Summary of the invention
The inventor is on the basis of a large amount of research trials, pleasantly surprised discovery, contain one or more Yellow active dyes and one or more Yellow active dyes of general formula (2) expression and the Yellow active dye composition of one or more Yellow active dyes that general formula (3) represents of general formula (1) expression, have very excellent dyeing behavior and every dyefastness.
Surprisingly, this Yellow active dye composition is compared with the dyestuff of general formula (1) expression, and its enhancing rate, degree of fixation, relative dye level and consistency all are significantly increased and improve.Yellow active dye composition of the present invention has excellent fast light discoloration and the fastness to chlorine of causing.
Yellow active dye composition provided by the invention contain by a certain percentage one or more that mix be selected from below shown in the dyestuff of general formula (1) expression and one or more be selected from below shown in the dyestuff of general formula (2) expression and one or more be selected from below shown in the dyestuff of general formula (3) expression;
General formula (1)
In the formula: Y
1Be selected from-CH
2CH
2OSO
3M or-CH=CH
2
M is selected from-H or basic metal;
R
1Be selected from-H ,-C
1-4Alkyl or-C
1-4Alkoxyl group;
R
2Be selected from-H ,-C
1-4Alkyl or-C
1-4Alkoxyl group;
R
3Be selected from-C
1-4Alkyl ,-NH
2,
Or
General formula (2)
In the formula: Y
2And Y
3Be independently selected from respectively-CH
2CH
2OSO
3M or-CH=CH
2
M is selected from-H or basic metal;
N is selected from 0 or 1;
M is selected from 0,1 or 2;
R
4And R
5Be independently selected from respectively-H ,-C
1-2Alkyl or-C
1-2Alkoxyl group;
General formula (3)
In the formula: Y
4Be selected from-CH
2CH
2OSO
3M or-CH=CH
2
M is selected from-H or basic metal;
X is selected from Cl or F;
R
6Be selected from-NH
2Or-C
1-4Alkyl;
R
7For-C
1-4Alkyl;
P is selected from 2 or 3.
Yellow active dye composition provided by the invention is applied to the dyeing of filamentary material and wool.
Specific implementation method
Yellow active dye composition of the present invention comprises three components that different ratios makes up, i.e. the dyestuff of the dyestuff of one or more general formulas (1) expression, one or more general formulas (2) expression and the dyestuff of one or more general formulas (3) expression.In Yellow active dye composition of the present invention, its weight ratio that forms dyestuff is: the dyestuff of general formula (1) expression: the dyestuff of general formula (2) expression: the dyestuff (weight ratio)=25~75 of general formula (3) expression: 20~70: 2~20, be preferably 30~70: 25~60: 5~15, more preferably be 35~65: 25~55: 7~13.
One preferred embodiment in, in the general formula (1)-SO
2Y
1Group is positioned on the benzene nucleus-ortho position or a position of N=N-group; R in the general formula (1)
1And R
2Group lays respectively on the benzene nucleus-ortho position and a position of N=N-group.
Another preferred embodiment in, general formula (2) left side-SO
3Y
2Group is positioned on the benzene nucleus-contraposition or a position of N=N-group; General formula (2) right side-SO
3Y
3Group, when n=1, be positioned on the benzene nucleus-the NH-group between position or contraposition.
One preferred embodiment in, the R in the general formula (2)
4And R
5Group lays respectively on the benzene nucleus-ortho position and a position of N=N-group; General formula (2) right side-SO
3The M group, when m=1, be positioned on the benzene nucleus-the NH-group between the position; When m=2, be positioned on the benzene nucleus-ortho position and a position of NH-group.
Another preferred embodiment in, in the general formula (3)-SO
3Y
4Group is positioned on the benzene nucleus
The contraposition of group or a position; General formula (3) left side-SO
3The M group when p=2, is positioned at 1,5 or 4,8 on the benzene nucleus; When p=3, then be positioned at 3,6,8 on the naphthalene nuclear.
The dyestuff of formula of of the present invention (1) expression for example comprises following example:
(dyestuff I-1)
(dyestuff I-2)
(dyestuff I-3)
(dyestuff I-4)
(dyestuff I-5)
(dyestuff I-6)
The dyestuff of formula of of the present invention (2) expression for example comprises following example:
(dyestuff II-1)
(dyestuff II-2)
(dyestuff II-3)
(dyestuff II-4)
(dyestuff II-5)
(dyestuff II-6)
(dyestuff II-7)
The dyestuff of formula of of the present invention (3) expression for example comprises following example:
(dyestuff III-1)
(dyestuff III-2)
(dyestuff III-3)
(dyestuff III-4)
(dyestuff III-5)
The reactive dyestuffs of general formula (1), general formula (2) and general formula (3) expression are known dye.
US 4,703, and 112 (1989) (Hoechst) disclose dye structure and the synthetic method thereof of general formula (1) expression.
CN 1118796 (1996) (Hoechst), CN 1443219 (2003) (Dystar), WO 02/08341 (2002) (Dystar), KR 20020094317 (2002) discloses dye structure and the synthetic method thereof of general formula (2) expression.JP 60215065 (1985) (Sumitomo) and US 4,378, dye structure and the synthetic method of general formula (3) expression announced in 313 (1983) (Sumitomos).
Yellow active 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.Inorganic salts for example is such as NaCl, Na
2SO
4, content 0-10 % by weight, dispersant 0-10 % by weight, pH adjusting agent, such as SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic, content 0-5 % by weight, dust-proofing agent 0-10 % by weight, solubility promoter 1-15 % by weight.Yellow active dye composition of the present invention also can be basically be comprised of the dyestuff of the dyestuff of the dyestuff of general formula (1) expression of certain weight ratio, general formula (2) expression and general formula (3) expression.
