollution of non-hexavalent chromium, thereby is widely used in the printing and dyeing of the fibers such as silk, wool and polyamide fibre and fabric.
In practice of the present invention, the inventor notices some black S type 1:2 chromium complex dyestuff kinds.The dye composition of these kinds as shown in general formula of the present invention (1).Its Representative Cultivars is C.I.Acid Black 107 (neutral black BGL) and C.I.Acid Black 168 (neutral black BL).These dye compositions have good dyeing behavior and fastness.But practice shows, is cited as regrettably, these dye compositions and of the same type or foreign peoples's type dye kind consistency is poor, thereby greatly limit the tint applications scope of numerous each color and lusters of its blending.
The inventor is on the basis of lot of experiments research, find to contain the composition of dye composition that a certain proportion of one or more general formulas (1) represent and the dye composition of one or more general formulas (2) expression pleasantly surprisedly, not only keep original every excellent dyefastness, level-dyeing property and water-soluble, and there is good consistency, particularly it,, in nylon/wool mixed fibre one-bath process, has splendid dyeing homochromatism.Thereby expand widely the tint applications scope of dye composite of the present invention.
Summary of the invention
The inventor is on the basis of a large amount of research trials, find pleasantly surprisedly, the dye composite that the azo-group 1:2 metallized dye compound that the azo-group 1:2 metallized dye compound that one or more general formulas (1) represent and one or more general formulas (2) represent etc. form, has excellent dyeing behavior and dyefastness.
It should be noted that azo-group 1:2 metallized dye composition of the present invention improves and improve consistency and the level-dyeing property of the azo-group 1:2 metallized dye compound of general formula (1) expression, thereby greatly expand the latter's tint applications field.
Azo-group 1:2 metallized dye composition provided by the invention, comprise that certain proportion mixes be selected from below shown in the dye composition that represents of general formula (1) and be selected from below shown in the dye composition that represents of general formula (2).
In formula:
R
1be selected from hydrogen atom or NHCOCH
3group;
R
2and R
3respectively independently selected from H, Cl or NO
2group;
Q is selected from alkali metal cation, is preferably sodium or potassium ion;
In formula:
R
4, R
5and R
6respectively independently selected from H, Cl or NO
2group;
Q is selected from alkali metal cation, is preferably sodium or potassium ion.
Azo-group 1:2 metallized dye composition provided by the invention, compare with the dyestuff that the logical formula I of its composition represents, the homochromatism of its nylon/wool BLENDED FABRIC one-bath process is significantly improved and improves, its consistency is also significantly improved, be particularly suitable for the dyeing of responsive colour system, thereby greatly expand the tint applications scope of dye composite of the present invention.
The present invention also provides the tint applications of above-mentioned azo-group 1:2 metallized dye composition in wool fabric, polyamide fabric and BLENDED FABRIC thereof.
Specific implementation method
One preferred embodiment in, the dye composition that azo-group 1:2 metallized dye composition of the present invention is represented by general formula (1) and general formula (2) forms in certain proportion.
In azo-group 1:2 metallized dye composition of the present invention, the weight ratio of the dye composition that the dye composition that general formula (1) represents and general formula (2) represent is 10～60%:90～40%, be preferably 15～55%:85～45%, more preferably 20～50%:50～80%.
One preferred embodiment in, the R in general formula (1)
2group, be positioned at azo group on benzene nucleus between position or contraposition; R in general formula (1)
3group, is positioned at 5 or 6 on naphthalene core; R in general formula (1)
1group, is respectively H or NHOCH
3group.
Another preferred embodiment in, the R in general formula (2)
4group, be positioned at azo group on benzene nucleus between position or contraposition; R in general formula (2)
5and R
6group, be separately located in respectively azo group on benzene nucleus between position or contraposition.
In the present invention, the dye composition that general formula (1) represents, for example, comprise following example:
In the present invention, the dye composition that general formula (2) represents, for example, comprise following example:
The azo-group 1:2 metallized dye compound that general formula (1) and general formula (2) represent is all known dye.
The azo-group 1:2 metallized dye compound that general formula (1) represents, its structural formula forms and synthetic method can be consulted following paper:
1) Zhang Shanzhong, synthetic [J] dyestuffs industries of neutral black BGL (C.I.Acid Black 107), 2000,37 (2): 4-6;
2) Zhang Manli, Zhao Jinyu, neutral black BL synthetic technology report [J] Dandong chemical industry, 1995,4,5-8,12;
The azo-group 1:2 metallized dye compound that general formula (2) represents, its structural formula forms and synthetic method can be consulted following paper:
Sun Guichun, synthetic [J] dyestuff and dyeing 2008,45 (6): the 1-3 of asymmetric 1:2 metallized dye (C.I. Basic Blue 3 17).
The full content of above-mentioned document is referred in the present invention.
Azo-group 1:2 metallized 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, is generally 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 substantially 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 azo-group 1:2 metallized 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 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.
Azo-group 1:2 metallized 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 dye by dip-dye method or printing method.
