CN104371366A - Disperse blue-to-black dye composition - Google Patents
Disperse blue-to-black dye composition Download PDFInfo
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- CN104371366A CN104371366A CN201410524391.7A CN201410524391A CN104371366A CN 104371366 A CN104371366 A CN 104371366A CN 201410524391 A CN201410524391 A CN 201410524391A CN 104371366 A CN104371366 A CN 104371366A
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- 0 CCN(*c1ccccc1)C(C=C1)=CC(C)[C@]1N=Nc1c(cc(cc2)[N+]([O-])=O)c2n[s]1 Chemical compound CCN(*c1ccccc1)C(C=C1)=CC(C)[C@]1N=Nc1c(cc(cc2)[N+]([O-])=O)c2n[s]1 0.000 description 7
Abstract
The invention discloses a disperse blue-to-black dye composition. The disperse blue-to-black dye composition is obtained by blending of original dye and an auxiliary agent. The disperse blue-to-black dye composition is characterized in that the original dye comprises an ingredient A and an ingredient B and/or an ingredient C, the ingredient A is selected from one or more of dye compounds shown in the formula (I), the ingredient B is selected from one or more of dye compounds shown in the formula (II), the ingredient C is selected from one or more of dye compounds shown in the formula (III), the original dye comprises 30-95wt% of the ingredient A, 0-50wt% of the ingredient B and 0-30wt% of the ingredient C, and the ingredient B and ingredient C contents are not equal to 0 simultaneously. The disperse blue-to-black dye composition has a high color yield, good level-dyeing properties and good lifting force, can be used for dying in a system with a pH value of 4.0-14.0 and widely widens a disperse dye application scope.
Description
(1) technical field
The present invention relates to a kind of disperse dye composition, be specifically related to the good EX-SF DISPERSE BLUE EX-SF 300 of a kind of alkali resistance to black disperse dye composition.
(2) background technology
Dispersed dye are applied under high temperature (125 DEG C ~ 135 DEG C) condition, have a chemical stability problems.When Value in Dyeing Process is in 3 ~ 6 scopes, acid-resistant stability is good, not easily causes obvious aberration.But when under dye bath pH > 6 condition, can there is hydrolysis reaction in many conventional dispersed dye, make Dry Sack shoal, and coloured light mutation, alkali stability is very poor.
In recent years, domestic DYE PRODUCTION producer, is proposed serial alkali resistance disperse dye.In fact great majority screen from alkali stability preferably conventional dispersed dye.As: the ADD series dispersed dye of Zhejiang Province Runtu intercalated Co., Ltd; The H-RPD type dispersed dye of Changzhou Ya Bang Dye Co., Ltd etc. (reference: [1] Cui Haoran. the compatibility technology [J] of dispersed dye. dyeing and finishing technique, 2011,33 (9): 49-50).
These so-called alkaline-proof disperse dyes, in the dye bath of 130 DEG C, the resistance to alkali ability of reality of most dyestuff is as follows: (with dye bath pH=4.8 compared with color depth)
During dye bath pH=8.1, obtain color depth fall within 4%;
During dye bath pH=9.0, obtain color depth fall within 6%;
During dye bath pH=10.0, obtain color depth fall 10 ~ 27%.
This shows, domestic alkaline-proof disperse dyes, only adapts to dye under the condition of below pH=9.0, if dye under the condition of pH ﹥ 9.0, it obtains color depth and Dry Sack coloured light, also noticeable change (only having the resistance to alkali ability of some dyes to reach pH=10) will occur.
Because alkaline-proof disperse dyes is of less types, and on the high side.Therefore, how to obtain that a kind of alkaline-resisting scope is broader, colour fastness is excellent and the new alkali resistance dyestuff of reasonable price becomes the focus of current research.
(3) summary of the invention
For expanding the troop of alkali resistance disperse dye, solve that dye yield in conventional alkali resistance disperse dye alkali system declines to a great extent, the problem of dyeing behavior instability, the invention provides a kind of alkali resistance EX-SF DISPERSE BLUE EX-SF 300 to black dye composition, this EX-SF DISPERSE BLUE EX-SF 300 is high to black dye composition dye yield, good level-dyeing property, lifting force is good, can be dye in the system of 4.0 ~ 14.0 in pH value, greatly expand the range of application of dispersed dye, part terylene fabric refining one-pass bath method for dyeing can not only be realized, also can be used for the alkaline burnt-out printing process under strong alkaline condition.