The preparation method of Yellow active dye composition of the present invention comprises can powder type with the dyestuff of the dyestuff of the dyestuff of above-mentioned general formula (1) expression, general formula (2) expression and general formula (3) expression, or with particle form, or exist with aqueous solution form.Mixing step can carry out in suitable shredder such as ball mill or sand mill and in kneader or mixing machine.
Yellow active dye composition of the present invention is suitable for the tint applications of cotton fibre and wool.
Yellow active dye composition of the present invention can be fixed on the fabric with the known several different methods of printing and dyeing, and for example available dip-dye method or pad dyeing method dye.
Every testing method of embodiment
The properties of embodiment is tested by the following testing method:
1. enhancing rate test: press respectively 60 ℃ of constant temperature dyeings of reactive dyestuffs, dyeing concentration is 0.5%, 1%, 2%, 4%, 6%o.w.f. (dyestuff is to the fabric weight).Fabric is tested its Apparent Depth K/S value and record with the Datacolor color measurement instrument after the dyeing after fixed temperature and humidity is processed.
2. just dye rate S value: the absorbance of dye liquor when adding before the alkali in the test dye dyeing course, calculate the S value according to formula.
Formula: just dye rate S value=(1-adds the absorbance of the front dye liquor of absorbance ÷ dyeing of the front dye liquor of alkali) * 100%
3. degree of exhaustion E value: the absorbance of dye liquor before and after the test dyeing, calculate the E value according to formula.
Formula: just dye rate E value=(absorbance of the front dye liquor of absorbance ÷ dyeing of dye liquor after the 1-dyeing) * 100%
4. degree of fixation F value: the absorbancy of the washing raffinate of fabric after the test dyeing, and calculate the F value according to formula.
Formula: the absorbance of dye liquor * 100% before the absorbance ÷ of the dye liquor dyeing after degree of fixation F value=E value-dyeing
5. photochromic properties test: the fabric after will dyeing is (intensity of illumination is with reference to ISO 105-B05) behind light fastness tester illumination certain hour, and the data before and after the test fabric illumination are judged photochromic power according to the total color difference DE in the CIE formula.
6. easily detergency test:
Fabric is dyed to carry out substep washing afterwards to it:
1) 30 ℃, cold wash in 5 minutes
2) 60 ℃, 5 minutes hot water wash
3) 95 ℃, soaped in 15 minutes
4) 60 ℃, 5 minutes hot water wash
5) 30 ℃, cold wash in 5 minutes
Test the absorbance of per step washing raffinate, and calculate per step according to absorbance and wash the proportions that the raffinate that gets off accounts for the washing of five steps what are.
7. colour fastness to perspiration (alkali sweat): testing standard is with reference to ISO 105 E04.
8. sunlight fastness: testing standard is with reference to AATCC 16E.
9. colour fastness to rubbing: testing standard is with reference to ISO 105-X12.
10. water-fastness colour fastness: testing standard is with reference to ISO 105 C03.
11. the colour fastness of anti-the chlorine water: testing standard is with reference to ISO 105-E03.
The employed dye composite of embodiment
Employed dye composite and binary dye mixture and single composition dyestuff are listed in table 1 in the embodiment of the invention and the reference example.Comprise following content:
1. the composition that contains three kinds of Yellow active dyes of different ratios of the present invention;
2. with the binary dye mixture and the single composition dyestuff that compare.
It is even with various dye component mechanically mixing to press kind of dyes listed in the table 1 and consumption, obtains required dye composite.
Table 1
The lifting force of test case 1 Yellow active dye composition of the present invention (maximum absorption wave strong point K/S value) is measured.
Table 2
By as seen from Table 2, three component Yellow active dye compositions of the present invention are compared with two components compositions with its single composition dyestuff, and its enhancing rate is significantly improved.The K/S measured value of Yellow active dye composition of the present invention surpasses it and adds and mean value, embodies its compound synergic effect.
First rate (S), degree of exhaustion (E) and the degree of fixation (F) of dying of test case 2 Yellow active dye compositions of the present invention measured
Table 3
By as seen from Table 3, S, E, the F value of the dyestuff I-1 of general formula (1) expression are excessively low, are difficult to have the using value of reality.
Yellow active dye composition of the present invention forms dyestuff with its single composition dyestuff and two components and compares, and has fairly obvious progress in improvement S, E, F value.
Being worth pleasantly surprised is, Yellow active dye composition of the present invention has very good consistency with red, blue active dye commonly used.(seeing Table 4)
Table 4
The test case 3 fast light discolorations that cause
Table 5
In the table: DE
*For cloth specimen behind illuminated certain hour under the standard light source with the total color difference of former state.
By as seen from Table 5, Yellow active dye composition of the present invention still keeps the good fast light discoloration that causes.
The easy scourability of test case 4 Yellow active dye compositions of the present invention
Table 6
By as seen from Table 6, Yellow active dye composition of the present invention has good easy scourability.
Every dyefastness of test case 5 Yellow active dye compositions of the present invention
Table 7
Table 8
Table 9
By table 7, table 8, as seen from Table 9, the Yellow active dye composition of the variant composition of the present invention has good every dyefastness.
The colour fastness of anti-chlorine of test case 6 Yellow active dye compositions of the present invention
Table 10
Amazingly in the table 10 be, Yellow active dye composition of the present invention is compared with the dyestuff of two components with its one-component, and its colour fastness of anti-chlorine makes moderate progress and improves.