Embodiment
Every testing method of embodiment
The properties of the present embodiment is tested by following every testing method
1, wool/nylon BLENDED FABRIC homochromatism test: by proportion of composing 80W/20N, wool/nylon BLENDED FABRIC of grammes per square metre 600g/m (felt cloth (purchased from Hangzhou Hua Beina company)), press after matching stain normal dyeing technique co-bathing dyeing, cloth cover to fabric is graded with chromatic effect, be divided in good and differ from 4 ranks, wherein excellently represent that cloth cover Dry Sack is even, there is no obvious heterochromatic streak; Poor expression cloth cover has significant heterochromatic phenomenon.
2, enhancing rate test: nylon knitting fabric is pressed to 98 ℃ of constant temperature dyeings of matching stain, and dyeing concentration is 0.1%, 0.5%, 1%, 2%, 4%o.w.f (dyestuff is to fabric weight).After dyeing, fabric, after fixed temperature and humidity is processed, is tested its Apparent Depth K/S value record with Datacolor color measurement instrument.
3, solubleness: take 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) with mechanical stirrer stirring after 5 minutes, observe filter paper residual condition.Reduce dye strength (G/L), until residual without dyestuff on filter paper, dye strength now (G/L) is the solubleness of dyestuff.
4, dyeing nylon exhaustion rate test: dye liquor preparation, by the acid dyeing dyeing of nylon.After dyeing finishes, test respectively the absorbancy of dyeing residual liquid and the absorbance (MTD 1%o.w.f.) of the front dye liquor of dyeing.
Exhaustion rate=(absorbance of the front dye liquor of absorbance/dyeing of dye liquor after 1-dyeing) * 100%
6, colour fastness to chlorinated water test: by dyeing nylon fabric, measure by international standard ISO 105E03.
7, sunlight fastness test: by dyeing nylon fabric, measure by international standard ISO 105-B02.
8, compatibility test: dyestuff of the present invention and turmeric yellow and Xylene Red are combined into coffee color, by the acid dyeing dyeing of nylon.Sectional sampling in dyeing course, according to the colouring situation of dying each stage in process on whole, dyes the quality of synchronism in judge, be divided into successively in good and differ from 4 ranks.On whole, dye in process, the form and aspect of each stage sampling do not have obvious difference, are only the difference of the depth, can be assessed as excellent; If there is obvious form and aspect difference, represent that the colouring synchronism of three kinds of dyestuffs is inconsistent, it is poor to be assessed as.
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 acid dye compositions of the preparation embodiment of the present invention.
" % " in table 1 all represents % by weight, and the gross weight of dye composite of take is benchmark.
Table 1
| Numbering | Dyestuff title | Form |
| 1 | A | 35% dyestuff 1-1+65% dyestuff 2-1 |
| 2 | B | 20% dyestuff 1-3+80% dyestuff 2-1 |
| 3 | C | 20% dyestuff 1-1+20% dyestuff 1-2+60% dyestuff 2-1 |
| 4 | D | 15% dyestuff 1-3+15% dyestuff 1-5+70% dyestuff 2-1 |
| 5 | E | 25% dyestuff 1-3+25% dyestuff 1-5+50% dyestuff 2-1 |
| 6 | Reference X | Dyestuff 1-1 |
| 7 | Reference Y | Dyestuff 2-1 |
Embodiment 1
The coloured light of azo-group 1:2 metallized dye composition of the present invention
Azo-group 1:2 metallized dye composition of the present invention, the ratio of the dyestuff that the dyestuff representing by fine setting general formula (1) and general formula (2) represent, can obtain the dye composite of the color and lusters such as dark navy, pewter, grey black, the dyeing and printing process of the textiles that is applicable to low key tone.The concrete color and luster of the present embodiment dye composite refers to described in following table 2:
Table 2
| Numbering | Dyestuff title | Form | Color and luster |
| 1 | A | 35% dyestuff 1-1+65% dyestuff 2-1 | Pewter |
| 2 | B | 20% dyestuff 1-3+80% dyestuff 2-1 | Mazarine |
| 3 | C | 20% dyestuff 1-1+20% dyestuff 1-2+60% dyestuff 2-1 | Grey black |
| 4 | D | 15% dyestuff 1-3+15% dyestuff 1-5+70% dyestuff 2-1 | Pewter |
| 5 | E | 25% dyestuff 1-3+25% dyestuff 1-5+50% dyestuff 2-1 | Black |
Embodiment 2
The test of wool/nylon BLENDED FABRIC homochromatism
Be determined as follows as stated above wool/nylon BLENDED FABRIC homochromatism, test result is recorded in table 3
Table 3
From table 3:
Azo-group 1:2 metallized dye composition of the present invention is compared compared with reference dyestuff, extremely remarkable with chromatic effect, has significant synergy phenomenon in this performance.
Embodiment 3
Enhancing rate test (the K/S value at absorbing wavelength 590nm place)
The enhancing rate that is determined as follows as stated above dyestuff, test result is recorded in table 4
Table 4
From table 4:
Azo-group 1:2 metallized dye composition of the present invention, has still kept splendid dyeing enhancing rate.
Embodiment 4
Solubleness test
The solubleness that is determined as follows as stated above dyestuff, test result is recorded in table 5
Table 5
From table 5:
Azo-group 1:2 metallized dye composition of the present invention, has good solubleness, and level-dyeing property is better.