Object of the present invention is achieved through the following technical solutions:
A kind of EX-SF DISPERSE BLUE EX-SF 300 is to black dye composition, formed by former dyestuff and auxiliary agent blending, former dyestuff mainly comprises component A and B component and/or component C, wherein component A is selected from one or more in dye composition shown in formula I, B component be selected from dye composition shown in formula II one or more, component C be selected from dye composition shown in formula III one or more, based on described former dyestuff, the weight percentage of component A is 30-95%, the weight percentage of B component is 0-50%, the weight percentage of component C is 0-30%, be 0 when wherein B component is different with the content of component C,
In formula I, R
1for hydrogen or C
1~ C
4alkyl; R
2for C
1~ C
4alkyl or cyanoethyl; M is 2 or 3;
In formula II, R
3, R
4respective is independently hydrogen or halogen; R
5for hydrogen, C
1~ C
4alkyl, halogen or C
1~ C
4alkoxyl group; R
6for cyanoethyl or C
1-C
6alkyl, n is 1,2 or 3;
In formula III, X
1, X
2respective is independently H, halogen or nitro, R
7for H or C
1-C
4alkyl; R
8for C
1-C
4alkyl or cyanoethyl; R
9for cyanoethyl, benzyl or styroyl;
And former dyestuff is not when comprising component C, if m=2 or 3, then n is only 1.
Further, former dyestuff is made up of component A, B component and component C.
Further, based on former dyestuff gross weight, the weight percentage of described component A is 40-90%, and the weight percentage of B component is the weight percentage of 1-50%, component C is 1-30%.
Again further, based on former dyestuff gross weight, the weight percentage of described component A is 45-85%, the weight percentage of B component be 1 ~ 45%, component C weight percentage be 1 ~ 25%.
Further, described component A is preferably following one or more mixture:
Further, described B component is preferably following one or more mixture:
Further, described component C is preferably following one or more mixture:
Further, component A is particularly preferably from formula (I-1) and/or formula (I-6), B component is particularly preferably from formula (II-1) and/or (II-12), and component C is particularly preferably from formula (III-1) and/or (III-9).
In the present invention, formula (I), (II), the dye composition shown in (III) can synthesize by mode well known to those skilled in the art easily, also with reference to the method introduced in patent US5824117, US3502645, GB1356695, CN101117446, JP60246885A or the preparation of similar method, also commercial goods can be adopted.Due to the singularity of dye industry; be difficult to also there is no need to make sterling; so " the former dyestuff " described in the present invention refers to that dye composition wherein uses the slurries obtained in preparation process to filter through pressure filter or other filter plants the filter cake obtained; usual meeting is with the impurity in some preparation process; disperse dye composition of the present invention also allows containing a small amount of physical impurity in preparation process, is advisable not affect dyeing behavior.
EX-SF DISPERSE BLUE EX-SF 300 of the present invention is to black dye composition, as commodity selling or be applied to textile materials painted time, usually also needing to add auxiliary agent carries out aftertreatment, described auxiliary agent be dispersed dye composite time conventional dispersion agent, diffusant and other tensio-active agent etc., preferred auxiliary agent is selected from one of following or its mixture: naphthalene sulfonic acidformaldehyde condensation product, sulfonated lignin, alkyl naphthalene sulfonic acid formaldehyde condensation products (as condensation compound of methyl naphthalene sulfonic acid and formaldehyde (Dispersant MF)), naphthalene sulfonic acidformaldehyde condensation product (dispersing agent NNO), benzyl naphthalene sulfonic formaldehyde condensation compound (dispersing agent CNF), sodium lignosulfonate (xylogen 85A, xylogen 83A) etc.Usually, the ratio of the gross weight of auxiliary agent and former dye component is 0.2 ~ 5:1.
EX-SF DISPERSE BLUE EX-SF 300 of the present invention is to black dye composition, and its commercial treatment method is as follows:
By the former dyestuff represented by component A, B component, component C by after the mixing of above-mentioned proportioning, under the existence of auxiliary agent, water or other wetting agent, carry out corpusculed with the pulverizer such as sand mill or shredder; Also mix with above-mentioned ratio after the former dyestuff represented by component A, B component, component C can being carried out corpusculed process with the pulverizer such as sand mill or shredder respectively under the existence of auxiliary agent, water or other wetting agent in addition.EX-SF DISPERSE BLUE EX-SF 300 of the present invention is to black dye composition, aqueous with can be after sand mill or shredder grinding, can be powdery, particulate state after spraying dry.
EX-SF DISPERSE BLUE EX-SF 300 provided by the invention is to black dye composition, dispersed dye normal dyeing method can be adopted as high-temperature and high pressure dyeing process contaminated the hydrophobic fiber materials such as polyester, polymeric amide or vinegar fibre, there is the interdependent scope of pH wider, can dye under the condition of pH4.0-14, every colour fastness is excellent, lifting force is good, and dye yield is high, and dyeing behavior is stablized.
(4) accompanying drawing explanation
Fig. 1 is the lifting force comparison diagram of the obtained dye composite of embodiment 1, comparative example 1, comparative example 2, comparative example 3.
(5) embodiment
Below in conjunction with specific embodiment, the invention will be further described, but protection scope of the present invention is not limited in this:
EXAMPLE l:
By 47 grams of formulas (I-1), 40 grams of formulas (II-1), 13 grams of formulas (III-1), 200 grams of Dispersant MFs, after adding 550 grams of water Mixed Pinyins, grinding distribution, dry, get product, this finished product can provide fabric black tone.
Embodiment 2:
By 85 grams of formulas (I-1), 10 grams of formulas (II-1), 5 grams of formulas (III-2), 250 grams of Dispersant MFs, after 600 grams of water Mixed Pinyins, grinding distribution, dry, get product, this finished product can provide fabric blue color
Embodiment 3 ~ 28:
According to the method described in embodiment 1 or 2, unlike the weight ratio and the auxiliary agent that adopt component A, B component, component C in table 1, slurries are made after the blending that adds water, controlling the solid content of slurries is 35 ~ 45% to be advisable, grinding distribution, drying, obtained finished product, can be supplied to fabric evenly and the good blueness of fastness ability to black tone.85A, 83A in table 1 are respectively xylogen 85A, xylogen 83A.
Table 1
Tint applications 1:
The dispersed dye taking 4 grams of embodiments 1 obtained are dispersed in 500 ml waters, mix, with sheet adjusting PH with base to 12.5 after drawing 20 milliliters with the water of 100 milliliters, put into 4 grams of polyester textiles, be warming up to 70 DEG C, continue with about 2 DEG C/min gradient increased temperature to 130 DEG C, insulation dyeing 45 minutes.Then be cooled to about 80 DEG C and use hot water wash 10min, dry.Observe the adopt international standards testing method of office (ISO) and rating scale of sample cloth coloured light and test its every dyefastness respectively: crock fastness (ISO 105-X12), washing fastness (ISO105-C03), sublimation fastness (ISO 105-X11), the results are shown in Table 2.
Table 2
According to the method described in above-mentioned Dyeing Example, the dyestuff of preparation in embodiment 2 ~ 28 is adopted to dye respectively, dye level 4.0%, unlike change dyeing pH value, the basically identical blueness of dyeing behavior or black fabric can be obtained equally, specifically in table 3.
Table 3
Tint applications 2:
Comparative example 1: the composite dispersed black dye that patent CN201210237613.8 embodiment 2 is obtained embodiment 1 as a comparison;
Comparative example 2: by the dye monomer shown in the dye monomer shown in patent CN200810094568.9 formula (a-1), formula (b-1) and the dye monomer shown in formula (c-2), black dyes is made, as a comparison embodiment 2 according to the method for the embodiment of the present application 1;
Comparative example 3: the composite dispersed deep blue dye that patent CN200910101329.6 embodiment 1 is obtained embodiment 3 as a comparison;
Composite disperse dye obtained in embodiment 1, comparative example 1, comparative example 2, comparative example 3 is carried out coloured differently Inner dyeing respectively according to the method for tint applications 1, namely unlike, often kind of dyestuff gets 0.5 gram, 1 gram, 2 grams, 4 grams, 6 grams, 8 grams separately respectively, obtains dye level and is respectively 0.5%, 1%, 2%, 4%, 6%, 8%.According to its lifting force of GB/T2397-2003 standard testing, gained lifting force result as shown in Figure 1.Can find out that from Fig. 1 the enhancing of the dispersed dye of the application is obviously better than each comparative example intuitively.