Embodiment 5
Dyeing nylon exhaustion rate is measured
The exhaustion rate that is determined as follows as stated above dyestuff, test result is recorded in table 6
Table 6
From table 6:
Azo-group 1:2 metallized dye composition of the present invention has splendid dyeing exhaustion rate.
Embodiment 6
Chlorinated water resist fastness
The colour fastness to chlorinated water that is determined as follows as stated above dyestuff, test result is recorded in table 7
Table 7
From table 7:
Azo-group 1:2 metallized dye composition of the present invention has splendid chlorinated water resist fastness.
Embodiment 7
Sunlight fastness
The sunlight fastness that is determined as follows as stated above dyestuff, test result is recorded in table 8
Table 8
From table 8:
Azo-group 1:2 metallized dye composition of the present invention has splendid sunlight fastness.
Embodiment 8
Dyeing compatibility test
Measure as stated above dyeing consistency, test result is recorded in table 9
Table 9
From table 9:
Azo-group 1:2 metallized dye composition of the present invention has splendid dyeing consistency.
Claims (8)
1. an azo-group 1:2 metallized dye composition, said composition comprises the dye composition that dye composition that one or more general formulas (1) represent and one or more general formulas (2) represent:
In formula:
R
1be selected from hydrogen atom or NHCOCH
3group;
R
2and R
3respectively independently selected from H, Cl or NO
2group;
Q is selected from alkali metal cation;
In formula:
R
4, R
5and R
6respectively independently selected from H, Cl or NO
2group;
Q is selected from basic metal.
2. azo-group 1:2 metallized dye composition claimed in claim 1, is characterized in that, the weight ratio of the dye composition that the dye composition that general formula (1) represents and general formula (2) represent is 10～60%:90～40%.
3. azo-group 1:2 metallized dye composition claimed in claim 1, is characterized in that the R in general formula (1)
2group, be positioned at azo group on benzene nucleus between position or contraposition; R in general formula (1)
3group, is positioned at 5 or 6 on naphthalene core.
4. azo-group 1:2 metallized dye composition claimed in claim 1, is characterized in that the R in general formula (2)
4group, be positioned at azo group on benzene nucleus between position or contraposition; R in general formula (2)
5and R
6group, be separately located in respectively azo group on benzene nucleus between position or contraposition.
5. azo-group 1:2 metallized dye composition claimed in claim 1, is characterized in that the R in general formula (1)
1group is H or NHOCH
3group.
6. azo-group 1:2 metallized dye composition claimed in claim 1, is characterized in that, the dye composition that general formula (1) represents is selected from dye composition as follows:
7. azo-group 1:2 metallized dye composition claimed in claim 1, is characterized in that, the dye composition that general formula (2) represents is selected from dye composition as follows:
In claim 1-7 the azo-group 1:2 metallized dye composition described in any one wool fabric, polyamide fabric with and blended fabric dyeing aspect application.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559314A (en) * | 2014-12-12 | 2015-04-29 | 青岛双桃精细化工（集团）有限公司 | Black dye composition and application thereof in polyamide microfiber leather dyeing |
| CN105970688A (en) * | 2016-06-17 | 2016-09-28 | 优纤科技（丹东）有限公司 | Acid bath dyeing method of chinlon 56 fiber fabric |
| CN106433214A (en) * | 2016-10-12 | 2017-02-22 | 苏州科法曼化学有限公司 | Black dye composition and dyeing application and method thereof on fibers |
| CN107841894A (en) * | 2017-10-18 | 2018-03-27 | 马多浩 | A kind of water-based levelling agent of superfine fiber synthetic leather dyeing |
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2014
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104559314A (en) * | 2014-12-12 | 2015-04-29 | 青岛双桃精细化工（集团）有限公司 | Black dye composition and application thereof in polyamide microfiber leather dyeing |
| CN105970688A (en) * | 2016-06-17 | 2016-09-28 | 优纤科技（丹东）有限公司 | Acid bath dyeing method of chinlon 56 fiber fabric |
| CN106433214A (en) * | 2016-10-12 | 2017-02-22 | 苏州科法曼化学有限公司 | Black dye composition and dyeing application and method thereof on fibers |
| CN106433214B (en) * | 2016-10-12 | 2018-04-13 | 苏州科法曼化学有限公司 | Black dye composition and its tint applications and method on fiber |
| CN107841894A (en) * | 2017-10-18 | 2018-03-27 | 马多浩 | A kind of water-based levelling agent of superfine fiber synthetic leather dyeing |
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|---|---|
| CN104194385B (en) | 2016-05-11 |
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Effective date of registration: 20220809 Address after: No.388, Jinyuan 6th Road, Jiading District, Shanghai, 201812 Patentee after: ARGUS (SHANGHAI) TEXTILE AUXILIARY Co.,Ltd. Address before: Room 275-278, Building 16, No. 388, Yindu Road, Xuhui District, Shanghai, 200231 Patentee before: SHANGHAI ARGUS TEXTILE CHEMICAL Co.,Ltd. |