As known from the above, not only every fastness ability such as washing fastness, sublimation fastness, crock fastness is excellent to black dye composition for complex dispersion blue of the present invention, and it is better than the enhancing of existing common alkali resistance dispersion blue-black dyestuff, dye yield is high, greatly improve alkali resistance disperse dye in alkali system and obtain the problem that color depth declines to a great extent, cost-saving.
So-called lifting force refers to that application is in time dyeing, progressively increase with dye dosage, dyeing and weaving thing obtains the corresponding degree increased progressively of color depth, the dyestuff that lifting force is good, its dye level can be deepened in the increase of the ratio of materials, illustrate that dyestuff has good depth, dye dark color is appropriate to the occasion usually selects the dyestuff that lifting force is good.
Claims (10)
1. an EX-SF DISPERSE BLUE EX-SF 300 is to black dye composition, formed by former dyestuff and auxiliary agent blending, it is characterized in that: former dyestuff mainly comprises component A and B component and/or component C, wherein component A is selected from one or more in dye composition shown in formula I, B component be selected from dye composition shown in formula II one or more, component C be selected from dye composition shown in formula III one or more, based on described former dyestuff, the weight percentage of component A is 30-95%, the weight percentage of B component is 0-50%, the weight percentage of component C is 0-30%, be 0 when wherein B component is different with the content of component C,
In formula I, R
1for hydrogen or C
1~ C
4alkyl; R
2for C
1~ C
4alkyl or cyanoethyl; M is 2 or 3;
In formula II, R
3, R
4respective is independently hydrogen or halogen; R
5for hydrogen, C
1~ C
4alkyl, halogen or C
1~ C
4alkoxyl group; R
6for cyanoethyl or C
1-C
6alkyl; N is 1,2 or 3;
In formula III, X
1, X
2respective is independently H, halogen or nitro, R
7for H or C
1-C
4alkyl; R
8for C
1-C
4alkyl or cyanoethyl; R
9for cyanoethyl, benzyl or styroyl;
And former dyestuff is not when comprising component C, if m=2 or 3, then n is only 1.
2. EX-SF DISPERSE BLUE EX-SF 300 as claimed in claim 1 is to black dye composition, it is characterized in that: former dyestuff is made up of component A, B component and component C.
3. EX-SF DISPERSE BLUE EX-SF 300 as claimed in claim 2 is to black dye composition, and it is characterized in that: based on former dyestuff gross weight, the weight percentage of described component A is 40-90%, and the weight percentage of B component is the weight percentage of 1-50%, component C is 1-30%.
4. EX-SF DISPERSE BLUE EX-SF 300 as claimed in claim 3 is to black dye composition, it is characterized in that: based on former dyestuff gross weight, the weight percentage of described component A is 45-85%, the weight percentage of B component be 1 ~ 45%, component C weight percentage be 1 ~ 25%.
5. the EX-SF DISPERSE BLUE EX-SF 300 as described in one of Claims 1 to 4, to black dye composition, is characterized in that: described component A is selected from following one or more mixture:
6. the EX-SF DISPERSE BLUE EX-SF 300 as described in one of Claims 1 to 4, to black dye composition, is characterized in that: described B component is selected from following one or more mixture:
7. the EX-SF DISPERSE BLUE EX-SF 300 as described in one of Claims 1 to 4, to black dye composition, is characterized in that: described component C is selected from following one or more mixture:
8. the EX-SF DISPERSE BLUE EX-SF 300 as described in one of Claims 1 to 4 is to black dye composition, it is characterized in that: component A is selected from formula (I-1) and/or formula (I-6), B component is selected from formula (II-1) and/or formula (II-12), and component C is selected from formula (III-1) and/or formula (III-9).
9. the EX-SF DISPERSE BLUE EX-SF 300 as described in one of Claims 1 to 4, to black dye composition, is characterized in that: described auxiliary agent is selected from one of following or its mixture: naphthalene sulfonic acidformaldehyde condensation product, sulfonated lignin, alkyl naphthalene sulfonic acid formaldehyde condensation products, naphthalene sulfonic acidformaldehyde condensation product, benzyl naphthalene sulfonic formaldehyde condensation compound, sodium lignosulfonate.
10. the EX-SF DISPERSE BLUE EX-SF 300 as described in one of Claims 1 to 4, to black dye composition, is characterized in that: the ratio of the gross weight of auxiliary agent and former dyestuff is 0.2 ~ 5:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113913027A (en) * | 2020-08-27 | 2022-01-11 | 青岛大学 | Dichloro-substituted benzothiazole high-alkali-resistance high-oxygen-resistance bleaching-resistant disperse dye |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3502645A (en) * | 1968-02-16 | 1970-03-24 | Martin Marietta Corp | Water-insoluble benzothiazole monoazo dyes |
| CN101265369A (en) * | 2008-05-14 | 2008-09-17 | 蓬莱华茂精细化工有限公司 | Azo dye composition and application thereof |
| CN102618079A (en) * | 2012-03-07 | 2012-08-01 | 浙江万丰化工有限公司 | Disperse dye composite, dyeing method and preparation method for disperse dye composite |
| CN102618080A (en) * | 2012-03-07 | 2012-08-01 | 浙江万丰化工有限公司 | Disperse dye composition, dyeing method and preparation method of disperse dye composition |
| CN102746713A (en) * | 2012-07-10 | 2012-10-24 | 浙江龙盛集团股份有限公司 | Blue-to-black disperse dye composition |
| CN103044964A (en) * | 2012-12-11 | 2013-04-17 | 苏州大学 | Dye composition and polyester fiber fabric alkaline dyeing method using same |
| CN103450707A (en) * | 2013-09-07 | 2013-12-18 | 张家港市杨舍丝印工艺厂 | Dye composition (black) and preparation method thereof |
| CN103509373A (en) * | 2013-09-07 | 2014-01-15 | 张家港市杨舍丝印工艺厂 | Blue dye composition and preparation method thereof |
| CN103554986A (en) * | 2013-09-07 | 2014-02-05 | 张家港市杨舍丝印工艺厂 | Red-light navy blue dye composition and preparation method thereof |
-
2014
- 2014-10-08 CN CN201410524391.7A patent/CN104371366B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3502645A (en) * | 1968-02-16 | 1970-03-24 | Martin Marietta Corp | Water-insoluble benzothiazole monoazo dyes |
| US3502645B1 (en) * | 1968-02-16 | 1984-07-03 | ||
| CN101265369A (en) * | 2008-05-14 | 2008-09-17 | 蓬莱华茂精细化工有限公司 | Azo dye composition and application thereof |
| CN102618079A (en) * | 2012-03-07 | 2012-08-01 | 浙江万丰化工有限公司 | Disperse dye composite, dyeing method and preparation method for disperse dye composite |
| CN102618080A (en) * | 2012-03-07 | 2012-08-01 | 浙江万丰化工有限公司 | Disperse dye composition, dyeing method and preparation method of disperse dye composition |
| CN102746713A (en) * | 2012-07-10 | 2012-10-24 | 浙江龙盛集团股份有限公司 | Blue-to-black disperse dye composition |
| CN103044964A (en) * | 2012-12-11 | 2013-04-17 | 苏州大学 | Dye composition and polyester fiber fabric alkaline dyeing method using same |
| CN103450707A (en) * | 2013-09-07 | 2013-12-18 | 张家港市杨舍丝印工艺厂 | Dye composition (black) and preparation method thereof |
| CN103509373A (en) * | 2013-09-07 | 2014-01-15 | 张家港市杨舍丝印工艺厂 | Blue dye composition and preparation method thereof |
| CN103554986A (en) * | 2013-09-07 | 2014-02-05 | 张家港市杨舍丝印工艺厂 | Red-light navy blue dye composition and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113913027A (en) * | 2020-08-27 | 2022-01-11 | 青岛大学 | Dichloro-substituted benzothiazole high-alkali-resistance high-oxygen-resistance bleaching-resistant disperse dye |
| CN113913028A (en) * | 2020-08-27 | 2022-01-11 | 青岛大学 | High-alkali-resistance high-oxygen-resistance bleaching disperse dye of monochloro-substituted benzothiazole |
| CN113913028B (en) * | 2020-08-27 | 2023-12-01 | 青岛大学 | Monochloro-substituted benzothiazole high alkali resistance Gao Naiyang bleach disperse dye |
| CN113913027B (en) * | 2020-08-27 | 2023-12-05 | 青岛大学 | Dichloro substituted benzothiazole high alkali resistance Gao Naiyang bleach disperse dye |
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